LIFE CYCLE RISK ASSESSMENT APPLIED TO CHEMICAL AND BIOTECHNOLOGICAL PRODUCT PROCESSES

M. DEL BORGHI*, L. CIRAOLO**, A. MACCHIAVELLO* and A. DEL BORGHI* * Institute of Chemical and Process Engineering G.B.Bonino, University of Genoa, Via Opera Pia 15, 16145 Genoa, Italy ** Institute of Commerce Technology, University of Catania, Corso Italia 55, 95129, Catania, Italy

INTRODUCTION

There is no doubt that the modern technology has the potential for creating less pressure on the environment, by reducing/avoiding emissions of pollutants, production of wastes and energy/resources consumption. For instance, the research of new processes for power generation is stressed in order to reduce dramatically pollutant emissions into the atmosphere. In the meantime, a partial but important result is obtained in reducing as much as possible the energy consumption or by recycling materials requiring a large amount of energy to be produced (i.e. glass). In the field of the plant technology and chemical processes, some general trends in the future are the followings: use of continuous reactors and continuous processes with reactions in gaseous or vapour phases (less releases and in gas or vapour form); choice of reaction at high conversion and selectivity (minimisation of residues); choice of reactions giving by-products easily recyclable; reduction of temperature and pressure conditions by employing new catalysts; limitations of raw materials and intermediates number; adoption of biological process instead of chemical process in case of difficulties of chemical synthesis or in case that the process gives less pollutants or by-products. The first approach to select a sustainable technology to produce any kind of goods is to make a deep analysis among the available production processes in terms of raw materials, energy, environmental impact due to atmospheric, liquid and solid emissions, hygienic and hazard aspects, potential risks. The above analysis is discussed in the following.

DEFINITIONS OF LCA (LIFE CYCLE ASSESSMENT) AND LCRA (LIFE CYCLE RISK ASSESSMENT)

The choice of the best technology to produce a good can be made in several ways but the recent and more rational is the so called LCA, the Life Cycle Assessment [1]. (Environmental) Life Cycle Assessment is defined as a process to identify, quantify and assess the (environmental) impacts caused by a product through its entire life (from cradle to grave). Traditionally, LCA considers only the environmental aspects caused by normal routine operation of the system. Recently, a

methodological framework to perform accidental risk in LCA practice, called LCRA (Life Cycle Risk Assessment), has been proposed.

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3 LCRA definition is quite similar to LCA definition. Life Cycle Risk Assessment is a process to identify, quantify and assess the risk caused by a product throughout its entire life cycle. In our opinion, both the assessments are necessary in identifying a sustainable technology among different possible technologies to produce a good and LCRA is comprehensive of both. Generally four phases can be distinguished as well in risk assessment as in life cycle assessment-it methodologies, such as: goal definition and scooping; inventory analysis (system description; inventory of energy and raw materials use and emissions; inventory of risk analysis); impact assessment including risk assessment; improvement assessment and risk reduction.

CHEMICAL PRODUCTION AND BIOTECHNOLOGICAL PRODUCTION

In principle the adoption of a biotechnological process as alternative to a chemical one gives better results in terms of environmental and risk impacts [2]. The advantages of biological processes are: adoption of renewable raw materials; huge variety of reactions; milder processing conditions; effluents of biological nature. specific selectivity; The disadvantages are: several raw materials are available only seasonally; products are obtained in diluted aqueous solutions; many organic substrates have low solubility and are toxic for micro-organisms; the costs are not ever competitive; necessity of product purification.

The scheme of a general biological process is very simple. The chemical process generally is more complex. Generally, biotechnology is characterized by positive environmental expectations. The production is carried out with relatively low energy consumption and the exhaustible raw materials for the production will be partly or mostly exchanged to renewable biological materials. On the other side, there are the negative expectations caused by the possibility of damage caused by the accidental release or careless disposal of new type of organisms or genetically engineered releases into the environment. So, it is important also for biotechnology processes to set up a technology assessment including risk assessment (LCRA).

4 4.1

EXAMPLE OF LCRA APPLIED TO ETHANOL PRODUCTION Goal definition and scooping

As well known, ethanol production has been increased in the last years because of its use in addition to gasoline to increase octane number or, in certain cases, substitutes completely or in part gasoline for motor vehicles. Ethanol is an example of good that can be produced by chemical or fermentation way. In the following we consider three type of processes to obtain ethanol and we apply to every one the LCRA, in order to understand which is the process that can be considered as sustainable technology. 4.2 Inventory

4.2.1 Indirect Hydration Gas containing ethylene with a C2H4 percentage variable from 35% to 95% reacts in adsorption towers at 55-80C and 10-35 bars with sulphuric acid with H2SO4 percentage varying from 94 to
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4 98%; eventually, the reaction is catalysed by Ag2SO4. The reaction is exothermic and gives monoand diethylsulphate. Both esthers are hydrolysed to ethanol in towers with antiacid coating at 70100C. During the hydrolysis at high temperatures, the by-product diethylether is obtained. The sulphuric acid is later concentrated from 50 to 98%. The process efficiency is of 86 %.
Figure 1 - Ethanol Production: From Ethylene by Esterification and Hydrolysis
Fuel Gas Sodium Hydroxide Solution Ethyl Ether Ethyl Alcohol (95%)

Sulphuric Acid 90% Absorption Tower Ethylene Stripping Column Ether Column Steam Fractionating Column

Hydrolyzer

Scrubber

Spent Caustic Water Diluted Acid Water Concentrator

4.2.2 Catalytic hydration of ethylene The catalytic hydration of ethylene is an heterogeneous process in gaseous phase on acid catalyst, where the catalyst is H3PO4, T = 300C and p = 70 bars. The ethylene conversion is only of 4% per passage. The reaction gas is recycled many times to increase total efficiency. The ethylene has to be of high purity to avoid inert gases concentration. The reaction gas is cooled to condense the liquid products and separate it from the ethylene to be recycled. Ethanol solution is concentrated and purified by extractive distillation. The ethanol selectivity is about 98%.
Figure 2 - Ethanol Production: from Ethylene by Catalytic Hydration
Bleed-Off Recycle Ethylene Phosphoric Acid Water Condenser

Ethylene Heater Water

Reaction Tower Separator

Scrubber Steam

Stripper

Caustic Soda Solution Waste Water Ether and Low Boilers Hydrogen

Separator Purification Column Column

Hydrogenator

Ethyl Alcohol

Waste

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5 4.2.3 Ethanol fermentation A distinction must be made from raw materials. Those which are specifically grown for ethanol production (sugar substrates such as sugar beet, fodder beet, sugar cane...; starch products such as potatoes; Jerusalem artichokes) and the residues: industrial and food processing wastes (waste sulphite liquors, whey, food industry wastes); agricultural and domestic residues. A different treatment is necessary, of course, to prepare the culture broth with different energetic and environmental impact. Once the culture broth is prepared, the process is common. The resulting wine, at a maximum ethanol concentration of about 10% by volume is decanted and centrifuged to separate the non fermentable matter and the yeasts. The obtained liquor is distilled, rectified and dehydrated to obtain absolute alcohol. The scheme of the process is illustrated in Figure 3.
Figure 3 - Ethanol Production: from Sugar by Catalytic Hydration
Water

Molasses

Water Carbon Dioxide Aldehydes Scrubber Condenser

Sulphuric Acid

Mixing Tank Ethyl Alcohol (95%)

Fermenter Ammonium Sulfate Beer Sterilizer Beer Still Yeast Culture Machine Yeast Tub Water Benzene Fuse Oil Water Aldehyde Column Rectifying Column

Slop

Anhydrous Column

Ethyl Alcohol (absolute)

4.3

Inventory of raw materials and energy consumption

4.3.1 Indirect Hydration The indirect hydration uses as principal raw material ethylene from different sources: coke production, cracking gas of ethane/propane mixtures, cracking gas of heavy gasoline or nafta. The gases have to be enriched in ethylene and made free from superior olephines. The natural resources necessary to produce ethylene are: natural gas (18 Nm3/kg ethanol), petroleum (11.6 kg/kg ethanol), carbon (100 kg/kg ethanol). The others raw materials are sulphuric acid and the sulphur (0.07 kg/kg ethanol) or pyrites (0.03 kg/kg ethanol). During the process a small quantity of NaOH and water are used. As far as energy consumption is concerned, it is necessary to consider the following steps. 1 - ethylene production; 5 - compressing ethylene; 2 - sulphuric acid production; 6 - distillation of ethanol; 3 - concentration of ethylene; 7 - concentration of sulphuric acid. 4 - heating ethylene and sulphuric acid; The total energy consumption can be calculated in about 29 MJ/kg.
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6 4.3.2 Direct Hydration The raw material used in direct hydration is only ethylene at high concentration (>97%). The ethylene sources are limited to the natural gas cracking (18 Nm3/kg ethanol) and petroleum cracking (11.6 kg/kg ethanol) to reduce the concentration expenses. The only other raw material is water (13.4 kg/kg ethanol). The reaction is catalyzed by H3PO4 supported on porous material. The consumption of catalyst is small and consequently small are the natural source consumption of tricalcium phosphate and NaOH neutralizing H3PO4 effluents. As far as energy consumption (= 26MJ/kg) is concerned, the following steps have to be considered: 1 - ethylene production; 5 - heating and compressing ethylene; 2 - ethylene concentration; 6 - pumping gases; 3 - phosphoric acid production; 7 - distillation of ethanol. 4 - NaOH production; 4.3.3 Fermentation As mentioned, the raw materials for ethanol fermentation are various: i.e. sugar substrates (fodder beet, sugar cane, etc.), starchy products, cellulose material, industrial residues. For our study we consider only the case of (fodder beet) molasses: sugar beet (95.0 kg/kg ethanol) and sugar beet molasses (3.024 kg/kg ethanol). Other materials and utility requirements are sulphuric acid (0.025 kg/kg ethanol) and ammonium sulphate (0.002 kg/kg ethanol) with a very reduced consumption of natural sources and water(12,600 kg/kg ethanol). As far as energy consumption is concerned (= 21MJ/kg), the following steps have to be considered: 1 - operation of agricultural machinery; 4 - preparation of worth; 2 - irrigation; 5 - fermentation; 3 - chemical products 6 - distillation. 4.4. Inventory of emissions [3]

Table 1. Comparison among various processes to produce 1000 kg ethanol Indirect hydration Direct hydration Fermentation of beet molasses Raw materials and involved land Petroleum Petroleum Sugar beets 11,600 kg (4,06 ha) 10,000 kg (3,50 ha ) 95,000 kg (1,87 ha) a) Energy consumption 15,000 MJ 12,930 MJ 10,800 MJ Raw materials production: 14,000 MJ 11,000 MJ 10,200 MJ Process: b) Air pollution - Raw materials production: 17.6 15.1 SOx (kg) 3.1 2.6 NOx (kg,) 76 63.3 CO (kg) 15.8 13.5 Organic compounds (kg) 9.6 2.7 Dust (kg) - Process (Before control): 40 H2SO4 (kg) 170 70 6.8 Organic compounds (kg) c) Water pollution 128,000 110,000 6,000 Raw materials (eq. popul.): 8,000 8,000 14,000 Process (eq. population): d) Solid wastes small small small (generally are recovered)

4.5

Inventory of risk and hygiene hazards [4]

In Table 2 a comparison among the various processes, on the basis of a qualitative risk analysis and hygienic hazard analysis, has been made.
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Table 2 - Inventory of risks and hygienic hazards. Indirect Hydration Direct Hydration Raw materials production: fire explosion hygienic hazard Process: a) Reaction: fire explosion hygienic hazard b) Distillation: fire explosion hygienic hazard *** high risk ** medium risk *** *** ** *** *** **

Fermentation * *

** ** *** * * * * low risk

*** *** ** * * * - no risk

* * * *

The major risks connected with the production of ethanol from indirect hydration are due to the flammability of ethylene and to the possibility of formation of explosive mixtures. Also the ethanol vapours during the distillation represent a risk source of fire or explosion. The concentration of sulphuric acid can cause formation of SO3 clouds in case of a damage to the boilers. As far as the health hazards are concerned, the following possibilities are detectable. The major risks connected with the process are due to danger of fire and explosion of ethylene and mixtures. Other risks are due to high temperatures and pressures in the reactor, which have to be controlled accurately. In the refining section too the danger is due to the flammability of ethyl alcohol and diethyl ether. Practically no risks are connected with fermentation processes, with the exception of those deriving from the distillation. In fact, only in that section the ethanol concentration can be dangerous because of the flammability of the mixture. Health hazards are individuated only in the possible exposition to carbon dioxide during the fermentation and to the ethanol vapours in distillation section.

CONCLUSIONS

A semi-quantitative LCRA analysis applied to the ethanol production shows that the biotechnological process presents the minor risk for the employees and the population, as well as the minor environmental impact from both pollution and resource conservation viewpoints. The future research will be in the sense of optimizing the process, by increasing the productivity (immobilized enzymes, entrapped cells [5], reducing environmental aspects, particularly due to liquid emissions (purification and recycling of culture broth) [6]. The paper represents a first approach to LCRA problems connected -with ecotech. Researches are in progress to deeply analyze the various aspects.

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[1] [2] [3] [4] [5]

REFERENCES
Vigon B W, Harrison C L et al., 1993. Life Cycle Assessment: Inventory guidelines and principles, United States Environmental Protection Agency, EPA/600/R-92/245, Feb., 1993. European Foundation for the Improvement of Living and Working Conditions, 1987. The impact of biotechnology on the environment, Dublin., Ireland, pp. l-11. Handbook of Environmental Control, 1974. Air Pollution, Vol. 1, CRC Press, Cleaveland. Cralley L V, Cralley L J, 1989. In-plant practices for job related health hazard control. Production Process, Vol. I, John Wiley & Sons, USA. Del Borghi M, Converti A, Parisi F, Ferraiolo G, 1985. Continuous alcohol fermentation in an immobilized cell rotating disk reactor. Biotechnol. Bioeng., 27, 761-768.

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[6] Converti A, Perego P, Lodi A, Fiorito G, Del Borghi M,. Ferraiolo G, 1991. In-situ ethanol recovery and substrate recycling during continuos alcohol fermentation. Bioproc. Eng., 7, 3-10.

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