PVC 1

Prog. Polym. Sci.
27 (2002) 20552131
www.elsevier.com/locate/ppolysci
Technical progresses for PVC production

Y. Saeki, T. Emura*
Former Shin Dai-Ichi Vinyl Corporation, 1-4-5, Tokyo 105-0003, Japan Received 19 October 2001
Abstract This review covers recent development of PVC production technologies of the suspension polymerization process, the bulk (mass) polymerization process and the emulsion polymerization process with some historical background. The development of process for the vinyl chloride monomer (VCM) production is also explained briey. Since the suspension process is regarded to be the most important process with its 80% share of the world total production, this review follows mainly the technology development of the suspension polymerization process. Because of the importance of hygienic problems caused by VCM, the technology development in the eld of emission control is also covered. q 2002 Elsevier Science Ltd. All rights reserved.
Keywords: PVC; Vinyl chloride monomer; Suspension process; Bulk process; Emulsion process; Emission control Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2057 2. Overview of world PVC industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2057 3. Outline of PVC production technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2059 3.1. Outline of development of VCM and PVC technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2059 3.2. Processes of PVC production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2062 4. Vinyl chloride monomer manufacturing processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2064 4.1. History of VCM processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2064 4.1.1. Acetylene process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2064 4.1.2. Ethylene and acetylene combined process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2064 4.1.3. Mixed gas process from naphtha [18] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2064 4.2. Development of oxy-chlorination process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2065 4.3. Ethane process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2069 5. Suspension polymerization process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2070 5.1. Outline of suspension polymerization process [29] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2070 5.2. Particle formation in the suspension polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2071 5.2.1. Nomenclature of morphology of PVC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2072 5.2.2. Mechanism of particle formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2072 * Corresponding author. Fax: 81-3-3595-1907. 0079-6700/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 0 7 9 - 6 7 0 0 ( 0 2 ) 0 0 0 3 9 - 4
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5.2.3. Example of particle structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2080 5.3. Reactor scale-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2083 5.3.1. History of reactor scale-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2083 5.3.2. Agitation scale-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2085 5.3.3. Technical problems for large reactor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2086 5.4. Scale prevention technology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2086 5.4.1. Pioneer works . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2086 5.4.2. Mechanism of scale formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2087 5.4.3. Classication of various patents for scale prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2087 5.4.4. Recent development of scale prevention technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2089 5.4.5. Reactor cleaning technology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2090 5.4.6. Long term closed operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2090 5.5. Improvement of heat removal technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2090 5.5.1. Effect of the reactor size on heat removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2090 5.5.2. Development of heat removal technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2092 5.6. Improvement of productivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2095 5.6.1. Production line system and production cost. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2095 5.6.2. Productivity index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2096 5.6.3. Reduction of cycle time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2097 5.6.4. High speed polymerization and quality improvement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2097 5.6.5. Minimization of production cost of suspension PVC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2098 5.7. Computer control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2099 5.7.1. The rst attempt of computer control by Huls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2099 5.7.2. Computer control for large reactor PVC plant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2100 5.7.3. Distributed control system (DCS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2101 5.7.4. Safety aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2102 6. Bulk polymerization process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2102 6.1. Outline of bulk polymerization process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2102 6.1.1. Description of the bulk polymerization process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2102 6.2. Development of bulk polymerization process of vinyl chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2103 6.2.1. Single stage process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2103 6.2.2. Two stage process with horizontal reactor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2103 6.3. Two-stage process with vertical second stage reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2104 6.3.1. History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2104 6.3.2. Description of the process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2105 6.3.3. Role of the rst stage polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2106 6.3.4. Role of the second stage polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2107 6.4. Economics of bulk process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2109 6.5. Product quality of bulk process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2109 6.6. World capacity of bulk process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2110 7. PVC paste resin manufacturing process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2110 7.1. PVC for paste application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2110 7.2. Paste resin manufacturing process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2111 7.2.1. Outline of process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2111 7.2.2. Particle structure and production conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2112 7.2.3. Micro-suspension polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2113 7.2.4. Emulsion polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2114 7.2.5. Drying of latex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2115 7.2.6. Bulk handling paste resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2116 7.3. Relationship between characteristics of paste resin and properties of plastisol and nal product . . . . . . . . . . .2119 8. VCM emission control of PVC plant. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2119
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8.1. Vinyl chloride toxicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2119 8.2. Occupational regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2120 8.3. Reduction of VCM emission form PVC plant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2120 8.3.1. Removal of residual VCM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2120 8.3.2. Other technology for reduction of VCM emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2124 9. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2126 Acknowlegements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2127 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2127
1. Introduction This article covers the recent developments of manufacturing processes of PVC. In the early 1930s industrial process of PVC has been developed in Germany and USA. From 1940s to 1960s commercial production of PVC, as a new material and a typical plastic, started in USA, Europe and Japan. Afterwards there were so many big changes of social circumstances, such as rapid economic development in industrialized countries, conversion of energy and raw material source from coal to oil, oil shock caused by soaring of oil price and environmental problem. Following these changes, production technologies of PVC have been improved during these years. There are some review articles and books on PVC production technologies [1 4]. This article covers the developments of production technologies of PVC mainly after 1970s and also covers briey the recent developments of vinyl chloride monomer (VCM) production technologies.
2. Overview of world PVC industries Fig. 1 shows a trend of world PVC demand from 1990 to 1997 and prediction to 2003 [5]. Annual growth rate of world PVC demand from 1990 to 1997 was 4.4%. Moderate growth rate after 1997 was predicted as 3.8% per year. In North America, USA and Canada, PVC demands are growing continuously at a rate of about 3% per year. Industrialized countries in Europe, such as Germany, PVC industries are already in matured stage. The growth rate of Western Europe is predicted as 1.7% per year. In Asia, growth rate is as big as 4.5%. This high rate is based on rapid growth of PVC industries in China, India and other ASEAN counties. In Fig. 2 are shown trend and prediction of PVC demand in Asia. Annual growth rate of Asian PVC demand from 1990 to 1997 was 6.6%. Growth rate after 1997 was predicted as 4.5% per year. Industrialized countries in Asia, such as Japan, Korea and Taiwan, PVC industries are almost in matured stage. Big growth rate is predicted in China and India. Especially in China growth rate will be very big and is predicted at 10.7% per year. Development of Chinese PVC demand at the beginning of 21st century is noteworthy because of their very big capacity of demand. Fig. 3 shows trends of PVC demand and production capacity in Japan from 1980 [6]. This gure is showing that domestic PVC demand in Japan has already saturated and industry matured at around 1990. On the other hand production capacity is increasing continuously through 1990 and the surplus of capacity over demand is widely increased. However, rapid increase of export to Asian countries, mainly China, lled these gaps.
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Fig. 1. Trend of world PVC demand. Reprinted with permission from Data of the advisory committee for the Basic Industries Bureau of Ministry of Internation Trade and Industry (MITI), Japan [5].
Rearrangement of world PVC producers has been dramatically progressed from 1980. In Table 1 are shown change of number of PVC producers in USA, Europe and Japan after 1980. PVC producers in all these regions were gathered and rationalized by merger or combinations and the result number of PVC producers decreased very much. This means these industrialized countries PVC industry has already matured.
Fig. 2. Trend of Asian PVC demand. Reprinted with permission from Data of the advisory committee for the Basic Industries Bureau of Ministry of Internation Trade and Industry (MITI), Japan [5].
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Fig. 3. Trend of PVC demand and production capacity in Japan. Reprinted with permission from Data of Vinyl Environmental Council, Japan [6].
In Asia, on the other hand, economic growth started in China and ASEAN counties from around 1990. PVC demand in these countries followed such economic growth. PVC industries started by importing PVC resin and then stepped forward by domestic production of PVC. Increase of PVC production capacity in these Asian countries were accelerated after 1990 as shown in Table 2. Such development of PVC industries in Asia will be followed by other developing countries. World PVC industries in the 21st century will expand by the lead of such developing countries.
3. Outline of PVC production technologies 3.1. Outline of development of VCM and PVC technologies In 1941, Nippon Chisso Fertilizer Company (now Chisso Corporation) started the rst VCM and PVC commercial production in Japan by its own technology. However, large-scale industrial production of VCM and PVC began at 1950s, which was the postwar reconstruction period of Japan. 21 companies
Table 1 Number of PVC producers 1980 USA West Europe Japan 21 22 16 1996 13 13 11 2000 12 8 7
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Table 2 PVC production capacity in Asia (1000 t) Country Korea Taiwan Thailand Malaysia Indonesia Singapore Philippines Vietnam ASEAN total Sub-total China Total 1980 324 541 48 24 48 12 48 0 180 1045 1998 1175 1480 743 70 614 28 48 80 1583 4238 1600 5838 2000 1225 1815 863 230 614 0 118 80 1905 4945 2300 7245
started commercial production of PVC by emulsion process. After the start of suspension PVC plant of Nippon Zeon and Mitsubishi Chemical, by technology introduced from USA, suspension process became predominant in Japan [7]. Table 3 shows the outline of technology development of VCM and PVC in Japan after 1950s [8]. In this table the main stream of development of VCM and PVC are shown with changes of social and economic situation of each decade. The dramatic change in Japanese PVC industry was the change of chemistry from coal to petroleum. Carbide acetylene from coal was substituted by ethylene from petrochemicals. Developments of ethylene dichloride (EDC) synthetic process an oxy-chlorination process were the main theme of PVC industry for changing law material. The price soaring of oil by the rst oil shock in 1973 required the overcome of theme of conservation of law material and energy in manufacturing process. The second oil shock in 1979 required another cost down in the process. In 1970s environmental problems such as environmental pollution and waste management became serious problem, which were minus inheritances of the rapid economic growth in 1960s. In PVC industry mercury pollution was the main environmental issue. In the electrolysis of salt for chlorine production, the mercury process was substituted by ion exchange process because of pollution problem of mercury into river or sea. Then the carcinogen problem of VCM happened as a severe problem of the PVC industry. Closed system of process was needed to solve VCM leakage problem in PVC manufacturing process. For technologies of PVC production the mass production process and low cost process were required to follow the rapid economic growth. The technologies for size up of production scale and for high productivity were strongly required to achieve the cost down of the process. At the same time the production for high quality and variety grades was required to satisfy the request of customers who wanted improvement of higher productivity of processing and product quality competitive internationally. As index of technological level of PVC production, reactor scale and productivity (t/m3 month) of process are listed in Table 3. Decades of 1950s and 1960s were special period for reconstruction after
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Table 3 Development of VCM and PVC Technologies in Japan [8]
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war in Japan. After 1970s, which was a period of achievement of international level of industries and technologies in Japan, technological theme in Japan became common with international theme. Therefore, Japanese trend of PVC technologies could be regarded basically identical with trend of whole world. In the following paragraph the details of technological development of VCM and PVC shown in Table 3 are mentioned. 3.2. Processes of PVC production There are four kinds of production process for addition polymerization, as shown below [9 12]. Bulk polymerization process Suspension polymerization process Emulsion polymerization process Solution polymerization process Bulk polymerization process included gas phase polymerization. Micro-suspension process was included in suspension process. There are two processes in the solution process, one is homogeneous process where polymer is soluble in solvent and the other is heterogeneous process (or slurry process) where polymer is insoluble in the solvent. In Fig. 4 simplied diagram of polymerization steps for four kinds of production process are shown [11]. Industrial production process for polymer consists of six steps (unit). The rst one is law material step where law material is stored and adjusted. The second is catalyst preparation step, where catalyst is synthesized or prepared. The third (the most important one) is the polymerization step. The fourth one is separation step, where unreacted monomer is recovered and product is separated from water or solvent. The fth one is recovery step, where unreacted monomer and solvent are recovered. The last one is nishing step, where separated polymer is dried, packed and stored. The most important step is different for each kind of polymerization process. And this difference shows the feature of each polymerization process as shown in Fig. 4. In this gure the importance of step are shown in large block and mesh is put on it. The importance of step is not a quantitative one but measured qualitatively by complexity, difculty of operation or bigness of equipment cost or running cost. In the case of bulk polymerization process, the polymerization step is the most important because of difculty of heat removal. But in the bulk polymerization only VCM and catalyst are indispensable, then other steps, such as law material step, separation step, recovery step and nishing step are very simple. Totally, bulk polymerization process is the simplest process. In the case of suspension polymerization process, water is applied as a medium for efcient heat removal. So the polymerization step of suspension process is much easier than bulk process. But water separation and wastewater treatment are needed. Recovery step is more important and dehydration and drying processes are needed and then equipment cost and running cost are higher than bulk process. In the case of emulsion polymerization process, water and emulsier are applied and control of polymerization reaction is much easier than the bulk process and equivalent with suspension process. The
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Fig. 4. Simplied diagram of polymerization processes. Reprinted with permission from Y. Saeki. q1971 Y. Saeki [11].
separation step is important because separation of polymer from latex stabilized by emulsier is needed. Drying process is also needed. Then equipment cost and running cost are higher than bulk process. In the case of solution polymerization process, solvent is applied. Then all steps are more complicate than other three processes because of solvent treatment. Then equipment cost and running cost are highest among four processes. As described above, method of polymerization step requires each polymer production process and decides its product qualities. So the selection of method of polymerization is very important at the stage of industrialization of polymer. In Table 4 are shown recent share of each process of polymerization in the case of PVC [13 15]. In this table the most predominant one is suspension process. This is because most common applications such as pipe, lm and sheet, prole extrusion are all made by commodity resin manufactured by suspension process. Resin from the bulk polymerization process is also applicable to such application. Recently, bulk process PVC is consumed as specialty PVC with high purity. Share of bulk process in the world is around 10%. In Japan, there is no bulk process for PVC.
Table 4 Share of PVC production processes (%) World [13] Suspension polymerization Micro-suspension polymerization Emulsion polymerization Bulk polymerization 80 12 8 USA [14] 75 3 12 10 Japan [15] 93 5 2 0
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Fine particle size PVC made by micro-suspension and emulsion process is used for paste (dispersion) application which is made by dispersing PVC in plasticizer and molded as paste form. Product made by solution process is used for special use such as lacquer and production amount is very small. 4. Vinyl chloride monomer manufacturing processes 4.1. History of VCM processes Fig. 5 shows historical change of VCM processes [1618]. 4.1.1. Acetylene process The early stage of PVC industry, started 1930s till middle of 1960s, VCM, as low material for PVC, was produced by the acetylene process. VCM is synthesized from acetylene and HCl by gas phase reaction with the presence of mercuric chloride as a catalyst at around 150 8C. Acetylene is produced from carbide made from coal CaC2 2H2 O ! CHyCH CaOH2 CHyCH HCl ! CH2 yCHCl VCM 4.1.2. Ethylene and acetylene combined process Cheap ethylene from the emerging petrochemical industry was then supplied as low material of EDC which is the adduct of ethylene with chlorine. EDC is precursor of VCM. Thermal decomposition of EDC produces VCM and HCl, which is useless in the petrochemical industry at that time. Acetylene process of VCM was a candidate for consuming HCl from decomposition of EDC. In Japan, the combined process of ethylene and acetylene for VCM production was introduced at end of 1960s as the transition stage of the coal and petrochemical industry CH2 yCH2 Cl2 ! CH2 Cl CH2 Cl EDC CH2 Cl CH2 Cl ! CH2 yCHCl VCM HCl CHyCH HCl ! CH2 yCHCl VCM 4.1.3. Mixed gas process from naphtha [18] In the case of above mentioned process acetylene from carbide is still needed. Both ethylene and acetylene were directly produced by high temperature decomposition of naphtha at 2000 8C. Mixed gas of ethylene and acetylene was rst reacted with HCl and acetylene was converted to VCM. Then, remained ethylene was reacted with HCl and converted to EDC. This process was called as mixed gas process and developed by Kureha Chemical at 1960s. Kureha Chemical then further developed this process by changing low material from naphtha to crude oil and succeeded to develop the new process in 1970. Nippon Zeon also developed similar VCM process of combination of acetylene and ethylene from naphtha decomposition. In this process, decomposition gas was rst separated to acetylene and ethylene
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Fig. 5. Historical change of VCM processes. Reprinted with permission from Hydrocarbon Process 1973;2:99, 1979;3:75. q1973, 1979 Gulf Publishing Company [16,17].
and then each gas was supplied to each reaction. Separation of acetylene from mixed gas was conducted by solution absorption method by using dimethyl formamide as a solvent. These processes disappeared at the end of 1970s because of lack of cost competitiveness compared with newly developed oxy-chlorination process. 4.2. Development of oxy-chlorination process In early 1960s, the oxy-chlorination process was developed by Dow Chemical, Stauffer and Goodrich in USA. In Japan, Tosoh started the oxy-chlorination process at 1966. Process ow sheet of oxy-chlorination process is shown in Fig. 6. This ow sheet represents Mitsuis oxygen process [20].
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Fig. 6. Mitsui pure oxygen based oxy-chlorination process. Reprinted with permission from Dewitt Petrochem Rev 1995;3:D1. q1995 Mitsui Chemicals, Inc [19].
The stepwise reactions of the oxy-chlorination process of VCM can be pictured as follows CH2 yCH2 Cl2 ! CH2 Cl CH2 Cl CH2 Cl CH2 Cl ! CH2 yCHCl HCl CH2 yCH2 2HCl 1=2O2 ! CH2 Cl CH2 Cl H2 O Then overall reaction of balanced oxy-chlorination process of VCM can be pictured as follows 2CH2 yCH2 Cl2 1=2O2 ! 2CH2 yCHCl H2 O (1) Direct chlorination. Direct chlorination reaction of ethylene with chlorine is conducted in the reactor made by carbon steel lled with EDC. Ferric chloride acts as catalyst of this reaction. Ethylene is usually supplied in excess amount to consume chlorine completely. In the advanced process for direct chlorination developed by Stauffer, the reaction is conducted at the temperature of boiling point of EDC. Energy generated in the chlorination reaction is utilized for the distillation of EDC purication (Fig. 7) (2) Purication of EDC. Impurities of EDC will cause prohibition of decomposition or deposition of coal inside the furnace tube. So the purication of EDC is needed for the succeeding decomposition process. Dehydration is also important for prevention of corrosion of machinery. Washing with alkali water is needed for EDC from the oxy-chlorination to remove HCl and chlorinated compounds.
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Fig. 7. High temperature direct chlorination process.
(3) Oxy-chlorination. The most important part of whole process is of course oxy-chlorination reaction. Efciency of the oxy-chlorination reaction is essential for the whole VCM process. Ethylene, HCl and oxygen react as gas phase contact reaction on the active alumina with cupric chloride as catalyst. There are two types of reactors, one is xed bed type and the other is the uidized bed type. Processes of Geon, Hoechst, Solvay, Tokuyama and Mitsui are uidized bed type and processes of Stauffer (now this process is owned by EVC) and Tosoh are xed bed type [20,21]. The oxy-chlorination processes can also be classied by oxygen source, air or pure oxygen. Oxygen process was developed at end of 1960s by PPG Industry in USA and Mitsui in Japan [2224]. Outlines of both air and pure oxygen processes are shown in Figs. 8 and 9, respectively, [25]. In the case of air process, nitrogen in the air acts as inert gas to prevent explosion. On the other hand in the oxygen process, excess amount of ethylene is supplied to prevent formation of explosive gas mixture. In the oxygen process unreacted ethylene is washed by alkali water and returned to the reactor. Volume of
Fig. 8. Air based oxy-chlorination processes. Reprinted with permission from Hydrocarbon Process 1976;3:81. q1976 Gulf Publishing Company [25].
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Fig. 9. Pure oxygen based oxy-chlorination processes. Reprinted with permission from Hydrocarbon Process 1976;3:81. q1976 Gulf Publishing Company [25].
vent gas from the oxy-chlorination reaction of the oxygen process is much less than that from air process. From the viewpoint of environmental protection this is the very strong point of the oxygen process. Typical break down of manufacturing cost of both processes is listed in Table 5 [20,21]. (4) Thermal decomposition of EDC. Puried EDC is decomposed in the furnace. Condition of decomposition is 15 40 bar for high-pressure process and 7 10 bar for middle-pressure process. Decomposition temperature is 500 550 8C and the conversion is around 50 60%. After heat exchange with feed EDC, decomposed gas is quenched for prevention of formation of high boiling products or tar. By the HCl tower HCl is separated and sent back to the oxychlorination process. Then VCM is recovered in the VCM tower. Undecomposed EDC is returned to the EDC purication process. (5) HCl recovery from efuent liquid and gas. Efuent liquid from the EDC purication zone and exhaust gas from the oxy-chlorination process are generated. These efuents are incinerated with auxiliary fuel in the process shown in Fig. 10 and steam is recovered from waste heat boiler. Burned gas is quenched and absorbed to water in the absorber and HCl gas is recovered by stripping the absorbed HCl solution [26].
Table 5 Economy indices of Mitui process and EVC process Mitui process [20] (200 000 t/yr) Raw material (kg/t VCM) Ethylene Chlorine Oxygen Utility (/t VCM) Electric power (kW h) Steam (t) Cooling water (m3) Fuel (Mcal) Operators (mens/shift) EVC process [21] (300 000 t/yr)
462 578 139 105 0.22 175 660 4
462 585 131 110 0.05 0.2 150 700 4
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Fig. 10. HCl recover system by efuent incineration. Reprinted with permission from Bunnri Gijutu 1993;23(4):207. q1993 Nittetu Chemical Engineering Ltd [26].
4.3. Ethane process Ethane in natural gas is cheap and almost inexhaustible source for petrochemical industry. In early 1970s Lummus and Armstrong Cork tried to develop single step process of VCM from ethane, chlorine and air by molten salt process (Fig. 11). Pilot plant work was done but this process has not been commercialized because of reactor corrosion [16]. Recently, EVC has developed the new direct process from ethane to VCM [27]. Semicommercial plant work is now accelerated to conrm catalyst life and materials of construction, test the recycle and to optimize the ow sheet. Results have conrmed an oxygen conversion rate of 99% and ethane to VCM of 90%. It is expected that further ne-tuning could lift the ethane conversion rate to 92 95%. Design of the rst commercial plant is scheduled to start 2000, with commissioning in 2003 [28].
Fig. 11. Lummus VCM direct process from ethane.
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5. Suspension polymerization process 5.1. Outline of suspension polymerization process [29] Process ow sheet of PVC suspension polymerization process is shown in Fig. 12 [10,30]. This ow sheet is representing basic PVC production process developed till 1970s. Polymerization reaction is batchwise operation, started by feeding raw material into the reactor and nished by discharging PVC slurry after polymerization. Into the reactor equipped with cooling jacket and agitator are charged pure (de-mineralized) water, VCM and protective colloid (suspending agent). VCM is dispersed into water by agitation. The reactor is warmed up to a certain temperature. By adding initiator, polymerization catalyst by common word, the radical polymerization of VCM is started. Typical polymerization recipe is shown in Table 6. In Fig. 13 are shown a general prole of reaction pressure, reaction temperature, conversion per hour and accumulated conversion. At the time the reaction pressure goes down to a certain value, the polymerization reaction is stopped. Then unreacted VCM is recovered. After discharge of PVC slurry the reactor is rinsed and remaining
Fig. 12. PVC suspension polymerization process in 1970s.
Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Table 6 Suspension polymerization recipe Polymerization degree 1000 (K value: 66) VCM Water (de-mineralized) Suspending agent (PVA, etc.) Initiator (peroxy compounds, etc.) Polymerization temperature Conversion Pressure at end of polymerization Polymerization time
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100 parts 120 parts 0.05 0.10 parts 0.03 0.16 parts 57 8C 85 90% 5 kg/cm3 8h
VCM is evacuated. Manhole of the reactor is disclosed and operators enter into the reactor for cleaning up the deposits on the reactor wall by the scraper. The reactor is again rinsed and evacuated. These are procedures for one batch operation and then charge for the next batch will start. Slurry from the reactor is blended with other several batches in the slurry tank. Then slurry is fed to the dehydrator and wet cake is fed to the dryer. After removing coarse particles by the screen, dried PVC powder is transferred to the product silo. After ensuring quality, products are shipped. Recovered VCM is puried and liqueed by compression and returned to the feed line. Till early 1970s waste water is, without stripping, transferred through the settlement pond to the waste water treatment facility. 5.2. Particle formation in the suspension polymerization Special feature of the PVC suspension polymerization exists in its sophisticated morphology of particles. Very poor solubility of PVC in VCM causes precipitation of PVC in the VCM droplet at early
Fig. 13. General prole of suspension polymerization reaction.
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stage of polymerization. While proceeding with polymerization complicated particle structure is generated. This PVC particle structure is very important for understanding process ability and qualities of nal product. Bulk density, porosity and grain size are important factors of gelation, plasticizer adsorption and sh-eye. 5.2.1. Nomenclature of morphology of PVC There are many literatures [31 42] on morphology of PVC in which different terminology were used for expressing the micro-structure of PVC particle. At the international symposium of PVC polymerization held at Lyon-Villeurbanne in 1976, the particle structure formation of PVC and its morphology were discussed. Geil [33] reviewed discussions of the symposium and proposed the standardized terminology for morphology of PVC. Allsopp [31] summarized their own studies on the mechanism of formation of PVC particle morphology and modied Geils terminology more clearly as shown in Table 7. Since structures of the micro-domain and the domain disappear with conversion proceed, both are only important to describe the particle formation at very early stage of polymerization. Then the primary particle is the smallest unit for describing the formation of grain size and porosity. Many different types of model picture of particle structure were proposed and illustrated in the literature. The simplied model picture of particle structure with indication of the morphological units recommended by Geil [33] is shown in Fig. 14 [15]. 5.2.2. Mechanism of particle formation A simplied scheme of particle formation of PVC suspension polymerization is shown in Fig. 15. Monomer droplets dispersed in water change to PVC particles through three different routes destined by the balance of agitation power strength and the stability of the protective colloid [31]. Rout 1 is the case of using protective colloid with medium surface tension in combination of week
Fig. 14. Model picture of particle structure. Reprinted with permission from Kagaku Keizai 2000;47(11):78. q2000 The Chemical Daily Co. Ltd. [15].
Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Table 7 List of PVC nomenclature Term Approximate size Range (mm) Grain 50 250 Av. (mm) 130 Origin or description
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Sub-grain Agglomerate
10 150 1 10
40 5
Primary particle
0.6 0.8
0.7
Domain
0.1 0.2
0.2
Micro-domain
0.01 0.02
0.02
Visible constituent of free owing powder, made up of more than 1 monomer droplet Polymerized monomer droplet Formed during early stage of polymerization by coalescence of primary particles (1 2 mm). Grows with conversion to size shown Grows from domain. Formed at low conversion (less than 2%) by coalescence of micro-domain: grows with conversion to size shown Primary particle nucleus. Contains about 103 micro-domains. Only observed at low conversion (less than 2%) or after mechanical working. Term only used to describe 0.1 mm species; becomes primary particles as soon as growth starts Smallest species so far identied. Aggregate of polymer chainsprobably about 50 in number
The domain is not a feature of PVC morphology in high conversion polymer samples since a growth of this species with conversion obliterates all memory of it. It may only be regenerted and observed after subsequent processing.
agitation. Dispersed particles keep their small size during polymerization and change to the ne and dense PVC particles. Rout 2 is the case of using protective colloid with low surface tension in combination of high agitation. Dispersed particles agglomerate each other by collision and change to the coarser particles with high porosity. Rout 3 is the case of improper condition, such as too strong agitation or less droplet protection, too much agglomeration causes solid batch or fail batch in other word. 5.2.2.1. Grain size. Droplets of vinyl chloride are produced in the continuous water phase with the share derived by reactor agitation power. A size of droplet is expressed in Taylors equation shown below 16s h0 h 1 a gh 19h0 16h where a is the radius of the droplet; s, the interfacial tension; g, the rate of share; h, the viscosity of continuous phase and h0 is the viscosity of the uid in the droplet.
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Fig. 15. Particle formation of PVC suspension polymerization. Reprinted with permission from Pure Appl Chem 1981;53:449. q1981 IUPAC [31].
Although the Taylors equation is applicable for droplet formation of the uid (VCM), it is not sufcient for expressing a grain size of PVC. Since the nal product grain size is controlled by the balance of droplet formation and coalescence, other factors related to the performance of protective colloid must be incorporated. Sarkar and Archer [47] proposed the modied Taylors equation as shown below K sG0:2 a gh1:2 h0 h 19h0 16h 2
where G is the interfacial gel strength of hydroxypropyl methylcellulose (HPMC) measured by a penetrometer. As shown in both Eqs. (1) and (2) the interfacial tension (s ) is the most important factor of particle size control and is controlled by choice of protective colloid, such as PVA and HPMC. 5.2.2.2. Protective colloid (suspending agent). For the protective colloid of PVC suspension polymerization many kinds of water soluble natural or synthesized polymers are used. Partially hydrolyzed polyvinyl acetate, commonly called PVA, and hydroxypropyl methylcellulose (HPMC) are two most popular suspending agents for commercial production of PVC. Since each has a different feature as the suspending agent of PVC, PVA and HPMC are separately described hereafter. PVA. In Table 8 typical PVAs used in the suspension polymerization of vinyl chloride are listed [13]. Primaries are PVAs which have higher degree of hydrolysis and act as protective colloid and control mainly particle size. As shown in Fig. 16 there is an optimum range of degree of hydrolysis for
Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Table 8 Typical PVAs used in the suspension polymerization of vinyl chloride [13] Trade name Primaries Alcotex 72.5 Alcotex 78 Poval L 10 Gohsenol KP08 Gohsenol KH20 Secondaries Alcotex 55 Polivic 404 W Gosenol LL02 Atlas G 72143 Manufacturer
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Degree of hydrolysis (%)
Harco Harco Kuraray Nippon Gohsei Nippon Gohsei Harco 3V-Sigma Nippon Gohsei ICI
71.5 73.5 76 79 71 73 71 75 78.5 81.5 54 57 55 45 51 50
controlling particle size. On the other hand, there is a straight line relationship between porosity of grain and degree of hydrolysis [13]. Lee [43] measured interfacial tension of aqueous solution of PVA as shown in Fig. 17. It is very clear that surface active performance of PVA is increased by decreasing the degree of hydrolysis. Secondaries are PVAs which have lower degree of hydrolysis, less than 60%, and higher solubility in VCM and increase the porosity of PVC particle. Since secondary PVAs are insoluble in water and no longer able to control particle size, they are usually adopted in combination with primary PVAs. Smallwood [41] conducted intensive work on PVAs investigating clarifying performance of PVAs as suspending agent for PVC. In Table 9 molecular structures of PVAs are listed. Average sequence length of acetate and alcohol group were determined by 220 MHz 1H NMR. Molecular weight distribution was determined by GPC. In Table 10 are shown results of vinyl chloride polymerization by using different fraction, classied by solubility in water at elevated temperature, of Alcotex 72.5 which is a popular PVA as suspending agent for PVC. The fraction, insoluble in water at 35 8C, gave the highest porosity, as
Fig. 16. Inuence of degree of hydrolysis of PVA. Reprinted with permission from J Vinyl Additive Technol 1996;2:287. q1996 Society of Plastics Engineers [13].
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Fig. 17. Interfacial tension of aqueous solution of PVA. Reprinted with permission from J Chem Engng Jpn 1999;32:97. q1999 The Society of Chemical Engineers, Japan [43].
expected from its low degree of hydrolysis. The fraction, soluble at 80 8C, gave granulation failure, possibly because of low adsorption at the VCM/water interfaces. HPMC. Cheng [38] studied effect of HPMC structure on the particle morphology of PVC. Both experimental and commercial products of HPMC with different characteristics were evaluated for their performance. And in the further investigation with Langsam [39], interfacial properties were studied. These studies are combined and summarized in Table 11. Conclusions of their extensive studies are as follows: 1. The particle structure of PVC is controlled by the substitution and molecular weight of hydroxypropyl methylcellulose while the molecular weight distribution shows no apparent effect. 2. HPMC with high substitution of methoxyl group showed higher partition coefcient, which is expressed as the weight fraction of the suspending agent in the organic phase (VCM). Such HPMC showed higher performance to obtain porous PVC particles. Cheng [38] investigated particle structure of PVC based on cellulosic suspension system and found that the higher partition coefcients (solubility) of HPMC in VCM creates the higher porosity of PVC
Table 9 Properties of various polyvinyl alcohols [41] PVA Hydrolysis degree (%) Average sequence length Acetate Alcotex 72.5 Poval L8 Gohsenol KP08 Polivic S202 Alcotex A55 72.1 71.0 70.4 49.0 56.1 2.9 3.1 3.4 3.0 2.5 Alcohol 6.1 5.8 6.9 2.2 2.7 Interch. 1.3 1.3 1.2 1.6 1.6 GPC molecular weights Mw 1023 114 122 101 16 23 Mn 1023 35 20 46 2 5.5 Mw/Mn 3.2 6.1 2.2 8.7 4.2
Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Table 10 Analysis and polymerization results with Alcotex 72.5 fractions Fraction Hydrolysis degree (%) GPC molecular weights Mw 1023 Parent PVA Insoluble at 35 8C 35 40 40 50 50 80 Soluble at 80 8C 72 66 70 70 72 79 114 476 522 307 268 77 Mn 1023 35 68.5 71.5 65 74 30 Mw/Mn 3.2 6.9 7.3 4.7 3.6 2.6 PVC Grain size (mm) 150 153 128 136 146 Coarse
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Plasticiser take up (%) 18.0 25.2 19.5 20.5 16.6
particles. Nilsson et al. [44 46] and Sarkar and Archer [47] also studied properties of various kinds of HPMC, mainly interfacial tension. As shown in Fig. 18, the solubility of HPMC in the organic phase is directly related to the grain porosity. This is understandable as HPMC dissolved in the VCM droplet acts as a stabilizer for the primary particles. Cebollada et al. [48] investigated the inuence of viscosity of the suspension (HPMC) medium is analyzed in relation to molecular weight distribution and particle morphology. Particle diameters exhibit a continuous increase until reaching conversions of about 70% (Fig. 19). In a liquid liquid suspension, the maximum (critical) diameter allowing stable droplets without rupture or coalescence is known to increase with an increase in viscosity in the continuous phase. In the suspension system of their study, an increase in viscosity results in a higher stabilization of the monomer droplets and the formation of unicellular particles or, equivalently, retaining their identity as VCM droplets. Consequently, low viscosity media should produce smaller particles (Fig. 20). Zilberman et al. [49] studied HPMCPVA water. 5.2.2.3. Effects of agitation. Johnson [50] investigated effects of agitation during VCM suspension
Fig. 18. Solubility of HPMC and porosity. Reprinted with permission from J Vinyl Technol 1991;13(1):26. q1991 Society of Plastics Engineers [47].
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Table 11 Characteristics and performance of HPMC Grade Composition Mn 1024 Methoxyl (%) Hydroxy (%) Properties of aqueous solution Viscosity (cP) Partition coefcient Interfacial tension (dyn/cm) PVC properties Gel temperature (8C) Pore volume (ml/g) Particle size (mm)
Experimental products XD-1 3.64 XD-3 7.65 XD-4 6.26 XD-5 3.51 XD-7 3.25 Commercial products Type-1 3.74 Type-2 5.14
23.0 23.9 23.5 22.8 23.1 21.0 28.1
11.1 8.4 10.1 9.5 9.5 8.4 8.5
38.9 108.0 81.0 28.7 31.0 31.2 42.9
1.69 3.31 2.70 1.40 1.75 1.45 4.00
7.2 6.8 7.1 6.4 6.9 6.4 3.8 70 56
0.21 0.15 0.17 0.19 0.16 0.18 0.30
180 180 180 180 180 180 180
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Fig. 19. Growth of particle diameters during polymerization. Reprinted with permission from J Appl Polym Sci 1989;37:145. q1989 John Wiley & Sons, Inc [48].
polymerization using Weber number as index for intensity of agitation. The actual Weber number used is shown as follows We
r N 2 D3 sgc
where r is the average density of the total dispersed mass; N, the agitator speed; D, the impeller diameter; s, the interfacial tension and gc is the gravitational constant. In Fig. 21, the mean particle size change vs Weber number, which were obtained in 5 m3 reactor, is shown. The relationship between mean particle size and Weber number is non-linear and approximately parabolic. This indicates that at very strong agitation the agglomeration of grain caused insufcient protective colloid action of suspending agent. In Fig. 22, the relationship between bulk density and Weber number is shown. Bulk density is not strongly effected by agitation over middle of the Weber number range. Lewis and Johnson [51] conducted the study on agitation scale-up also using Weber number as index for intensity of agitation. The study covered three different size reactors of bench scale, pilot plant, and commercial production. But there is no consistency in relationship between various properties of PVC and Weber number. These results suggest that the particle formation cannot be explained only by the intensity of agitation. Since the agglomeration phenomena of both sub-grain (monomer droplet) and grain is the most important factor of the particle formation, as mentioned above, the performance of protective colloid is much important to understand the mechanism of particle formation. 5.2.2.4. Combined effect of protective colloid and agitation. Belopolski proposed the equation for expressing mean particle diameter of PVC resin, incorporating two factors, the specic stirrer power (kW/m3) and the sum of the suspending agent concentrations (wt% relative to VCM) as shown
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Fig. 20. Effect of viscosity on particle diameters. Reprinted with permission from J Appl Polym Sci 1989;37:145. q1989 John Wiley & Sons, Inc [48].
below d50 P 875 V 20:6 X 20:67 S 4
where d50 is the mean P particle diameter of PVC resin; P=V; the energy consumption rate per unit 3 volume (kW/m ) and S is the concentration of suspending agent. Kirschbaum and van Dierendonk [52] and Lee [43] tried to modify Belopolskis equation by their own experimental results. Comparison between the experimental and calculated mean particle diameter of PVC resin is listed in Table 12. Lee modied Belopolskis equation and proposed new one incorporating the physical properties of suspending agent as shown below 20:30 X 20:48 0:52 20:30 P S 5 d50 32:04s mc V where s is the interfacial tension (mN/m) and mc is the viscosity of continuous phase (mPa s). 5.2.3. Example of particle structure In Fig. 23 two types of PVC grains are shown as FE-SEM pictures of cross-cut of particle, (a) a compact particle and (b) a porous particle. As common feature of PVA and HPMC described in Section 5.2.2.2, the solubility of PVA or HPMC in the organic phase is directly related to the grain porosity. For explanation of this phenomena following
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Fig. 21. Particle size vs Weber number. Reprinted with permission from J Vinyl Technol 1980;2(3):138. q1980 Society of Plastics Engineers [50].
speculations can be proposed: 1. Soluble part of PVA or HPMC in VCM acts as protective colloid for primary particle of PVC in the VCM droplet. 2. Discreteness of primary particle is kept by the protective colloid effect of dissolved PVA or HPMC even at higher conversion. However, from observation by the FE-SEM of cross-section of particles there is no such difference of
Table 12 Comparison between the experimental and calculated mean particle diameter of PVC resin P S (%/VCM) Experimental value (mm) Calculated value (mm) P=V (kW/m3) Belonski 1.88 1.16 1.16 0.058 0.067 0.113 136.5 140.6 109.8 64.0 77.6 54.7 Kirshbaum [52] 109.2 126.2 126.2 Lee [43] 132.1 142.5 110.9
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Fig. 22. Bulk density vs Weber number. Reprinted with permission from J Vinyl Technol 1980;2(3):138. q1980 Society of Plastics Engineers [50].
discreteness of primary particle. On the other hand, in pore distribution measured by mercury intrusion method, difference can be seen that peak of pore size is around 0.6 mm for the compact particle and 0.9 mm for the porous particle. Pore volume is 0.179 ml/g for the compact particle and 0.277 ml/g for the porous particle. Combining these results it can be concluded that the difference in particle structure of the compact particle and the porous particle exists in the distance from the agglomerate to adjacent agglomerate, which consists of 20 30 primary particles. The simplied model of such compactness of agglomerate is shown in Fig. 24.
Fig. 23. FE-SEM pictures of cross-cut of particle: (a) compact particle (left); (b) porous particle (right).
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Fig. 24. Simplied model for compactness of agglomerate: (a) compact structure (left); (b) porous structure (right).
Such difference in compactness of agglomerate can be explained as follows: 1. With the increase of conversion the contraction of grain (there is a density change from 0.85 of VCM to 1.4 of PVC) is promoted by the compaction force of interfacial tension. 2. The interfacial tension can be weakened by suspending agent system both of water phase and monomer phase. 3. The weaker the compaction force creates the wider distance of the agglomerate, which has same meaning with larger pore volume. 5.3. Reactor scale-up 5.3.1. History of reactor scale-up The rst industrialized reactor for PVC in Japan was the 200 l autoclave which rotates itself around axis like tumbler drier developed by Chisso in 1941 for emulsion polymerization [53]. In 1950s the reactor for suspension polymerization introduced from USA was 4 m3 made of stainless steel. At that time 4 m3 was a standard size. As shown in Table 3 reactor size became larger step by step. In 1960s, the decade of high economic growth, the reactor size grew from 20 to 50 m3. At the end of 1960s Shinetsu Chemical in Japan [54] and Huls in Germany [55,56] developed almost same time extremely big reactor for PVC production with sizes of 130 and 200 m3, respectively. For economical reason the scale-up of production capacity is the natural industrial trend. In the case of suspension polymerization, especially, polymerization step is batchwise and the larger the amount of one batch output is more efcient. As an inevitable result the size of the reactor grew larger. The rst merit of large-scale production is the relatively lower construction cost because of Williams law of 0.6 power for scale-up of main machinery and equipment. The second merit is the relatively lower cost for manpower. In Table 13 is shown the comparison of economy for the cases of 40 reactors of 20 m3 volume and four reactors of 200 m3 volume calculated by Huls [55]. The advantage of large-scale production is obvious from the table. From 1960s, many attempts were done for scale-up of reactor for PVC suspension polymerization [57 60]. Change of reactor shape with scale-up are shown in Fig. 25 [61]. Small reactors with 4 m3 volume at early stage were made by stainless steel. Then, medium size
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Table 13 Characteristics of a suspension PVC polymerization unit using 200 m3 reactors compared with a plant using 20 m3 reactors based on 160 000 t/yr production [55] Capital investment (including emergency system, Gulf Coast basis) Space requirements Utility consumption Manpower 75% 65% 90% 50%
reactors of 20 30 m3 became popular and they were glass-lined type which was developed to prevent scale deposition on the reactor wall. Top entering shaft with bull-margin or Pfaudler type, three retreating blades, were popular agitation systems at that time with several types of bafe, plate or ngershape. Next stage larger size reactors with 30 60 m3 volume were developed which were equipped with bottom entering agitation shaft to prevent the shaft vibration. Water injection into sealed part of agitation shaft was applied to prevent gel formation of PVC. These reactors were glass-lined or clad material of
Fig. 25. Change of reactor shape with scale-up. Reprinted with permission from Y. Saeki. q1971 Y. Saeki [61].
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stainless steel on carbon steel type. Turbine type or Pfaudler type agitation blades were popular at that time. To increase productivity the reux condenser technology was developed. Since heat transfer area for unit volume decreases with increase of reactor volume, in the case of larger reactor than 60 m3, adoption of auxiliary heat removal by the reux condenser is inevitable for keeping high productivity. 5.3.2. Agitation scale-up As described in Section 5.2 particle formation in suspension polymerization of VCM is very complicate. Effect of agitation is one of the most important factors to control particle formation. It is therefore a different thing, to describe phenomena for results obtained from same size reactors with different agitation conditions and results obtained from different size reactors, which is necessary to develop scale-up theory. Lewis and Johnson [51] conducted the study on agitation scale-up using Weber number as index for intensity of agitation. The study covered three different size reactors of bench scale, pilot plant, and commercial production. But there is no consistency in relationship between various properties of PVC and Weber number. Ozkaya et al. [62] conducted computer regression analysis for the results of 10 l to 27 m3 reactors and obtained following equations d50 4346:8N20:905 D20:901 T0:514 Hl 20:131 d50 =D 273 292:1We20:51 Nmin 3049:1D 2 1:1T=D20:113 6 7 8
where d50 is the mean particle size (mm); N, the impeller speed (min21); D, the impeller diameter (m); T, the reactor diameter (m); Hl, the liquid height; V, the reactor volume (m3) and Nmin is the minimum impeller speed at which complete dispersion of VCM in water can be achieved. In the equations only the values 4346.8, 273 292.1, 3049.1, 20.113 depend on recipe. The authors also conducted same type study on the results obtained from 2 m3 pilot plant reactor and commercial reactors with different volume size from 20 to 150 m3 as shown in Fig. 26. From the empirical line shown in this gure the following equation is obtained: d50 =D 223 872We20:57 9
Our results covered much bigger reactors, the biggest 150 m3, compared with 27 m3 reactors of Ozkaya et al., and there is a very good correspondence between Eqs. (7) and (9). As Ozkaya et al. pointed out, the shear rate distribution in small reactors and commercial scale reactors differs, it is therefore essential to change the ratio of impeller diameter to reactor diameter for adjustment of some nal PVC properties. In our experience of wide range scale-up to adjust nal PVC properties we found the following points important: 1. Power consumption per volume must be kept at constant. 2. Pumping capacity per volume also must be kept at constant. 3. As a result, relatively larger blade D=T is needed for large reactors.
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Fig. 26. Particle size vs Weber number. Data obtained from reactors with different size from 2 to 150 m3.
5.3.3. Technical problems for large reactor With enlargement of reactor size the difculty of manual cleaning inside the reactor became more severe because of deep and wider reactor wall. In addition to this difculty another difculty caused by VCM hygienic problem, carcinogen problem, has been actualized. To solve these problems the cleaning technology by high-pressure water jet, around 300 bar, was developed. By this technology the frequency of manual cleaning inside the reactor was dramatically decreased but not completely eliminated. Then development of the new technology to prevent scale formation becomes crucial especially for a large reactor. 5.4. Scale prevention technology As mentioned in Section 5.1 the scale formation is the essential drawback of PVC suspension polymerization. Scale on the wall causes a fatal damage on the heat transfer capacity. Contamination of scale into PVC causes sh-eye of product. So perfect reactor cleaning is needed to attain heat transfer capacity and also product quality. Even after the development of high-pressure water cleaning devices, reactor cleaning needs big manpower and long operation time and was the main obstacle for development of large reactor technology. 5.4.1. Pioneer works Pioneer works of this eld were done by Kitamura et al. of Shinetsu Chemical in late 1960s. The rst patent application was led in 1967 [63]. A clue of these epoch-making inventions was a nding of no PVC scale deposition around meniscus mark by marking ink on the VCM glass gauge. The famous patent assigned to Shinetsu Chemical [64] consists of dyestuff or color pigment, which is ingredient of marking ink. These pioneer works on scale prevention technology supported the successful development of large reactor system of Shinetsu Chemical. After this innovative invention made by Shinetsu Chemical [63 68], numerous numbers of patents, mainly coating of anti-fouling agents of both monomeric and polymeric chemicals, and addition of anti-fouling agents to polymerization recipe were applied.
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5.4.2. Mechanism of scale formation The literature in this eld consists of almost all patents. There are many explanations about the mechanism of scale formation on the reactor wall in patent statements but no one understand which one is correct. To develop the technology of scale prevention effectively, the proper understanding for the mechanism of scale formation is very important. But the early stage of development of this eld was a kind of trial and error type. The nding of effective method for preventing scale formation always preceded and the explanation for its mechanism followed. There are few literatures, which are proposing the mechanism of scale formation and scale prevention [69 71]. Bilgic and Savasci [69] summarized the mechanism of scale formation as follows. The exact cause of scale formation is not completely understood; however, the process appears to occur in two steps. The rst is the adsorption and subsequent polymerization of VCM on the wall. The second is the deposition of PVC formed in the bulk of the reactor onto the formerly existing scale layer. There are two different explanations of VCM polymerization on the reactor walls. 1. PVC has a very low solubility in its monomer, so that polymer radicals growing in the liquid phase precipitate out almost as soon as they are formed. The formation of new nuclei is less favored thermodynamically; therefore the polymerization occurs in the adsorbed VCM layer, on the reactor walls. At the beginning of polymerization, when few or no nuclei exist in the suspension, these macroradicals will tend to precipitate out on any available imperfections on the wall where VCM is most likely adsorbed. 2. The water-soluble part of the initiator polymerizes with the dissolved VCM in the water phase and the resulting PVC precipitate on the reactor walls. This precipitation of macro-radicals results in a rapid transfer of radical activity from monomer phase to polymer phase. Once PVC had adhered to the reactor walls and has radical activity, it can be swollen by fresh VCM and can continue to grow into very large, less porous lumps until all the VCM is consumed. In addition of above we propose the third mechanism. 3. Active site on the reactor surface. In the case of stainless steel surface there is some active site in the sense of local cell, which may act as polymerization catalyst or play a role of strong adhesive point with PVC. This hypothesis was supported by the work of Meinel and Behrens [70] who observed polymerization of VCM at the surface of stainless steel without the presence of initiator. 5.4.3. Classication of various patents for scale prevention Kitamura [72] classied the technologies of scale prevention as shown in Table 14. Sekiguchi and Kondou [73 76,77 80] classied Japanese patents applied in the period from 1970 to May 1976 and consecutive period of June 1976 1979 as shown in Table 15. Judging from the number and increasing trend of classied patents, (A) addition of anti-fouling agents and (B) coating of anti-fouling agents of both monomeric and polymeric chemicals, are important technologies. Bilgic and Savasci [69] also classied patents into additive type and coating type. 5.4.3.1. Material of reactor surface. To decrease an afnity to VCM, or decrease adhesive strength to PVC deposit, many kinds of materials were proposed for reactor wall or other equipments, impeller blade and bafe. Glass-lining, nickel or chromium plating, particular types of stainless steel lining are examples of this category. Glass-lined reactor has an advantage of smooth surface and less afnity to
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Table 14 Mechanism of scale prevention [72]
VCM but has a large disadvantage of low heat transfer coefcient. Glass-lined reactor has another disadvantage, that is limitation of reactor volume because of the limitation of furnace for enamel baking on the steel. By the practical reason of construction cost and heat transfer efciency, common stainless steel plated on carbon steel with mechanically or electrically polished smooth surface is the predominant material for reactor wall. Electrical polishing has another advantage that is the elimination of the active site of metal surface by the electrolysis.
Table 15 Classication of patents for scale prevention [73 76,77 80] 1970 to May of 1976 Scale suppress technology Special reactor material Chemical coating on reactor wall Polymeric chemical coating on reactor wall Addition of chemical during polymerization Cleaning of inner surface of reactor during polymerization Special agitator or scraper Other method for scale prevention Remove or cleaning of scale Chemical cleaning Other cleaning method June of 1976 1979 Trend
4 18 7 44 17 17 43 13 2 165
3 63 23 57 4 3 9 0 0 162
21 45 16 13 2 13 2 14 2 34 2 13 22 23
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5.4.3.2. Scale prevention by polymerization additives. So many chemicals were proposed as scale suppressing additives. These additives can be classied by their mechanism as follows: 1. Adsorbent. Chemicals which have ability of adsorption on stainless steel surface are always effective anti-fouling agent. These chemicals cover the active site of stainless steel surface and disturb the scale formation by the third mechanism mentioned above. Boiler compound and anti-corrosion chemicals which make stainless steel surface passive, such as hydrazine, EDTA, phosphate or nitrate compound, hexamethylenetetramine show excellent performance as anti-fouling agent. 2. Polymerization inhibitor. To prevent the scale formation by the second mechanism mentioned above, addition of polymerization inhibitor is effective. Addition of excessive amount of polymerization inhibitor causes elongation of reaction time. 3. Alkali or buffer agent. Simple inorganic alkaline compounds, such as sodium hydroxide or phosphate, are also effective anti-fouling agents. These alkaline compounds weaken the adhesive force of scale deposit on the reactor surface both glass-lined and stainless steel. By ionic decomposition of peroxide, alkaline compounds usually act as a polymerization inhibitor and prevent scale deposition by the second mechanism mentioned above. 5.4.3.3. Scale suppression by surface coating. (a) Monomeric chemicals. The famous epoch-making patent applied by Shinetsu Chemical proposing coating reactor surface by dye and/or pigment [64] is the typical example of this category. Following the classication shown in Table 14 made by Kitamura, who is the inventor of this technology, coated dye and/or pigment act as both anti-corrosion agent and polymerization inhibitor. More than hundreds of chemicals were proposed as coating type anti-fouling agents and many of them can be classied as both anti-corrosion agent and polymerization inhibitor. (b) Polymeric chemicals. Mechanism of coating of polymeric chemicals is similar to coating of monomeric chemicals with the difference of duration of performance. By increasing molecular weight solubility to water phase and VCM can be controlled. Co-polymerization is very convenient to introduce various natures into polymers, such as hydrophilic, polymerization inhibition and adhesive property. Nearly all coating type polymeric anti-fouling agents cited in the patents are co-polymers with a functional group which has free-radical inhibition or free-radical trapping activity. Phenolic compound is the most common chemical for introducing free-radical inhibition activity into co-polymer. By changing the composition of co-polymer adhesive property, solubility to organic solvent or an aqueous caustic soda can be controlled. 5.4.4. Recent development of scale prevention technology Yearly number of patent applications in this eld is still high. There are already many substances with sufcient performance of scale deposition. Recent object of development in this eld is supposed to be the improvement of duration of performance. Another object is the easiness of handling of chemicals, such as easiness of spraying. There are several commercially available anti-fouling or non-scaling agents. They are all mixture of chemicals, which consists of polymeric coating compound as a main scale preventive component and wetting agent or adhesive agent as auxiliary additives.
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5.4.5. Reactor cleaning technology Various cleaning technologies for removing scale from reactor surface, agitation blade and bafe were developed. Solvent cleaning technology by using EDC, DMF or pyrrolidone were developed but not widely adopted because of higher construction cost for recycling of solvent. The high-pressure water cleaning is the most common technology for reactor cleaning. Two- and three-dimensional spray nozzle for water jet are developed. Recently, automatically retractable lance which can be used without manhole open, has been developed [81]. 5.4.6. Long term closed operation By combination of the advanced anti-fouling agent with water jet cleaning once for several batches, very long term non-manhole open operation has been developed. The progress of anti-fouling agent to ultimate performance will eliminate necessity of high-pressure water cleaning. 5.5. Improvement of heat removal technology 5.5.1. Effect of the reactor size on heat removal As the size of the reactor increases, its surface area to volume ratio decreases in the case of keeping the reactor height to diameter ratio H=D constant. This is a serious disturbance for achievement of high productivity by adopting large reactors. Then the improvement of heat removal technology is very important for developing large reactor technology. In Fig. 27 are shown a typical shape of the reactor for suspension polymerization [59]. The reactor has a jacket for heating or cooling, an agitator driven from bottom and water-cooled bafes. In the case of the reactor height to diameter ratio constant as 2, the surface area changes with reactor volume as shown in Table 16 assuming that the reactor shape is cylindrical and the surface of elliptical bottom is neglected [29]. The table shows that the available surface area decreases to 70% for the scale-up of three times of reactor volume. Since the ratio of surface area (S ) to the reactor volume (V ) can be expressed as follows: S=V k1 D2 =k2 D3 k=D k0 =V 1=3 10
For the scale-up of A times in the reactor volume, S=V (surface/volume ratio) decreases to 1=A1=3 : In the case of three times scale-up, S=V decreases to 69% and for 10 times scale-up S=V decreases to 46%. It is possible to increase surface/volume ratio by changing reactor shape and increasing H=D ratio. But there
Table 16 Effect of reactor size on heat transfer surface area [29] Reactor volume (m3) 1 3 10 30 100 300 Length (m) 1.72 2.48 3.71 5.34 7.98 11.52 Diameter (m) 0.86 1.24 1.85 2.67 3.99 5.76 Surface area (m2) 5 10 22 45 100 208 Surface area volume (1/m) 4.65 3.22 2.16 1.49 1.00 0.70
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Fig. 27. Typical shape of the reactor for suspension polymerization. Reprinted with permission from Chem Engng 1975;Sep15:121. q1975 McGraw-Hill Companies.
is a limitation of H=D ratio for homogenous agitation, which is around 1.6 for single stage Pfaudler type agitation and around 2.0 for multiple stage turbine type agitation. There is an additional factor that actual thickness of the reactor wall must increase as the diameter of the vessel increases to keep same pressure rating as shown in Fig. 28 [82]. The wall thickness for 10 m3 reactor is 20 mm and overall coefcient of heat transfer is 550 kcal/m2 h 8C. In the case of 100 m3 wall is 40 mm and overall coefcient of heat transfer decreases to 400 kcal/m2 h 8C. It is inevitable to develop effective heat removal technology for developing large reactor system with high productivity.
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Fig. 28. Reactor wall thickness and overall heat transfer coefcient. Reprinted with permission from Kagaku Sochi 1995;37(8):71. q1995 Kigyo Chosakai [82].
5.5.2. Development of heat removal technology 5.5.2.1. Increase of heat transfer area. It is possible to increase to some extent by putting jacket on the upper elliptical head. Increase of the number of bafes with water cool system is also effective to increase heat transfer area. But for number of bafes there is a limitation, which comes from homogeneous agitation and difculty of scale prevention or cleaning. 5.5.2.2. Adoption of coolant. Chilled water of around 10 8C cooled by ice machine can attain almost double of heat removal capacity compared with cooling tower water of around 30 8C in the case of polymerization at 50 8C. But the cost of machine and running cost of electricity for ice machine is very expensive. There is a technology to adopt coolant, such as ammonium or Fureon directly into jacket or bafe. This technology has also the drawback of high cost. 5.5.2.3. Reux condenser. By adoption of reux condenser the latent heat of vaporization of VCM can be removed from the reaction media by evaporation of VCM. Evaporated VCM gas is then cooled at the condenser tube and condensed to the liquid VCM, which returns to the reaction media. Tower water is
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sufcient to condense VCM gas and very economical. Large cooling capacity of reux condenser can be easily attained by adoption of large number of cooling tubes. By the addition of reux condenser to the conventional reactor system, it is possible to increase polymerization capacity by around 50%. But it is needed to know how to adopt reux condenser. Evaporation of very large volume of VCM gas from reaction media and return of big amount of liquid VCM affect on the dispersing system of suspension polymerization. It is necessary to solve foaming problem, clogging of condenser tube by entrainment of slurry, to control accumulation of inert gas and temperature control in combination with jacket cooling system, etc. During 1980s, many patents proposing how to utilize reux condenser were led. At late 1980s, the practical technology for reux condenser has been almost developed and widely adopted to the commercial plant. 5.5.2.4. Cooling by slurry heat exchanger. There are some patents proposing circulation of slurry outside the reactor through heat exchanger [83 89]. There are two big obstacles in this technology. One is the clogging problem of slurry heat exchanger by PVC scale deposition. The other is the difculty of particle size control because of high share rate of impeller of the slurry circulation pump. It is not clear that this
Fig. 29. Inner jacket type reactor. Reprinted with permission from Kagaku Sochi 1992;34(2):15. q Kigyo Chosakai [91].
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technology has been already commercially applied or not. But if the advanced technology of scale prevention is adopted and the clogging problem of slurry heat exchanger by scale deposition is overcome, the slurry heat exchange technology may be one of the candidates for auxiliary cooling system for the large reactor. 5.5.2.5. Development of inner jacket reactor. As already described in Section 5.5.1 the actual thickness of the reactor must increase as the reactor size increases to attain design pressure rating. Then heat transfer by conventional jacket cooling through thick wall inevitably decreases as shown in Fig. 28. Kureha Chemical and Shinko Pfaudler (now Shinko Pantec) developed innovative reactor with socalled inner jacket in 1980 [90 93]. An appearance of the inner jacket type reactor is shown in Fig. 29 [91] and the detailed structure of inner jacket is shown in Fig. 30 [92]. Because of the structure of inner jacket, thickness of heat transfer wall is very thin (11 mm) and almost constant for all reactor size as shown in the bottom of Fig. 28. The overall heat transfer coefcient U is given by the following equation [92] 1=U 1=hi 1=his 1=ht 1=hos 1=ho 11
where hi is the process side thin lm coefcient; his, the process side fouling coefcient; ht, the thermal conductivity of the jacket wall itself; hos, the jacket side fouling coefcient and ho is the jacket side thin lm coefcient. In Table 17 heat transfer coefcient for both conventional jacket and inner jacket are listed [94]. The overall heat transfer coefcient, U for inner jacket of both 70 and 150 m3 is 1300 and almost double of conventional jacket. The main difference comes from the big difference in the thermal conductivity of the jacket wall itself. There is another signicant difference in the jacket side thin lm coefcient. In the case of conventional jacket, to improve the jacket side thin lm coefcient, special nozzle or bafes of jacket
Fig. 30. Detail structure of inner jacket. Reprinted with permission from Shinko Pfaudler Tech Rep 1988;32(3):21 [92].
Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Table 17 Heat transfer coefcient of the reactor [94] (kcal/m2h 8C) Conventional jacket 70 m3 Main material Cladding material Thermal conductivity of the jacket wall Process side thin lm coefcient Jacket side thin lm coefcient Overall heat transfer coefcient, U 27 mm carbon steel 3 mm stainless steel 1200 3500 3000 690 Inner jacket 70 m3 7 mm carbon steel 2 mm stainless steel 3550 3500 5000 1300
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Inner jacket 100 m3 9 mm carbon steel 2 mm stainless steel 3025 3500 6500 1300
Both process and jacket side fouling coefcients are assumed as innite.
(Fig. 27) are developed to keep cooling water in contact with the wall moving as much as possible. But the improvement by these attempts is not sufcient mainly because of some leakage of cooling water through clearance of jacket bafes. In contrast to these insufcient cooling water circulation of the conventional jacket, the channel of cooling water of the inner jacket is perfectly closed by welding (Fig. 30). Then it is possible to improve the jacket side thin lm coefcient signicantly by increasing velocity of cooling water circulation in the case of inner jacket reactor. There are several patents led in this new eld [95,96]. Sumitomo Heavy Industry developed a new type inner jacket reactor, which has a structure of cooling water channel isolated from the outside reactor wall [97,98]. This new type inner jacket reactor has been already adopted for the new commercial line in Japan [99]. 5.6. Improvement of productivity 5.6.1. Production line system and production cost There are many documents, which discuss the economy of PVC production, such as the production cost and utility consumption [100 105]. Tomishima [104] calculated the production cost of suspension polymerization by changing the number of reactors and polymerization time for different size of the reactors and different type of heat removal system as shown in Fig. 31. In this gure there are two groups, one is a group of chilled water system drawn by a solid line and the other is a group of reux condenser drawn by a dot line. In the case of rst group the ice machine is utilized to improve the productivity. The sizes of reactors are 50, 100 and 150 m3 for both cases. Figures shown on the curve indicate polymerization time from 3 to 10. Each curve represents the results for different polymerization time of the same production line of total reactor volume of 300 m3. Different curve shows the different reactor size and number but same total volume of 300 m3. The X-axis is the production capacity. In the case of chilled water cooling the conversion cost increases steeply with short polymerization time because of soaring of electricity, especially in the case of larger reactor. On the other hand, in the case of adoption of reux condenser as auxiliary cooling, the conversion cost shows minimum at 4 h polymerization time. The cost for 3-h polymerization is slightly higher than minimum. This is because of increasing initiator cost for attaining 3 h polymerization. For the reactor size results of 100 and 150 m3 are on the same curve and result of 50 m3 is slightly higher. This is opposite tendency of the case of chilled water cooling. From this gure it is obvious that the system of adoption of reux condenser is far more efcient than
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Fig. 31. Production cost of suspension polymerization. Solid line: adopted chilled water system; dotted line: adopted reux condenser; gures on the curve: polymerization time. Reprinted with permission from Polyvinyl chloride-base and application 1988 p. 108 q1988 Nikkan Kogyou Shinbunsha [104].
chilled water cooling system in the sense of production cost. Four hours polymerization by using three 100 m3 or two 150 m3 reactors equipped reux condenser is most effective. This investigation was done in early 1980s and extensive works were done to blush up the technology for reux condenser as mentioned in Section 5.5. 5.6.2. Productivity index In Japan, the productivity of PVC polymerization line is expressed by the index of the efciency of reactor for unit volume (m3) as follows: [t PVC/m3 month]. The annual production capacity is calculated by multiplying this index by 11.5 months (half month is for maintenance). Since polymerization reaction of PVC is done by batchwise operation, the productivity of PVC is determined by cycle time of one set operation, which consists of charge time of VCM, water and other chemicals, polymerization reaction, slurry discharge and cleaning of the reactor. As shown in Table 3 of Section 3.1, the productivity of PVC polymerization line was improved signicantly from 10 t PVC/m3 month of 1970s to around 30 t PVC/m3 month of 1990s.
Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Table 18 Reduction of cycle time for batch operation of suspension polymerization (h) Operation Charge and heat up Polymerisation VCM purge and blow down Cleaning Preparing for cleaning Cycle time 1960s [10] 0.5 13.0 0.5 2.0 2.0 18.0 1980s [1] 0.8 1.7 4.7 6.7 0.7 1.2 0.8 1.7 7.0 11.3
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2000 [94] 0.5 4.0 0.5 0.5 5.5
5.6.3. Reduction of cycle time In Table 18, the trend of reduction of cycle time is shown with details of each operation of 1960s, 1970s and 2000 [10,1,94]. (1) Reduction of charge time. There is no difference in charge time of 1960s and 2000. But there is 10 times difference of reactor volume. For the large reactors longer time is needed to heat up through jacket because of small surface/volume value as described in Section 5.5. To solve this problem the hot water charge technology has been developed [106 108]. Hot water is prepared in advance of polymerization in the hot water tank outside and charged with VCM and other additives into the reactor. The most common suspending agent, HPMC and PVA are soluble in water but the properties of their aqueous solution are very sensitive to the temperature. Since by contact with hot water both HPMC and PVA precipitate from solution, the procedure of hot water charge requires some precaution to avoid such problem. (2) Short polymerization. As shown in Table 18 polymerization time, which is a main portion of cycle time, were signicantly shortened from 13 to 5 7 h, and then recently to 4 h. For reactor cleaning in 1960s it took around 4 h for preparing for manual cleaning inside the reactor and cleaning itself. As mentioned before development of jet water cleaning and scale prevention technology, cleaning time became shorter. By the completion of development of non-manhole open operation, cleaning time can be almost eliminated. The cycle time then reduced from 18 h in 1960s to 5.5 h and productivity increased signicantly. 5.6.4. High speed polymerization and quality improvement In each element of cycle time the polymerization time was most markedly decreased. This reduction of polymerization can be attained by the improvement of heat removal technology as mentioned in Section 5.5, such as inner jacket reactor and reux condenser. The polymerization time can be shortened by increasing amount of initiator. But simple increase of initiator amount leads negative effect on PVC quality, such as increase of sh-eye number and inferior of initial color and heat stability. Number of patents have been applied by Shin Dai-Ichi Vinyl, which are proposing technologies for improving qualities of PVC in the case of short polymerization time [109 114]. These technologies consists of following basic technologies or combination of two or three of them: (1) Choice of initiator. The most common and efcient initiators for VCM suspension polymerization in the sense of cost performance are dialkyl peroxydicarbonates, such as di(2-ethylhexyl) peroxydicarbonate. The typical reaction prole by using peroxydicarbonates is peaky at the end stage
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Fig. 32. Reaction prole of short polymerization. Dotted line: di-2-ethylhexyl peroxy dicarbonate (OPD); solid line: OPD cumyl peroxy neodecanoate.
of polymerization (Fig. 32). Simple increase of initiator amount in the case of sole usage of peroxydicarbonates leads severe peak reaction (dotted line in Fig. 32) and causes deterioration of PVC quality. Peroxyesters, such as peroxyneodecanoate of tertiary alcohol [13], are much more preferable for short polymerization. The combination usage of peroxydicarbonate with peroxyester is usually applied to make at reaction prole as shown in Fig. 32 by solid line. (2) Choice of suspending agent. By using the same suspending agent system with long polymerization time, sh-eye number increases very much for short reaction. Change of recipe to the direction of increase porosity is needed, such as increasing the ratio of PVA with lower degree of hydrolysis or increasing amount of secondary PVA. (3) Agitation condition. As described in Section 5.2 strong agitation is essential to make porous particle. Some portion of agitation energy is consumed for dispersing monomer droplet and tearing off VCM/PVC particle to ner one. In the patent assigned to Shin Dai-Ichi Vinyl [109] proper agitation condition was proposed by equation as shown below 5 # Pv T # 13
3
12
where Pv is a power consumption of agitation per unit reactor volume (kw/m ) and T is a reaction time (h). This equation indicates the importance of total energy consumed for dispersion and coalescence of particles against the force of interfacial tension. 5.6.5. Minimization of production cost of suspension PVC In Table 19, various economic indices for suspension process are shown from data of literatures with authors assumption for different decades. For each decade unit production capacity, volume and number of reactors, cycle time and productivity are shown. Consumption of VCM and utility, as indices for production cost are also listed in the table. Improvement of the economic indices with decades can be read from the table.
Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Table 19 Improvement of cost of PVC suspension polymerization Item Production capacity Reactor volume number Cycle time Productivity VCM Chemicals Electric power Steam Pure water Unit t/yr m3 h t/m3 month t/t PVC kg/t PVC kW h/t PVC t/t PVC t/t PVC 1960s 34 000 13.3 17 18 13.6 1.045 1.2 340 1.7 5.0 1980s 114 000 170 2 7 11 30.4 1.020 1.2 350 2.2 2.2
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2000 120 000 150 2 5.5 36.4 1.003 1.2 230 0.9 3.1
In Fig. 33, production costs calculated by using typical unit cost are shown for 1970s, 1985 and 2000 [115]. Manufacturing cost is the total of exible costs which consists of VCM cost, conversion cost consists of additives cost and utility cost, and plant xed cost which consists of depreciation cost of production facility, labor cost and administration. Overall cost is the total of manufacturing cost and selling cost consists of delivery cost and overhead. Higher cost in 1985 was caused by high VCM price which came from oil price of second oil shock. The balance subtracted VCM price from manufacturing cost is called as the conversion cost from VCM to PVC. The smaller conversion cost indicates the higher level of manufacturing technology. In other words, percentages of VCM price to manufacturing cost can be used as the index of maturity of technology. From the investigations for various processes of other polymers, the technology with monomer price percentages higher than 70 can be called as matured one. The suspension PVC process may be understood as almost completed technology, since its monomer price percentages was already 76% in 1970s. After that there was another signicant improvement in the technology as mentioned before, this index rose to 80%. The suspension PVC process should be considered as the perfectly matured process and its production cost already reached to the ultimate level. 5.7. Computer control 5.7.1. The rst attempt of computer control by Huls At the conference held at Chicago in 1967, Huls in Germany reported the application of the direct digital control (DDC) to synthetic rubber plant and suspension PVC plant [116 118]. This presentation affected strong impact on computer utilization in world polymer plant. For batch polymerization of PVC, a DDC computer system, the Foxboro PCP-88 conguration was selected. This conguration consists of two central processing units, one control computer and one standby computer. The two computers communicate with process variables via a single data bus sub-system and with each other via the communication link. This conguration was selected to minimize the probability of a complete system failure and to minimize the necessary analog instrument backup.
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Fig. 33. Production costs for 1970s, 1985 and 2000. Reprinted with permission from Kagaku Keizai 2001;47(2):83. q2001 The Chemical Daily Co. Ltd [115].
Huls PVC plant with this computer control system has the following capacity: Batch blending system consists of 10 mixing vessels, grouped into six material feed line stations, Batch reactor system consists of 80 reactors, grouped into 10 lines of eight reactors each. Only one operator is needed to run this PVC plant under DDC. In a similar scale plant under conventional analog control, four operators are necessary. The system controls preparation of chemicals according to stored recipes, sets up batch transfer to reactor, provides batch sequence control to prepare reactors for the charge, performs DDC of batch temperature during polymerization reaction cycle and initiates safety and alarm procedures. The basic variable to be controlled during polymerization cycle in the reactor is temperature. A cascade control mode (PID-PI) is used to control the ow rate of either cooling jacket surrounding the reactor. 5.7.2. Computer control for large reactor PVC plant In 1970, Nakagawa et al. of Shinetsu Chemical disclosed a new computer control system for their Kashima plant consists of 130 m3 reactor [119 123]. Together with the scale prevention technology and
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the large reactor technology, the development of this computer control system realized the rationalization and safety of whole PVC plant. The most important feature of this system is the hierarchy construction combining computers for both operation (upper computer for administration) and control purpose (lower computer). Operating computers have the following functions: 1. 2. 3. 4. Calculation of optimal production commands based on external and process information, Automation of product handling and shipping service, Automatic process analysis and optimal judgment, General data logging and monitoring.
These computers are expected to play a major part in labor saving, in improving the plant performance, in ensuring effective use of the equipment and in promoting safety. Control computers have the following functions: 1. Program sequence processing of all batch processes, 2. Internal feed-forward control and DDC, 3. Back check operation. These computers are expected to help a great deal in the centralization of operation control functions, improvement of control accuracy and controllability. Marked improvements have been made in terms of reliability and safety. The control system for reaction temperature is the most important part of PVC plant instrumentation. The shortening of polymerization time for improving productivity causes large heat generation of the polymerization reaction, which requires quick response of cooling system. But there is time lag for cool down in the system using conventional feedback system Shinetsu developed feed-forward control system to overcome this difculty. By taking action in advance by predicting the amount of heat generation of polymerization reaction, combined with DDC system, the short polymerization in the large reactor was achieved. By adopting such computer control system: 1. improved economic characteristics due to increased plant size, 2. greatly stabilized product quality due to large plant scale and new technologies, 3. absence of polymer scale deposition, not only quality but also labor productivity and safety are markedly improved. By applying such computer control system Kashima PVC plant of Shinetsu Chemical needs small number of operators only one tenth of conventional plant operators. After the successful operation of Kashima plant, Shinetsu Chemical licensed this technology worldwide. 5.7.3. Distributed control system (DCS) From the early 1970s computer control systems were widely applied to the PVC plant. But there were some drawbacks of application of DDC system [124 126]. At that time computers for such purpose were very expensive. Since the reliability of computers were not so high, the backup system by standby
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computer or analog system was needed. Because one computer covers many loops, single defect of one part of the control system may affect all the systems. Another drawback was the difculty of changing computer programs, because of lack of exibility of programs at that time. In addition to PID control and feed-forward control, for temperature control and reaction rate control various systems were proposed, such as programming control of polymerization rate, conversion control by calculation of heat generation and others [127 134]. In the late 1970s DCS became popular in this application. At the same time, price of computers signicantly decreased and the reliability of computers were improved very much. Recently the instrumentation venders are supplying a ready-made sub-system for each unit operation for polymer process. Then together with the price reduction of hardware, the easiness of programming accelerated the spread of DCS for PVC plant. 5.7.4. Safety aspects Safety level of PVC plant was signicantly improved by introduction of computer control systems. Not only because of reduction of human error attained by substitution of such manual operation by computer control but also continuous monitoring of whole plant by computer system, the probability of trouble can be almost perfectly suppressed. Abnormal reaction behavior can be detected in early stage by computer monitoring and the accident can be avoided by quick and proper automatic action. Very quick action in the case of emergency situation, such as automatic charging of short stopping agent, can also be realized by computer control.
6. Bulk polymerization process 6.1. Outline of bulk polymerization process 6.1.1. Description of the bulk polymerization process As mentioned in Section 3.2 the bulk polymerization process is the simplest process among four polymerization processes as shown in Fig. 4. Also in the PVC manufacturing processes the bulk polymerization process is simpler than the suspension polymerization process [11]. There are many articles on the PVC bulk polymerization process [135 153]. Advantages of the bulk polymerization process described in the article of Rhone-Poulenc, who is the only process owner in the world, [145] are: Simplication of the plant. Only VCM and initiators are used in bulk polymerization; there is no need for water and suspending agents and de-mineralized water. It also suppresses a number of procedures: no preparation of solutions of suspending agents no centrifugation of the slurry after polymerization no drying no waste water treatment.
A small steam generator with low-pressure steam is sufcient. This combined advantage reduces investment cost. High productivity. Due to the absence of water and the use of a reux condenser, productivity is very
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high. A V 50 unit with one pre-polymerization reactor of 30 m3 and ve post-polymerization reactors of 50 m3 produces 100 000 t/yr in 8400 h (11.7 months), i.e. 370 t/m3/yr (or 31.7 t/m3/month). Operating cost. VCM consumption with 1007 kg for 1000 kg PVC is particularly low. Steam consumption is less than half of the amount necessary in suspension processes. Power consumption is also reduced. Labor and maintenance costs are minimized. Products. The V 50 process allows to manufacture a large range of products covering a great number of uses. The requirements of the French market have led Rhone-Poulenc to manufacture ve different products for rigid and exible applications covering all the standard, market and meeting RhonePoulencs customers requirements. 6.2. Development of bulk polymerization process of vinyl chloride 6.2.1. Single stage process In Table 20, the history of development of bulk polymerization process of vinyl chloride are shown. The rst attempt was done by Saint-Gobain in 1938, at France. And the development was continuously proceeded only by the same single company, although company name changed frequently by merging and acquisition start from Saint-Gobain (France), then Pechiney Saint-Gobain, Rhone-Poulenc, RhoneProgil, Chloe-Chimie, Atochem and today AtoFina. Then, AtoFina is the only company in the world who owns this unique bulk polymerization technology. In 1939, St Gobain had developed their rst commercial process for the bulk polymerization of vinyl chloride, consisted of 0.8 m3 reactor. In 1956 a modied process, called as the L 51 technology, had been developed by Saint-Gobain. This process consisted of a 12 m3 horizontal reactor revolving around its own axis, a roller ball autoclave in other word. A number of stainless steel balls were introduced into the reactor for grinding lump of PVC and preventing scale deposition on the reactor surface. This process was the rst practical bulk process of PVC and was licensed to Germany and Japan. This process, however, had a principal defect derived from the structure of the rotating reactor. The speed of rotation of the reactor had to be kept within limits. Then product qualities were strictly limited. 6.2.2. Two stage process with horizontal reactor From 1958 the main objective of development of Saint-Gobain was focused on a process that had
Table 20 History of development of bulk polymerization process Year 1939 1956 1962 1975 1978 Process code Contents First commercial process, 0.8 m3 Roller ball reactor, 12 m3 Two stage process 2nd stage 1 reactor: horizontal 1st stage 23 m3 1 reactor 2nd stage 46 m3 5 reactors: horizontal 1st stage 30 m3 1 reactor 2nd stage 50 m3 5 reactors: vertical Change of company name Saint-Gobain Saint-Gobain Pechiney Saint-Gobain Rhone-Poulenc Rhone-Poulenc
L-51 M-66 N-8 V-50
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better control of particle morphology. In 1962, the two-stage process has been in commercial operation at St Fons. The rst stage polymerization, pre-polymerization, is conducted in a vertical reactor by high speed agitation of a turbine type agitator and stopped at about 10% conversion. In this step the seed PVC particles are prepared in VCM liquid and transferred to the second stage. The second stage polymerization, post-polymerization, is achieved in a horizontal reactor equipped with low speed agitation and stopped at about 80% conversion. The reactor for second stage, generally known as popos, is a horizontal stationary reactor with a slowly rotating ribbon blender type agitator. Reactor volume was rst 16 m3, then 25 m3. This process was known as M 60 and then renamed M 66, N 7 and N 8 with its growing capacity attained by enlarging reactor volume and improvement of cooling system. Reactor volume for N 7 and N 8 are 30 and 50 m3, respectively. In the N technique, a special shaft-less cage agitator was designed when the size of the autoclaves have been enlarged. By adoption of two-stage process it became possible to control the particle size and morphology and produce almost same product with suspension processes. This unique bulk process has been licensed worldwide and total capacity exceeded one million ton. 6.3. Two-stage process with vertical second stage reactor 6.3.1. History The horizontal second stage reactor is effective for heat removal and removal of residual VCM but has a drawback of difculty of PVC powder. Remaining PVC powder may cause sh-eye and obstacle for removal of residual monomer in the resins.
Fig. 34. Flow sheet of two stage bulk process with vertical second stage reactor. Reprinted with permission from J Vinyl Technol 1984;6:35. q1984 Society of Plastics Engineers [146].
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Fig. 35. Temperature diagram of two stage bulk polymerization. Reprinted with permission from J Vinyl Technol 1984;6:35. q1984 Society of Plastics Engineers [146].
Since 1978, vertical 50 m3 reactors are under operation in Saint-Fons. Before reaching such a size, smaller reactors had been operated for 15 years and the agitation system has been progressively improved. Today, one screw agitator is introduced through the top while a scraper agitator is introduced at the bottom. This system allows a fast discharging of the reactor and an easy cleaning. 6.3.2. Description of the process In Fig. 34, ow sheet of two-stage process with vertical second stage reactor is shown. Outline of procedures of two-stage polymerization is known from the temperature diagram shown in Fig. 35 [146]. In the single vertical pre-polymerization reactor a half of VCM is introduced with initiator. The polymerization temperature of the rst stage is higher than post-polymerization for stable particle formation. The rst polymerization is conducted for around 20 min with vigorous agitation by turbine agitator till 10% conversion. Polymerization system at this stage is still liquid. Generated polymerization heat is removed by jacket cooling and reux condenser. From the rst stage reactor the seed PVC dispersed in VCM is consecutively delivered to each of ve post-polymerization reactors, where second half of VCM and different kind of initiator are charged. The temperature of the second stage polymerization is dened at certain point to control molecular weight, K value, as required. The reaction medium has become powdery beyond 20 25% conversion. Under controlled conditions of temperature, pressure and agitation, polymerization is carried out till 80 85% conversion. Diagram of a vertical second stage reactor is shown in Fig. 36. [146]. The reactor has two independent system of agitation, one is a single screw agitator introduced from the top and the other is a scraper agitator introduced from the bottom. Heat removal is done by jacket cooling, cooling by screw and reux condenser. Improvements of agitation system bring several advantages, such as suppression of dead area and deposits on the screw, improved powder mixing and improved heat exchange via screw. In addition to
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Fig. 36. Diagram of a vertical second stage reactor. Reprinted with permission from Vinyl Technol 1984;6:35. q1984 Society of Plastics Engineers [146].
these advantages the new agitation system create many advantages in combination to the feature of the vertical position of reactors: 1. It can be possible to equip thermo-probe on the reactor wall which is not scraped by agitator. Then the temperature of powder can be measured even at the stage of degassing. 2. The vertical position of reactors allows a very short discharge time. 3. Two high-pressure water cleaning systems can be installed. In the V 50 process there is no specic device for stripping residual VCM in the resin, which is done in the second stage reactors. There is a classication section also in the V 50 process, which is peculiar only for bulk process. 6.3.3. Role of the rst stage polymerization The role of the rst stage polymerization in the two stage bulk polymerization process of PVC are preparation of the stable seed PVC particles and control of morphology, which is derived from the seed.
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Since these processes must be done within very short period till 10% conversion, the control of particle formation in combination with polymerization reaction rate is very important. After initiation the growing polymer chain rapidly becomes insoluble in VCM and precipitates. The formation of primary particles is similar to the mechanism of particle formation of suspension process described in Section 5.2. Since in the case of bulk process no suspending agent is adopted, aggregation of the primary particles is controlled by agitation condition, polymerization temperature and some additives. Many authors have presented their own proposal for the mechanism of particle formation in bulk process. Fisher [146] explained the mechanism by the formation of particles, initially consisting of strings of beads, which is formed at low conversion less than 1% with agitation. The tip speed of a at turbine agitator affects the formation of primary particles, and particle size of nal PVC grain can be controlled by intensity of agitation at this early stage of the rst stage polymerization. The higher agitation speed causes the smaller particle size of nal PVC grain. The number and the size of these primary particles depend on the reaction temperature and on the nature and the proportion of the initiators. The higher reaction temperature is favorable for aggregation of particles and makes seed PVC stable. Then the rst stage is always polymerized above 62 8C. However, there is a limitation of the higher reaction temperature, because it causes decrease of porosity of nal PVC grain. There are some attempts to control the particle size by addition of some monomer soluble polymers or surface active agents at the rst stage polymerization. The rst half of VCM and initiators is introduced to the rst step reactor. Active initiator with very short half-life time, such as acetyl cyclohexyl sulfonyl peroxide, ACSP, is used in the limited amount. After around 20 min the reaction rate of the rst stage is automatically decreased because of vanish of the initiator, which is consumed totally during such a short time. This system is convenient in the sense of safety because elimination of danger for auto-acceleration of polymerization reaction can be attained by limitation of the initiators. 6.3.4. Role of the second stage polymerization The reaction mass, PVC particle dispersed in VCM liquid, is transferred to the second stage reactor. An additional amount of VCM and initiators is introduced during this transfer (Fig. 35). For the second stage initiators with longer half-life time is introduced usually in combination of two or three of them to attain at heat generation. The medium very rapidly thickens and the available liquid VCM is absorbed into the pore of particles and has become powdery beyond 20 25% conversion. Polymerization proceeds only inside the grain. Chun and Jung [151] investigated an anomalous polymerization rate behavior at around 20% conversion only in commercial bulk polymerization of vinyl chloride. They proposed kinetic model for commercial scale polymerization and explained such behavior by non-equilibrium of the reuxed monomer between monomer and polymer phase. Fisher explained the mechanism of particle formation also for the second stage polymerization. The polymerization continues in each grain, progressively lling the spaces left free between the compartments (agglomerates of primary particles) of the grains. The internal densication of the grains takes place through growth of the particles, which gradually fuse together to produce solid compartment of increasing density. In Table 21, the change in the average size of agglomerates of primary particles is shown for the changes of conversion from 60 to 85% [146]. In Fig. 37, the relationship of porosity and conversion is shown for different molecular weights [146]. Apart from the effect of conversion, the coalescence of the primary particles is affected by the polymerization
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Table 21 Inuence of the degree of conversion on the size of the internal compartment [146]. Bulk PVC VI 130 (KV 72) Conversion (%) 53 63 79 Average size of the internal compartment (mm) 2.40 2.68 3.30
temperature; an increase in this temperature causes an increase in the size of the compartments, or agglomerates and hence a reduction in the porosity. The resin with higher viscosity index of 130, or K value 72, shows much higher porosity than the resin with lower viscosity index of 80, or K value 57. The control of conversion, therefore, is very important to control porosity for producing resins with certain molecular weight. The excess of conversion rate will cause lling of pore and densication of particles and in the extreme case cause a vitreous grain. Such resins cannot be deformed during processing and cause many sh-eyes. In the case of insufcient cleaning some remaining powder may be introduced into next batch and
Fig. 37. Porosity vs conversion. Reprinted with permission from J Vinyl Technol 1984;6:35. q1984 Society of Plastics Engineers [146].
Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Table 22 Comparison of economy indices between suspension and bulk process Item Production capacity Reactor volume Number of reactor Productivity VCM Sub-material Steam Electric power, x Pure water Unit t/yr m3 t/m3 month t/t PVC $/t PVC kg/t PVC kW h/t PVC t/t PVC Suspension process 100 000 105 3 29 1.004 25 900 230 2.3
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Bulk process 126 000 30 1 50 5 41 1.005 10 330 200
absorb VCM with initiators. This is also the origin of vitreous particles and cause many sh-eyes. The importance of perfect discharge of polymer and perfect cleaning of reactor surface are supposed to be a driving force for development of vertical second stage reactor. 6.4. Economics of bulk process Tomishima compared the production cost of bulk process with suspension process (Table 22). Utility consumption, especially steam consumption, is better for bulk process because of simplicity of the process. Needless of dryer and waste water treatment contributes for decrease of steam consumption in bulk process. Difference of electricity consumption is not signicantly large because the classication section is additionally needed for bulk process. VCM consumption is slightly inferior to suspension process mainly because of the loss of product by screen over. In this comparison productivity is signicantly higher for bulk process at that year. As mentioned in Section 5.6 the productivity of suspension process has been signicantly improved. It is very interesting to compare the productivity and production cost for the latest process both of bulk and suspension. 6.5. Product quality of bulk process During ages of the horizontal reactor process, product quality of bulk PVC, especially sh-eye in exible applications and product color, was apparently inferior to suspension PVC. Contamination of remaining polymer and insufcient homogeneity of powder mixing are causes of these defects. Product
Table 23 Plasticized mixtures, number of defects (sh-eye) [146] Resin Bulk PVC-vertical reactors Suspension A Suspension B Suspension C Defects per 1000 cm2 10 25 20 10 30
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Table 24 Regional capacity of two-stage bulk process Country North America West Europe East Europe Northeast Asia Capacity (1000 t/yr) 390 310 130 240 0 1070
(Including Russia) (Korea and Taiwan) (Japan)
World total
quality of latest bulk process characterized by vertical second stage reactor [146] is comparable with suspension PVC as shown in Table 23. 6.6. World capacity of bulk process In Table 24, the capacity of world bulk process for each region is listed. These gures include capacities of both of horizontal and vertical process. In Japan, Toa Gosei introduced L 51 process but stopped operation many years ago. In 1970s, another Japanese company studied to get license of two-stage process with horizontal second stage reactor. Mainly because of quality level at that time, the bulk process failed to invade into Japanese market. The product from the new vertical process, however, has not been evaluated in Japan.
7. PVC paste resin manufacturing process There are some review articles on paste resin manufacturing process [154 158]. 7.1. PVC for paste application Because of mixed usage of terms for polymerization process with terms for application, wordings of emulsion, dispersion, paste and plastisol are very confusing. In ISO (the International Organization Standardization) 1060-1:1998, the designation and specication system of PVC are described. In data block 1 of designation of this system, the polymerization process is indicated by code letters. S represents suspension polymerization; E, emulsion polymerization; M, bulk (mass) polymerization or X, other process. There is no code letter for micro-suspension. In data block 2 information about intended application is given. Code letter P is for paste resins, F, for ller resins (in other word blending resins or extender resins) and G is for general-purpose resins. In ISO 4612:1999 the denition for paste (also known as plastisol) is applied as paste (plastisol): a homogeneous dispersion of resin in an organic liquid (which is usually plasticizer). In USA, paste resin is called as dispersion resin. PVC resin for paste application is usually ne powdery PVC, which is agglomeration of primary particle with diameter of 0.1 5 mm. Paste (plastisol) is prepared by mixing process of appropriate PVC,
Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Table 25 Processing of PVC paste resin and products Processing Coating Paste coating on exible substrates by knife or roll and fusion in heated oven Deposit on former and article by dipping and fusion in heated oven Forming on inside of heated hollow mold and fusion in heated oven Forming and fusion on inside of rotating heated mold Products
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Leather, wallpaper, foamed ooring, under body coating Glove, metal parts coating Doll, boot Headrest, armrest, toy
Dipping Slush molding Rotational casting
plasticizer and other ingredients, such as ller, thermal stabilizer, pigment. Plastisol is then applied to many processing methods, such as coating on paper or fabric, dipping on the mold, slush molding or rotation molding. By curing in the oven, plastisol looses its uidity (gelation) and gives the nal product such as wallpaper (wallcoverings), articial leather, foamed ooring, doll and various automobile parts. In Table 25, main processing methods and their applications are listed. Major end-use shares of paste resin in USA, Europe and Japan in 1998, speculated by authors, are listed in Table 26. In each region there is a big difference in end-use share. Percentage of paste resin to total PVC consumption is around ve for USA and seven for Japan. 7.2. Paste resin manufacturing process 7.2.1. Outline of process The ow sheet of paste resin process is shown in Fig. 38. There are two different processes for paste resin; one is emulsion process the other is micro-suspension process, both shown in the gure. Product quality of paste resin from each process is slightly different mainly because of the difference of particle size distribution. Only polymerization section is different and other section is common for both processes. Separation of PVC resin from latex is conducted usually by spray drying, which is the most typical characteristic of paste PVC process. Dried PVC, agglomerate of primary particle is collected by cyclone and bag-lter and then usually ground (milling) by pulverizer. Because of small plant capacity compared with suspension process and many number of grades, size
Table 26 Applications of PVC paste resin, 1998 (%) USA Flooring Wallpaper Under body coating and sealant Molding and dipping Coated fabric Others 37 0.5 15 33 14 0.5 Europe 30 15 11 1 28 15 Japan 30 43 8 6 3 10
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Fig. 38. Flow sheet of paste resin process.
of polymerization reactor for paste process is relatively small, around 20 50 m3 with exception of 200 m3 of Huls. Large impeller is usually used for agitation of the reactor for paste process and power consumption is very low for preventing the formation of coagulum. Efciency of heat removal by jacket cooling is very bad because of weak agitation. Chilled water or reux condenser is applied for improving productivity. 7.2.2. Particle structure and production conditions Qualities of paste resin, such as composition, molecular weight, mean particle size, particle size distribution, kind and amount of emulsier for polymerization recipe, affect on the properties of plastisol. Particularly mean particle size and particle size distribution of paste resin, which have direct relation with production process, are the important factors for controlling properties of plastisol. Roughly speaking the larger mean particle size produces the lower viscosity plastisol. And particle size distribution of paste resin affects on rheological characteristics of plastisol. Recipe and condition of polymerization process and drying condition affect on mean particle size and particle size distribution of paste resin. Since paste resin is a dried product from a latex (from the emulsion or micro-suspension polymerization), which after drying consists of agglomerates of the particles formed at the polymerization stage, the degree to which these agglomerates break down in the paste is signicant in the nal particle size distribution. Thus, the nal distribution is a mixture of primary particles
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Fig. 39. Particle size distribution of paste resin. (Left) Micro-suspension process; (middle) emulsion polymerization; (right) seeded emulsion polymerization.
(distributions containing particles 0.1 5 mm formed during polymerization) and secondary particles (grains: mean particle size 30 60 mm formed during drying and subsequently reduced to 5 20 mm by milling). These nomenclatures for paste PVC particle, such as primary particles, secondary particles, agglomerates, are not same with those of suspension PVC. Photographs of primary particles and particle size distribution for three different polymerization processes are shown in Fig. 39. (Left). The particle size distribution of paste resin made by micro-suspension process is very wide as shown. (Middle) Emulsion polymerization. The particle size distribution of emulsion polymerization is very sharp, almost mono-disperse, with mean particle size around 0.3 mm. Viscosity of plastisol prepared from this resin will be very high. (Right) Seeded emulsion polymerization. The particle size distribution of seeded emulsion polymerization is bimodal as shown in the gure. 7.2.3. Micro-suspension polymerization In the patent detail procedure of micro-suspension polymerization can be seen. Example of polymerization recipe for micro-suspension process is shown in Table 27 [159]. In general, the ingredients and polymerization reactor used in micro-suspension polymerization are similar to those used for the emulsion reactors. The principal differences are that a monomer-soluble initiator is used and some or all of the monomer is emulsied to small droplets using a mechanical means prior to the start of the polymerization.
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Table 27 Micro-suspension polymerization recipe and condition [159] VCM Pure water Oil soluble initiator Emulsier Conditions Homogenization Lauroyl peroxide Sodium dodecylbenzene sulfate High-pressure pump 1st stage 2nd stage Temperature Conversion Particle size 100 parts 137 parts 0.2 parts 1 parts
Polymerization Product
1500 psi 500 psi 50 8C 76.5% 0.1 1.2 mm
A typical procedure, as shown in left-top of Fig. 38, is to homogenize a mixture of VCM, water, emulsier, and monomer-soluble initiator and pump this mixture into reactor. The mixture is then heated, with agitation, to the desired temperature, which allows polymerization to take place to yield a stable emulsion with a particle size distribution of 0.1 5 mm. Homogenization of the mixture before polymerization is carried out by the application of high shearing forces. Suitable equipment is a highspeed pump, colloid mill, homogenizer or high-speed stirrer. Examples of emulsier are alkyl aryl sulfonate, alkyl sulfate. Examples of monomer-soluble initiator are long chain diacyl peroxide type, such as lauroyl peroxide and more active peroxy dicarbonate. In the case of peroxy dicarbonate, aid of long chain chemicals, such as higher alcohol, esters, ethers and other long chain hydrocarbons are needed to stabilize latex [159]. Literatures and many patent applications, which propose improved technology, in the sense of particle size control or efciency of homogenization step, have been issued [159 164]. One example is the discovery that it is not necessary to homogenize all the VCM or water, thus reducing capital and energy costs associated with the homogenization step [164]. In another process, a seed latex is made by the micro-suspension process described above but using a large excess of initiator, typically lauroyl peroxide. In the second stage, a portion of this seed is used together with VCM, water, and emulsier. The polymerization is activated using a redox system consisting of copper sulfate and ascorbic acid. As the copper sulfate and ascorbic acid forms a complex which is soluble in the monomer phase, the excess lauroyl peroxide contained in the seed particle is activated. In this way the seed latex can be grown to large particles without the problem of secondary initiation [161]. Addition to this technology by introducing emulsion latex with the micro-suspension seed latex, the particle size distribution further can be changed to bimodal. Low paste viscosity can be obtained by this technology [162]. 7.2.4. Emulsion polymerization In the case of emulsion polymerization water soluble initiators are applied and polymerization takes place either in the micelles or in water, where always exists a certain amount of solved VCM [165 167]. One of the most important components of the emulsion polymerization recipe is the emulsier. The quantity used has a major effect on the nal latex particle size achieved, by determining the number of particles initiated. The nature of the emulsier can also affect the number of particles initiated,
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particularly at low concentrations. Usually, anionic emulsiers are used for this purpose, such as sodium or ammonium salts of alcohol sulfates, alkyl sulfonates, alkyl aryl sulfonates, sulfosuccinates, and fatty acids. The initiator used in emulsion polymerization is soluble in water, such as potassium perperoxydisulfate (potassium persulfate), or ammonium persulfate, hydrogen peroxide. Initiation takes place in the aqueous phase by free radicals, which are generated from the initiator. The rate may be increased signicantly by the addition of a reducing agent. Such systems were commonly called as redox catalysis. Three component systems, involving the use of a metal salt also, give further benets and typical systems are ammonium persulfate/sodium bisulte/copper sulfate or hydrogen peroxide/ascorbic acid/ferrous sulfate. Using such systems, polymerization may be carried out at lower temperature. Better control of reaction rates may be achieved, particularly if some of the compounds are injected continuously. In the case of normal emulsion polymerization the particle size distribution is very sharp as shown in Fig. 39 (middle) and mean particle size of primary particles is around 0.3 mm in the maximum case. For paste application, however, the presence of large particles is essential to prepare plastisols of low viscosity. In this case therefore the particle size distribution is wider and some particles larger than 1.0 mm are desirable. A typical particle size distribution of a PVC latex is shown in Fig. 39 (right). Seeded emulsion polymerization. Although the emulsier has a strong inuence on the number of particles initiated, and therefore on the nal latex particle size distribution, the use of preformed seed latex in the polymerization recipe is a useful technique for controlling particle size distribution, particularly if large particles are required. By suitable choice of size and quantity of seed latex, growth to a predicted size distribution can be achieved with minimum or controlled initiation of new particles. It has been shown that the absence of free emulsier in the aqueous phase is not the only requirement for the suppression of fresh initiation of particles and the surface area of the seed latex employed plays a major role. To achieve this condition calculated amount of emulsier is introduced to the polymerization site by monitoring growth of particle size. To make the particle size distribution wider, many techniques have been proposed by patents. One is the technique of latex blending, which is designed at certain ratio by blend of latex with different particle size. A merit of this technique is the precise control of the particle size distribution and a demerit is that this process requires many latex tank and blending tank. The other is the technique of modication of seeded emulsion polymerization, which is achieved by initiation of new particles controlled by excess amount [165]. The continuous emulsion process. The continuous emulsion process for the production of PVC was rst developed by I.G. Farbenindustrie in Germany in the 1930s [154]. Such a process is still operated in Germany by several companies. These companies have continued to develop the continuous emulsion. In the case of the continuous emulsion process different techniques are applied to make the particle size distribution wider [168 171]. 7.2.5. Drying of latex In order to isolate the product from the latex it is necessary at some stage to remove the water. Coagulation techniques are commercially applied in some country. But for paste application these are limited to certain types of products, because of their special rheological behavior. The structure of the particles (agglomerates) formed by removing the water is important in determining the nal properties of the plastisol. For this reason a spray drier is normally employed to
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Table 28 Effect of dryer conditions on resin agglomeration in plastisol [172] (%) Dryer (8C) Inlet 150 150 180 180 Outlet 60 75 60 75 Atomizer tip speed (m/s) 79 8 35 18 35 98 17 45 20 50 118 25 60 30 60 138 35 70 35 70
Agglomeration are dened as particles 4 mm.
isolate the solid product [172,173]. There are three types of spray dryer with different types of atomizer, spinning disc type (disc atomizer), pressure nozzle type and two uid nozzle type. In combination with the type of atomizer there are different types of dryer chamber assemblies, co-current and counter current. The performance of the atomizer is very important because it creates the spray of latex droplets which determine the size of agglomerate of the product. Hoffmann and Saffron [172] undertook a study to determine the effect of drying parameters on resin particle size distribution and subsequent plastisol viscosity and viscosity aging (Table 28). Effect of atomizer speed. Higher atomizer tip speed produced higher percentage of coarse particles. Increasing atomizer speed is known to produce smaller spray droplets. This should result in more highly fused resin agglomerates. Effect of dryer inlet temperature. The amount of agglomerates present in the plastisol increases with increasing inlet temperature. The droplets should be more highly fused because of the high inlet temperature, and therefore, will produce more agglomerates in the plastisol. Effect of dryer outlet temperature. As shown in Table 28 the amount of agglomerates present in the plastisol increases with increasing outlet temperature, which can be attained by decreased latex feed rate to the atomizer. Increasing the outlet temperature causes two changes, both of which should increase the degree of agglomerate fusion. First, decreasing feed rates to centrifugal disc atomizers produce smaller spray droplets, which dry faster and should be more highly fused because of their longer heat history. Second, the higher dryer temperature should more thoroughly fuse the agglomerates. The highly fused agglomerates do not readily break apart during plastisol mixing and result in more agglomerates in the plastisols. By the same reasoning, low dryer outlet temperature obtained by increasing the feed rate to the atomizer should produce larger, loosely fused agglomerates in the dried resin. These would be expected to fall apart more easily during plastisol mixing and should produce few agglomerates in the plastisol. 7.2.6. Bulk handling paste resin Unlike large particle suspension resins, ne particle paste resins have a tendency to lump and cake, thus bag shipment rather than bulk is applied. Moreover, it scatters easily during bagging or when it is taken out from the bag and mixed during sol preparation. This worsens the working environment. Since the owability of the powder is poor, it is difcult to rationalize powder handling as in automatic measurement and transportation. Various attempts have been made to solve the problems of handling or scattering by converting ne
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Fig. 40. Bulk-handleable paste resins.
particles into granules by properly aggregating them. For example, in 1960s agglomeration techniques, addition of water to dry powder and rotation on the disc, have been investigated but these are not in general use because of higher cost by additional equipment and drying. In late 1970s Stauffer Chemical developed the technology for producing a granular paste PVC [174,175]. The dried extender resin (blending resin) is mixed into latex of paste resin. Then the mixture is dried. This procedure involves spray drying the mixed latex which results in the formation of a substantial number of agglomerates with 100 mm diameter. Structure of the resin is described in the patent claim as a dry blend of a dispersion and extender resin characterized in that each extender resin particle is centrally positioned and is in contact with and surrounded by a plurality of dispersion resin particles. Paste resins produced by this technology show good owability and have features of bulk-handleable and dust free. Because of containing a certain amount of extender resin (blending resin) this resin is not suitable for some application, especially for thin coating. In late 1980s mainly in Japan the development of bulk-handleable paste resin have been restarted. Starting from the large customers, such as wallcovering and ooring, bulk shipment by tank truck and automated handling of resins have been started. The external structure of such bulk-handleable paste resins are shown in Fig. 40 in comparison with conventional paste resin. (1) Spray method. As described in this section the size and easiness of breaking of agglomerate can be controlled both by selection of dryer type and changing spray condition (Table 28). For producing paste resins with coarse grain size and easy dispersion behavior at plastisol preparation mild drying conditions are preferable. In this case grinding (milling) process must be omitted to keep coarse grain size [176, 177]. (2) Granulation in water. Unique process for production of granular paste resin has been developed
Table 29 Characteristics of bulk handling PVC paste resin (granular PVC paste resin) PVC paste resin General Particle size (mm) Bulk density (g/cm3) Angle of repose (8)a Index of powder owb
a b
Spray method 35 120 0.48 0.57 32 37 50 70
Aggregated method 100 300 0.50 0.60 38 41 75 80 100 200 0.50 0.60 38 40 80 85
1 10 0.20 0.30 56 60 20 30
Small value is good. Large value is good.
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Table 30 Relations between characteristics of PVC paste resin and properties of plastisols and products Composition of paste resina Viscosity of plastisolsb Fusion (gelation) of plastisols Defoaming of plastisols Strength of products Water resistance of products Transparency of products Electronic properties of products Density of foam cell
a b
Polymerization degree of paste resin 2 2 2 2 2
Distribution of primary particles 2 2 2 2
Aggregated secondary particles 2 2
Quantity and type of emulsiers 2 2
2 2 2 2
Vinyl acetate co-polymer, etc. Rheolgical behavior of plastisols.
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by Nippon Zeon [178 182]. A granular paste PVC is produced by mixing an aqueous dispersion of a vinyl chloride polymer with an organic liquid being difculty to be soluble in water and incapable of dissolving or swelling the PVC to prepare an aggregate of particles of the PVC, dehydrating the aggregate and then drying it. Drying is carried out by using a uidized dryer under such conditions that the temperature of the PVC is not more than 40 8C in the constant rate period of drying and not more than 50 8C in the falling rate period of drying. Product is in the granular form with an average size of around 100 300 mm and has very good handling behavior. After aggregation process in water, it is possible to remove water by ltration. Therefore, energy consumption of drying can be reduced. Properties of bulk-handleable paste resins are shown in Table 29 in comparison with suspension PVC and conventional paste PVC. 7.3. Relationship between characteristics of paste resin and properties of plastisol and nal product In Table 30, the qualitative relationship between characteristics of paste resin and properties of plastisol and nal product are listed. It is very important to nd out the quantitative relationship for whole of matrix.
8. VCM emission control of PVC plant 8.1. Vinyl chloride toxicity VCM is a sweet smell gas at ambient temperature with a boiling point of 213 8C. Because of ammable nature of VCM gas with explosive limits in air 3.6 33 vol%, VCM and PVC plants were designed to avoid explosion risk by minimizing probability of leakage of VCM. It is supposed that VCM concentration of working condition at that time was 1001000 ppm. Till the early 1960s VCM was assumed to be low toxic and used as an aerosol propellant in some countries, especially in USA and Japan. AOL. In the mid 1960s the occurrence of a bone disease called acrosteolysis (AOL) in a very small number of PVC plant operators, especially engaged in cleaning PVC reactors, was found. AOL is a bone disease, which usually takes a form of a degeneration of bone in the tips of the ngers. This accident incited the development of the cleaning and the scale prevention technologies, such as high-pressure water cleaning. ASL. In early 1974, B.F. Goodrich PVC reported to the National Institute of Occupational Safety and Health (NIOSH) the discovery of cases of angiosarcoma (ASL), a very rare form of liver tumor, among workers of their PVC plant. And the possibility of relationship of this rare cancer and exposure of operators to high concentration of VCM were subjected to the most urgent theme of the world PVC industry. In Table 31, topics of these VCM problem at that time are listed. Prior to the discovery of cases of angiosarcoma among workers of the B.F. Goodrich PVC plant, VCM has been already proven as an animal carcinogen by the tests for the purpose of reproducing AOL in rats. After nding of human cases, the additional detailed animal experimentation has been conducted by Professor Maltoni. At the same time epidemic studies has been started to nd out the safety limit of VCM exposure.
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Table 31 Topics of VCM hygienic problem and regulations Year 1965 1969 1973 1974 Problem and regulation Finding of acrosteolysis (AOL) FDA: Prohibition of PVC bottle for alcoholic drink Reporting of deaths of B.F. Goodrichs workers by Angiosarcoma (ASL) FDA: Prohibition of spray with VCM gas OSHA: VCM concentration of working condition. Temporary regulation OSHA: Final regulation FDA: Permission system of rigid and semi-rigid PVC for food (proposed) EPA: Regulation of VCM concentration at discharge point (proposed) Ministry of welfare (Japan): VCM concentration of PVC packaging for food
1975
Jan Apr May Dec Sep Dec Dec
50 ppm 10 ppm 10 ppm 1 ppm
8.2. Occupational regulations Number of ASL cases in the world PVC industries were registered as 118 at the end of 1984 [182]. Almost all cases of ASL are for the operators who engaged mainly to the manual cleaning inside reactor. The average of duration of engagement to such operation of patients was 17 yr. The average of the latency period for ASL was around 20 yr. The number of ASL in Japan is only 2. This relatively small number can be explained by frequent job rotation of operators in PVC plant in Japan. By the detailed epidemic studies it was founded that there is a clear threshold exposure level for ASL cases. Simonato [183] reported that the accumulated VCM exposure of 288 ppm yr is the minimum value for occurrence of ASL. For 45 yr operation of reactor cleaning, supposed to be the longest case, the threshold concentration is 6.4 ppm 288 ppm=45 yr: There is no case of ASL in operators who started working in PVC plant after the Occupational Safety and Health Administration (OSHA) in USA specied 1 ppm as the maximum average personal exposure at 1974. The VCM regulation for working condition of other countries lies between 1 and 5 ppm. 8.3. Reduction of VCM emission form PVC plant There are some review articles on VCM emission form PVC plant [184,185]. In Fig. 41, the amount of VCM emission is shown on the ow sheet of suspension PVC process, both for 1970s (upper) and 1990s (lower, Gothic gure). We call such ow sheet with amount of emission or efuent as a negative ow sheet. From these gures it is obvious that there is a signicant improvement in reduction of VCM emission form PVC plant during these years. The main souses of VCM emission in 1970s were (1) VCM in the dryer exhaust gas, (2) VCM purging with inert gas and (3) VCM leakage during manhole open operation. Amount of VCM emission from each source has been reduced by the different technologies, which are described in the following sections. 8.3.1. Removal of residual VCM Although in the early stage of investigation of counter measure for the dryer exhaust gas, various technologies were tested, such as adsorption of VCM by active carbon, incineration and others. But these were not effective or economical way because of large volume and humidity of exhaust gas. Then
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Fig. 41. Negative ow sheet of suspension PVC process. Upper: 1970s; lower: (Gothic gure): 1990s. Reprinted with permission from Y. Saeki q1979 Y. Saeki [185].
reduction of VCM in the dryer exhaust gas both of suspension and emulsion process is achieved only by stripping of VCM from slurry or latex prior to drying. 8.3.1.1. Diffusion coefcient. It is essential to understand properly the mechanism of diffusion of VCM in PVC particle for development of stripping technology. Berens of the B.F. Goodrich is a pioneer and has done many important works in this eld [186 189]. He clearly explained the mechanism of diffusion of VCM in PVC particles both of suspension and emulsion process. At very low relative VCM pressure, the sorption and de-sorption of VCM by PVC was found to follow simple Fickian kinetics ! 1 Mt 6 X 1 24Dn2 p2 t 12 2 exp 13 M1 p n1 n2 d2 where Mt is the weight of VCM entering or leaving the sphere in time t; M1, the total weight change between initial and nal uniform concentrations and d is the sphere diameter. If t0.5 is the time when Mt =M1 0:5; Eq. (1) gives D 7:66 1023 d2 t0:5 14
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Thus knowing d, D can be obtained experimentally from half sorption of de-sorption times, provided the diffusion is Fickian. Berens obtained D 1:9 10212 cm2/s at 25 8C, from measuring sorption for a mono-disperse emulsion PVC of 0.44 mm particle diameter. For suspension PVC, d is not a diameter of PVC grain but of primary particle obtained from specic surface area measured by nitrogen adsorption. Sorption data of suspension PVC with primary particle diameter of 1.85 mm gives diffusion coefcient D 2:0 10212 cm2/s, which is in very good agreement with a mono-disperse emulsion PVC. This means that diffusion of VCM through the pore and through pericellular membrane around the particle must be very rapid. Berens obtained D 1:9 10212 cm2/s at 25 8C, from measuring sorption for a mono-disperse emulsion PVC of 0.44 mm particle diameter. For suspension PVC, d is not a diameter of PVC grain but of primary particle obtained from specic surface area measured by nitrogen adsorption. Sorption data of suspension PVC with primary particle diameter of 1.85 mm gives diffusion coefcient D 2:0 10212 cm2/s, which is in very good agreement with a mono-disperse emulsion PVC. This means that diffusion of VCM through the pore and through pericellular membrane around the particle must be very rapid. Berens also investigated the temperature dependence of the diffusion coefcient from half sorption and de-sorption time at temperatures from 25 to 110 8C for various PVC samples. An activation energy of diffusion coefcient was determined as 17 kcal/mol from an Arrhenius plot. Then the diffusion coefcient D can be expressed as function of temperature T as follows: D 3:7 exp217 000=RT 15
8.3.1.2. Slurry stripping technology for suspension process. The experimental data of slurry stripping at elevated temperature are shown in Fig. 42. Residual VCM was measured by changing residence time at different temperatures for medium molecular weight (average polymerization degree: 1050, K value 66) and low molecular weight (average polymerization degree: 750, K value 57). These results show good agreement with the data of Berens. PVC of low molecular weight is relatively difcult to remove VCM. This can be explained by larger size of primary particle of low molecular weight PVC. The most difcult and important aspect of slurry stripping is the prevention of color change or deterioration of heat stability of product caused by excess heat treatment. A number of patents have been applied in this eld. Many kinds of design were proposed in these patents. Judging from the license results, however, stripping column system is the best. In common case, the PVC slurry is fed from the top of the column, which consists of many perforated tray and steam is fed from the bottom. Key point of major number of these patents exist in how to improve the sharpness of residence time of slurry in the heated zone to avoid excess heat treatment [190]. One of such example patented to Chisso Corporation, Japan is shown in Fig. 43. Each tray has channel for forcing slurry path long like a rivulet. Loop pipe for cleaning the back of tray by hot water is equipped to each tray [191 193]. There are many other patents [194 202]. As shown in Fig. 41 by introducing effective stripping system, residual VCM in the slurry, which is almost all exhausted from dryer, has been dramatically reduced from 1500 to 45 g for 1 t of PVC product. 8.3.1.3. Stripping of latex for emulsion process. To solve environmental problem the technology for VCM removal from latex, prior to the spray drying step, is very important. In theory, because of the small size of the PVC latex particles, the removal of VCM from such polymers should proceed at a high
2123
Fig. 42. Slurry stripping at elevated temperature.
rate. It is, however, very difcult to remove VCM from latex, because of foaming trouble caused by the presence of anionic emulsiers and coagulation trouble caused by weak stability of latex. In the case of suspension process the effective stripping systems, mainly column system by counter current steam treatment for slurry, have been already developed. It is therefore difcult to apply such stripping systems for slurry to latex as it is, because of severe foaming trouble. Many attempts for VCM removal from latex have been done, such as: 1. Heating of latex by steam in the vessel, column or rotating drum under vacuum condition. 2. Babbling of latex by inert gas or vapor of organic solvent. 3. Complete polymerization of VCM by introduction of co-monomer and initiators after polymerization. Among these methods (2) and (3) are not commercially applicable. There are many patent issue for the latex stripping [203 205]. One example of method (1) is explained by US patent [204]. The dispersions (latex) are sprayed against the wall of the evacuated vessel by means of at least one spray nozzle. Mean diameter of sprayed latex is controlled from 0.05 to 3 mm. The sprayed latex makes thin lm on the wall of vessel and runs down the wall. By keeping the pressure in the vessel lower than the saturation pressure of water in the latex by 200 500 mm Hg, foaming is suppressed. There are many resembling patent applications. The key point of suppressing foam and preventing coagulation caused by dry up of wall may exist in spraying condition and pressure control as described in the above patent.
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Fig. 43. Chisso slurry stripping system.
8.3.1.4. VCM removal from bulk PVC. In V 50 process, as described before, there is no special apparatus for removing residual VCM from the product, such as slurry stripper for suspension process. The removing of residual VCM is conducted in the vertical second stage reactor. Without the presence of heat transfer medium like water, it is difcult heat up PVC particles in the case of bulk process. Powder form PVC is mixed by agitator systems and heated from jacket. By the several cycles of pressurizing by nitrogen and evacuation through vacuum line, removal of residual VCM is attained. To improve efciency of removal of residual VCM, addition of small amount (from 0.01 to 0.8%) of water is proposed [142]. Fisher investigated adverse effect of remaining polymer on the removal of residual VCM by testing intentional addition of PVC powder prior polymerization. As mentioned above, remaining polymer may convert to vitreous particle during the next polymerization batch. In the case of vertical second stage reactor equipped with automatic devices of pressurized hydraulic cleaning, together with good temperature control, very effective degassing is achieved as shown in Fig. 44. 8.3.2. Other technology for reduction of VCM emission 8.3.2.1. Inert gas treatment. Second largest amount of VCM emission was VCM in the exhaust gas from the VCM recovery section. In 1970s, this VCM emission was assumed to be 1200 g/t PVC. Since the polymerization reaction is stopped at conversion of around 80 90% in commercial plant, 10 20% VCM is evacuated from the reactor. Recovered VCM is treated in the VCM recovery section and recycled to the polymerization section as shown in Fig. 41.
2125
Fig. 44. VCM removal from bulk PVC. Reprinted with permission from J Vinyl Technol 1984;6:35. q1984 Society of Plastics Engineers [146].
From the storage drum of recovered VCM the inert gas must be purged periodically to the atmosphere to reduce the pressure of the drum. In such purge operation some amount of VCM is exhausted with inert gas. For recovering such VCM emission from the VCM recovery section, the absorption technologies by solvent or active carbon are developed. For the solvent absorption technology, two different solvents are applied, one is solvent with low boiling point, such as gasoline or kerosene, the other is chemicals with very high boiling point, such as plasticizer. For the active carbon technology, there are mainly two different processes, one is for dilute VCM gas and the other is for thick VCM gas. As shown in Fig. 41 by introducing effective absorption system for the VCM recovery section, VCM emission has been dramatically reduced from 1200 to 8 g/t PVC. 8.3.2.2. Closed operation. VCM from the manhole was also important emission source and estimated at about 700 g/t PVC in 1970s. At that time the manhole was opened every batch for charging chemicals or reactor cleaning. The amount of VCM escaping from polymer deposit on the reactor wall was signicantly large. As described in Section 5.4, by development of clean wall technology consists of
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Fig. 45. Typical ow sheet for 1990s of suspension PVC process. Incorporated facilities for reduction of VCM emission.
automatic water jet cleaning system and scale prevention technology, the necessity of the opening of manhole has been almost perfectly eliminated. 8.3.2.3. Efuent water treatment. Main sources of water efuent from the suspension process are drainage from the decanter, reactor cleaning and seal water for compressor. By steam stripping in the column, VCM in the efuent water can be recovered. In Fig. 45, ow sheet of the suspension process incorporated above mentioned system for reducing VCM emission is shown as the typical process for 1990s. The development in emission control technology during decades is obvious in comparison with those of 1970s (Fig. 12). 9. Concluding remarks Annual growth of the world PVC consumption is around 5%. In developing countries PVC consumption per capita is 1 kg and less than one tenth of those of developed countries. PVC is the essential material for construction of infrastructure of these developing countries. Aiming more efcient plant, the process for PVC production has been continuously improved as mentioned above. Batch operation process is normally inefcient than continuous process. But with aid of computer control in combination of the perfect scale prevention technology, the recent suspension polymerization
2127
process for PVC production is, in the sense of productivity of whole plant, almost equivalent with continuous one. Acknowledgements The authors would like to thank Teruyuki Suzuki for drawing of ow sheets and comments on scaleup technology; Shin Dai-Ichi Vinyl Corporation for permission to publish this article.
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Y. Saeki, T. Emura / Prog. Polym. Sci. 27 (2002) 20552131 Nakagawa M, Bujo A, Koyanagi S, Arai S, Kiyono J. Kagaku Kogaku 1973;37:557 64. Koyanagi S, Kitamura H. Petrotech 1978;1:378 83. Koyanagi S. Nikkakyo Geppo 1981;34(7):37 44. Asano K. In: Saeki Y, Omi S, editors. New production processes of polymers. Tokyo: Kogyo Chosakai Publishing; 1994. p. 59 82. Research report of Chemical Engineering Study Club. Application of computer to production processes of polymers (1). Japan: Society of Polymer Science; 1983. Research report of Chemical Engineering Study Club. Application of computer to production processes of polymers (2). Japan: Society of Polymer Science; 1985. Macoveanu M, Nagacevschi V, Feldman D. Die Ange Makro Chemie 1977;64:19 28. Nilsson H, Silvegren C, Tornell B. Br Polym J 1981;13:161 4. Fowler JR, Harvey DJ. Chem Engng Prog J 1978;74:61 6. Kennedy JP. AIChE Ind Process Control Proc Workshop (CONF, PROC) 1979;18 23. Miura N, Imaeda M, Hashimoto K, Wood RK, Hattori H, Onishi M. J Chem Engng Jpn 1998;31:626 32. Havlena H, Barva P. Proceedings of the IEEE International Conference on Control Applications, Hawai, August. Kato N. Kagaku Kogaku 1993;57:338 40. Wakabayashi K, Shimizu M, Yoshimura K, Nakamura M, Kamiya S, Yamakawa M, Ohno H. Anzen Kogaku 1983;22: 145 54. Japanese Examined Patents 43-2,464, 43-2,465, assigned to Pechniey Saint-Gobain; 1968. Krause A. Chem Engng 1965;Dec 20:72 4. Thomas JC. Technical Conference of Society of Plastics Engineer, Detroit; May 1967. Thomas JC. SPE J 1967;23(10):61 5. Thomas JC. Hydrocarbon Process 1968;47(11):192 6. Eur Chem News 1968;Sep 27:54 5. Saeki Y. Production processes of polymers. Tokyo: Kogyo Chosakai Publishing; 1971. p. 170 7. Allsopp MW. Bulk process for the manufacture of PVC. In: Burgess RH, editor. Manufacture of processing of PVC. London: Applied Science Publishers; 1982. p. 39 61. Langsam M. In: Nass LI, Heiberger CA, editors. Encyclopedia of PVC, 2nd ed. New York: Marcel Dekker; 1985. p. 12738. Eur Chem News 1979;Sep 3:24. Anonymous. Elastomerics 1980;3:26 8. Fisher N. J Vinyl Technol 1984;6:35 49. Fisher NJ, Goiran L. Hydrocarbon Process 1981;60:143. British Patent 1,506,981, assigned to Rhone-Poulenc; 1976. US Patent 4,198,376, assigned to Rhone-Progil. US Patent 4,277,585, assigned to Rhone-Progil. Chung ST, Jung SH. J Vinyl Additive Technol 1996;2(4):295 303. Guyot H. Plast Mod Elastomere 1983;35(8):29 30. Jambon C. Oil Gas J 1984;82(11):60 1. Evans DEM. The manufacture of PVC paste and emulsion polymers. In: Burgess RH, editor. Manufacture and processing of PVC. London: Applied Science Publishers; 1982. p. 63 81. Tester DA. In: Burgess RH, editor. Manufacture and processing of PVC. London: Applied Science Publishers; 1982. p. 258 69. Langsam M. In: Nass LI, Heiberger CA, editors. Encyclopedia of PVC, 2nd ed. New York: Marcel Dekker; 1985. p. 13853. Igarashi T. Processing of PVC paste. Tokyo: Rubber Digest; 1998. p. 36 50. Tomishima Y. Kagaku Sochi 1996;37(8):49 54. Japanese Examined Patent Sho40-19,591, assigned to ICI; 1965. Lukas R, Paleckova V, Mrazek Z, Kolinsky M. Int Polym Sci Technol 1982;9(11):T66 9. Fischer N, Boissel J, Kemp T, Eyer H. British Patent 1,435,425, assigned to Rhone-Progil; 1974. Kemp T. British Patent 1,503,247, assigned to Rhone-Poulenc; 1976. Dewald RC, Hart LH, Carroll WF. J Polym Sci, Polym Chem Ed 1984;22:2923 30. Evans DEM, Robson E. British Patent 1,458,367, assigned to ICI; 1976.
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Prog. Polym. Sci.

Technical progresses for PVC production

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Table 3 Development of VCM and PVC Technologies in Japan [8]

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Fig. 7. High temperature direct chlorination process.

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462 578 139 105 0.22 175 660 4

462 585 131 110 0.05 0.2 150 700 4

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Fig. 11. Lummus VCM direct process from ethane.

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Fig. 12. PVC suspension polymerization process in 1970s.

Fig. 13. General prole of suspension polymerization reaction.

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Degree of hydrolysis (%)

71.5 73.5 76 79 71 73 71 75 78.5 81.5 54 57 55 45 51 50

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Plasticiser take up (%) 18.0 25.2 19.5 20.5 16.6

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23.0 23.9 23.5 22.8 23.1 21.0 28.1

11.1 8.4 10.1 9.5 9.5 8.4 8.5

38.9 108.0 81.0 28.7 31.0 31.2 42.9

1.69 3.31 2.70 1.40 1.75 1.45 4.00

7.2 6.8 7.1 6.4 6.9 6.4 3.8 70 56

0.21 0.15 0.17 0.19 0.16 0.18 0.30

180 180 180 180 180 180 180

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below d50 P 875 V  20:6 X  20:67 S 4

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Table 14 Mechanism of scale prevention [72]

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2000 [94] 0.5 4.0 0.5 0.5 5.5

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below d50 P 875 V 20:6 X 20:67 S 4