Resources, Conservation and Recycling, 10 (1994) 1-9

Elsevier Science B.V.

Recycling of spent hydroprocessing catalysts: EURECAT technology

G. Berrebi, P. Dufresne* and Y. Jacquier
EURECAT- European Reprocessing Catalysts, Quai Jean Jaurbs, 07800 La Voulte sur Rh6ne, France

ABSTRACT Disposal of spent catalyst is a growing concern for all refiners. Environmental regulations are becoming stricter and stricter and there are State recommendations to develop disposal routes which would emphasize recycling as much as possible, and processing the wastes as near as possible to the production center. In this context, EURECAT has developed a recycling process for the hydroprocessing catalysts used in the oil refineries (NiMo, CoMo, NiW on alumina or mixed alumina silica). The process starts with a regeneration of the catalyst to eliminate hydrocarbons, carbon and sulfur. After a caustic roasting, the material is leached to obtain a solution containing mainly molybdenum (or tungsten) and vanadium, and a solid containing essentially alumina, cobalt and/or nickel. Molybdenum and vanadium are separated by an ion exchange resin technique. The solid is processed in an arc furnace to separate the alumina. Nickel and cobalt are separated by conventional solvent extraction to obtain pure metal. Alumina is disposed of as an inert slag. The strength of the process lies in the combination of proven technologies applied by companies whose reliability in their respective field is well known. The aspects concerning spent catalyst handling, packaging and transport are also discussed.

S P E N T CATALYSTS A N D A D S O R B E N T S

Oil refineries, as other major industries, generate different types of wastes - liquid or solid - which must be handled in accordance with today's environmental regulations. The solid wastes are essentially spent chemicals, contaminated soils, catalysts and adsorbents [ 1 ]. Fluid cracking catalysts, hydroprocessing catalysts, precious group metals catalysts and polymerisation catalysts comprise the bulk of spent refinery catalysts. Spent adsorbents are aluminas, molecular sieves, charcoals and clays. Various technologies are available to refiners for handling these solid wastes: regeneration for catalysts or adsorbents reuse or metals reclaiming, use of spent catalyst as a secondary raw material, disposal for land farming or land filling. The choice of a given option depends upon the type of catalyst and its chemical composition, process economics, applicable waste regulation and considerations about future liability for potential post-disposal environmental damage. Refinery operators con*Corresponding author.

0921-3449/94/$07.00 1994 Elsevier Science B.V. All rights reserved.

G. BERREBIET AL.

sider today that solutions involving land farming or land filling will concern fewer and fewer products and that recycling is the best alternative whenever possible.
HYDROPROCESSING CATALYSTS

Hydroprocessing catalysts are used in oil refineries for two main applications: desulfurisation and cracking of various petroleum cuts [2 ]. The first application is becoming more and more important with the more stringent regulations applied and predicted for the sulfur content for diesel and fuel oil [3,4 ]. The annual consumption of hydroprocessing catalysts is estimated to be about 45 000 t, which is therefore the annual production of these wastes (expressed on a calcined basis) [ 5 ]. One must first define the term 'spent catalyst': the hydroprocessing catalyst loaded in a reactor deactivates as a function of time on stream for two main reasons, viz. fouling by carbonaceous deposits (coke) or by inorganic type materials [6]. A typical cycle length is one or two years. The so-called coke can be removed by controlled combustion outside the reactor. This off-site regeneration, which is one of the major activities of EURECAT, can be practised once or twice on a given batch of catalyst, and the regenerated material is reloaded into the reactor as a fresh material. Usually after 2 or 3 cycles, the catalyst cannot be reused any more because of loss of its catalytic and/or mechanical properties. On the other hand, the hydroprocessing catalysts which are especially dedicated for heavier feeds upgrading are often not reusable for a second cycle: they are poisoned by vanadium and nickel sulfides originating from the decomposition of organometallic compounds contained in the crude.
METAL CONTENT OF SPENT CATALYSTS

The hydroprocessing catalysts are typically made of molybdenum or tungsten oxides associated with nickel or cobalt oxides on a support, usually gamma alumina [ 7 ]. Systems with cobalt and molybdenum are used when the main objective is desulfurisation of the petroleum cut, and the associations nickel/ molybdenum or nickel/tungsten are used for hydrogenation or hydrocracking purposes. In this last application, alumina is partly replaced by silica alumina-based materials. Spent catalysts contain some carbon, usually 5-25% (w/w) sometimes more, and sulfur, as the active phase is a mixed Co (Ni)Mo (W) sulfide. The quantity of sulfur is highly dependent upon the amount of metal contaminants such as vanadium and nickel trapped during the processing of heavy cuts [ 8 ]. Other typical contaminants are iron, originating from corrosion of tanks, pipes and heat exchangers; lead due to a pollution by leaded gasoline; silica from the decomposition of anti foaming agents; arsenic which exists in small concentrations in specific crudes. Table 1 lists

RECYCLING OF SPENT HYDROPROCESSINGCATALYSTS TABLE 1 Typical analyses of spent hydroprocessing catalysts, expressed on a calcined basis in % ( w / w ) Catalyst type A1 Mo V Ni Co W Pb Si Fe As P Na A CoMo 35 8.8 1.2 0.3 3.2 < 0.05 < 0.05 0.5 0.21 < 0.05 <0.05 0.2 B NiMo 33.1 12.3 0.05 2.60 <0.04 < 0.05 < 0.05 0.30 0.12 < 0.05 3.2 0.03 C NiW 17.7 0.47 <0.04 2.5 <0.05 15.2 < 0.05 13.2 0.18 < 0.05 0.2 0.04 D CoMo 32.5 6.4 2.6 0.49 1.6 < 0.05 < 0.05 0.29 0.29 0.20 <0.05 0.13 E CoMo 28 6.2 10.5 3.1 2.1 < 0.05 < 0.05 1.2 0.7 0.4 0.05 0.5

the chemical analysis of typical hydroprocessing catalysts.Catalysts A, D are C o M o type catalysts slightlypoisoned by nickel and vanadium, while E is more heavily loaded with these contaminants. Catalyst B is a typical N i M o type hydrogenation catalyst containing phosphorus from its manufacturing process. Catalyst C is a N i W hydrocracking catalyst containing a silicaalumina support.
EURECAT'S PROCESS

EURECAT's main activities are entirely devoted to catalyst business: preconditioning of catalysts before use (presulfiding, prereduction), regeneration after the first or second cycle by carbon and sulfur burn-off, and then recycling by complete metal recovery. EURECAT has been involved in these three off-site catalyst services for the past ten years and is currently revamping and expanding its metal reclaiming facilities in its French plant of La Voulte. The recycling process described in Fig. 1 has been designed for a complete recycling of metals. It uses a combination of hydrometallurgical and pyrometallurgical steps. The spent catalyst is first of all screened to eliminate ceramic inert balls mixed with the catalyst during the reactor unloading. The material is then directed to a regeneration furnace in order to eliminate the carbon. The amount of free hydrocarbons is usually less than 5 wt%, but can be higher in some special cases and then the material requires a prior stripping treatment. Coke content is usually 5 to 20 wt% (expressed in carbon), but can be up to 30%. The metals, such as Mo, W, Ni, Co, V, Fe, which are chemically in the sulfide form in a spent catalyst, are transformed into the

4 loTs (~i/mln)
' 'HEAT #LOW (mt'cPoV) 30~0 EXO

G. BERREBI ET AL.

'TS m f OI

-0.2

I 200

-'5

t50

I
'A -t0 1
-t5

-0.4

tO0

-50 -0 R 50 t00 150 200 250 300 350 400 TEMPERATURE (C) ~ 600 _~

450

500

Fig. 1. Flow scheme of the recycling process of spent catalysts.

corresponding oxides during the regeneration process. This transformation takes place at a moderate temperature (220-270C) whereas coke combustion is completed at a higher temperature (420-480 C ). The analytical technique of thermogravimetry (TG) associated with differential thermal analysis (DTA) characterizes this 2-step transformation as illustrated in Fig. 2. The regenerated catalyst, which contains usually less than 0.5% (w/w) of carbon, is impregnated by caustic soda and roasted in an oven to achieve the chemical combination of the soda and the metals. The solid is then leached by hot water in order to remove metals such as molybdenum, tungsten, vanadium, arsenic and phosphorus. Nickel, cobalt and iron and most of the alumina are not extracted. Leaching is carried out continuously and in countercurrent in a series of 12 tanks by percolation. This original percolation technique designed by EURECAT seems to be the most efficient as far as molybdenum and vanadium extraction yields are concerned. The leaching parameters (pH, concentration, liquid/solid ratio, potential redox, residence time, flow rates, etc. ) are adapted to the catalyst type to get the highest yields of metal extraction and avoid dissolving too much alumina. After filtration, two products are obtained: ( 1 ) a solid containing alumina, silica, cobalt, nickel, a small concentration of iron as well as traces of molybdenum or tungsten, vanadium; and (2) a solution containing molybdate or

RECYCLING OF SPENT HYDROPROCESSING CATALYSTS

Spent cotalyst

1
/
Alkaline solution AI, Mo,V, P,As

-....
Solid AI,Si, Ni,Co

A I , P . A s ~ I ~ I Purification

IbSlag: AI

Solution Mo,V

Moire Ni.Co

I Sepo o ion L
Mo V

[ Se o otioo I
Ni
Co

Fig. 2. Air regeneration of a spent hydroprocessing CoMo catalyst: differential thermal analysis (DTA) and thermogravimetry ( TG and DTG).

tungstate, vanadate, as sodium salts and impurities such as arseniate, phosphate and small amounts of alumina and silica. With the treatment of the solution, the target is to obtain pure molybdenum, tungsten and vanadium compounds from the alkaline solutions which contain a substantial quantity of impurities. The method chosen is to separate the molybdenum/vanadium or tungsten/vanadium by means of ion exchange resins. This technique was designed jointly by EURECAT and a public research laboratory and is patented. It requires a preliminary purification to eliminate the elements which could bother the separation. Moreover, arsenic has to be removed at this step in order to avoid this element associating with molybdenum, tungsten or vanadium. This pre-purification is carded out by precipitation of the compounds containing alumina, phosphorus and arsenic. The residue containing these impurities which represents a very small amount compared to the inlet catalyst volume is in an inert physico-chemical form and can therefore be stored, transported and retreated eventually. The purified solution can then be sent to the resin unit for complete separation of molybdenum and vanadium. Tailings with the treatment of the solid contain typically 2-4% (w/w) nickel

G. BERREBIET AL.

and/or cobalt associated with alumina and/or silica, and can be accepted as an ore by a mining company. Their valorization is carded out by EURECAT's partner, a large mining company specialized in nickel metallurgy. This consists of a fusion of the solid in an arc furnace, to separate cobalt and nickel in a matte form from the aluminium and residual impurities which are eliminated in the slag. The nickel/cobalt matte is then treated conventionally by solvent extraction to separate nickel and cobalt before electrolysis of the metals.
PRODUCTS

The valuable metals extracted from the spent catalysts are marketable due to their high purity. These are electrolytical nickel and cobalt metals, molybdenum oxide, ammonium or sodium molybdate (or tungstate), and vanadium sulfate. These products can be used directly in metallurgical or chemical industries; a typical market could be the use of nickel, cobalt, vanadium, molybdenum and tungsten metals in the catalyst industry. The yield recovery for molybdenum, vanadium and tungsten is over 90% and for cobalt and nickel as high as 97%. Three types of effluents or residues are produced with EURECAT's process. The first one is a solid residue-containing alumina. This residue is extracted during the fusion in an arc furnace in slag form mixed with the conventional cobalt/nickel ore residue. The main part of the alumina from the spent catalyst is found in this inert residue. A small part of it is dissolved during the leaching step and then precipitated during purification. This second solid residue which is produced in small quantities contains mainly alumina and impurities such as arsenic and phosphorus. Arsenic is trapped in a stable alumina phosphate compound which is unleachable in an acidic or a slightly basic solution. Then there are the liquid effluents from the hydrometallurgical plant. Their quantity will be minimized by recycling of the solutions at different stages of the process.
ADVANTAGES OF THE PROCESS

EURECAT's process is flexible, easy to use, reliable, requires a rather low investment and has a relatively competitive cost of metal production. The originality of the process lies in the sensible combination of conventional regeneration, roasting, pyrometallurgical, hydrometallurgical techniques and an innovative ion exchange resin technology. Therefore, the first step for spent catalyst regeneration is fundamental in the continuation of the treatment. This step is perfectly mastered due to the use of regeneration techniques in a rotolouvre furnace, well-known to EURECAT. The project for spent catalyst retreatment forecasts a capacity of around 4000 t per year, which represents

RECYCLING SPENT OF HYDROPROCESSING CATALYSTS

approximately 8% of the potential world market. At present, EURECAT can treat 2000 t per year.
SPENT CATALYST HANDLING

United Nations experts have defined the tests applied to evaluate the dangerous character of a product [ 9 ]. The results of these tests applied to spent unreusable catalysts or adsorbents has led to the classification of these products as self-heating materials, and not as pyrophoric products (except for rare exceptions). They fall therefore into a precise classification and regulations concerning transport and handling, named class 4.2. Certain unloading techniques are supposed to eliminate or reduce the selfheating character of the spent catalysts and adsorbents [ 10,11 ]. It has to be pointed out that packing of spent catalysts and adsorbents under nitrogen does not mean they can be transported as non-dangerous goods, as it does not eliminate the potential self-heating character of these products. According to present regulations, unreusable catalysts or adsorbents must be considered as self-heating type waste. In these conditions, they must be packed, labelled, stocked, transported, controlled and destroyed according to the present regulations for dangerous products (see Table 2 ). The definition of secondary raw material is being examined, and could lead to a change in the definition of waste. The quality of secondary raw material could apply in future to certain catalysts or adsorbents recycled directly or after treatment in the iron and steel industry, chemistry, fertilizers, cements, etc.
PACKING OF SPENT CATALYSTS

Class 4.2 spent catalysts and adsorbents must be packed in Group 2 packaging material marked according to the latest UN recommendations. Metal 55-gallon open top drums with complete opening can be used for the transport of these products by sea, land or rail, as long as they carry the appropriate mark. The metal drum is the only acceptable packaging for products classed 4.2 when they must be shipped [ 12 ]. Metal containers may be used for land or rail transport of spent catalysts and adsorbents provided that they have undergone tests for resistance to impact and tightness, as described in the UN texts, and that they are marked accordingly. This use of metal containers is encouraged by EURECAT provided that the containers are manufactured by specialized companies and that they are properly maintained (covers-bottom valves). The Material Safety Data Sheet or Transport Emergency Group Card should mention the name and the nature of the product, its legal classi-

G. BERREBI ET AL.

TABLE 2 Legal classification of spent catalyst for sea, land and rail transport Type of transport Reference code Danger class Class denomination Paragraph denomination Reference Sea IMDG Land and Rail ADR/RID

4.2 Self-heating substances

4.2 Self-heating substances

No. UN 3088 IMDG code. p. 4260

No. 9 Mixture of granular or porous combustible materials with components still liable to spontaneous oxidation Dangerous Goods Loading Certificate

Necessary documents

Dangerous Goods Declaration and container/trailer packing certificate Material Safety Data Sheet

Material Safety Data Sheet

fication, the nature of the hazards, the protective devices and the necessary emergency action in case of fire, spillage or man injury.
CLASSIFIED INSTALLATIONS

Industrial waste inevitably supposes reprocessing on a classified industrial site. The EURECAT site at La Voulte is one of the few industrial sites in Europe which is qualified for retreatment/recycling/destruction of non-reusable spent catalysts or adsorbents [ 13 ]. EURECAT can help the customer to prepare the necessary documents for transport of spent catalysts or adsorbents to La Voulte and often organises the collection of the products by adequate trucks. After treatment, EURECAT supplies customers with a Certificate of Destruction and invoice.
CONCLUSION

EURECAT has designed a process to recycle spent catalyst, which allows a complete recycling of valuable metals with high recovery yields and minimum production costs. The respect of the environmental legislation has been one of the key criteria of the process options. The process is adaptable to

RECYCLING OF SPENT HYDROPROCESSING CATALYSTS

future modifications in the elementary composition o f spent catalysts. It is obvious that, in the coming years, the world market part of hydroprocessing catalyst treating heavier fractions o f the crude will increase due to the necessity o f heavy fuel oil desulfurization. The average v a n a d i u m and nickel contents o f these catalysts will therefore rise considerably. The m e t h o d chosen by E U R E C A T will allow an optimal valorization o f these two elements. In this project, E U R E C A T is associated with partners for the valorization o f the tailings containing nickel, cobalt and alumina. Most of the treatment is c a r d e d out at La Voulte, i.e. regeneration, roasting, leaching, separation and purification o f m o l y b d e n u m / v a n a d i u m . The whole project will offer producers o f spent catalysts a safe way to eliminate these wastes at reasonable costs, with the assurance o f a complete treatment, including the issuing o f a certificate for the destruction o f spent catalysts.

REFERENCES 1 A. De Roocher et al., CONCAWE. Oil & Gas Journal, August 28 (1989) 53. 2 M.L. Occelli and R.G. Anthony (Editors), Hydrotreating Catalysts. Proc. Int. AIChE Meeting, Washington, DC ( 1988). 3 J. Fache, P6troles et Techniques, 367 ( 1991 ) 36. 4 P. Soogard-Andersen, Paper l M 92-50, 1992 NPRA Annual Meeting, New Orleans, LA. 5 H.L. Hoffman, Hydrocarbon Processing, (Feb. 1991 ) 37. 6 D.L. Trimm, S. Akashah, M. Absi-Halabi and A. Bishari (Editors), Catalysts in Petroleum Refining. Proc. Conf. March 5-8, 1989. Studies in Surface Science and Catalysts, 53. Elsevier, Amsterdam (1990), p. 41. 7 R. Prins, V.H.J. de Beer and G.A. Somorjai, Catal. Rev. Sci. Eng. 31 (1/2) (1989) pp. 341. 8 J.B. Butt and E.E. Peterpen, Activation, Deactivation and Poisoning of Catalysts. Academic Press, San Diego, CA (1988) 278 pp. 9 Transport of Hazardous Products, ST/SG/AC. 10/1Rev. 5, United Nations Publications, Geneva ( 1987). l0 T. Kaijima et al., US Patent 4912071 (1990). 11 Kawakami et al., Jap. Patent 44755 (1977). 12 IMDG Code (International Marine Dangerous Goods), p. 4260. 13 Arr~t6 Pr6fectoral No. 91/209, Pr6fecture de Privas, France.