United States Patent (19) 11) 4,182,747 Gravey Et Al
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United States Patent (19) 11) 4,182,747 Gravey et al. 45 - Jan. 8, 1980 54 PROCESS FOR PREPARATION OF 3,565,820 2/1971 Coons et al. ......................... 252/419 ANHYDROUS METALLC CHLORIDES 3,985,639 10/1976 Suggitt et al. ....................... 252/415 FROM WASTE CATALYSTS FOREIGN PATENT DOCUMENTS 75) Inventors: Guy Gravey; Jean Le Goff; Christian Gonin, all of Moutiers, France 65929 11/1972 Poland ....................................... 423/60 Primary Examiner-Earl C. Thomas 73) Assignee: Metaux Speciaux S.A., Paris, France Attorney, Agent, or Firm-Dennison, Dennison, (21) Appl. No.: 862,594 Meserole & Pollack (22 Filed: Dec. 20, 1977 57 ABSTRACT 30 Foreign Application Priority Data A process is disclosed for recovering metallic constitu Dec. 30, 1976 FR France ................................ 7639842 ents of spent or waste catalysts containing metallic com pounds fixed on an aluminous support. The process is 51) Int. C.’................................................ C01B 9/02 particularly applicable for the recovery of metals such 52 U.S. Cl. ...................................... 423/491; 423/60; as Al, Mo, V, Ni and Co, contained in spent catalyst. 423/62; 423/116; 423/137; 423/150; 423/492; The process comprises transforming the metals to be 423/493; 423/496; 252/411 R recovered into volatile chlorides by carbochlorination 58) Field of Search ............... 252/415, 416, 419, 411, and then separating the chlorides obtained by dry means 252/414; 423/60, 62, 65, 116, 136, 137, 150, and fixing them successively in a selective manner. The 492, 493, 495, 496 separation of AlCl3 is accomplished by passage through 56) References Cited granules of anhydrous NaCl, and the separation of U.S. PATENT DOCUMENTS MoCls by passage through granules of crystallized KCl. 1,911,505 5/1933 Herold et al. .......................... 423/60 The process is particularly suitable for the treatment of 3,066,010 11/1962 Horning et al. ... 423/60 waste catalyst from the catalytic hydrocracking or hy 3,172,864 3/1965 Unverferth ..... 252/419 drodesulfurization of oils. 3,180,706 4/1965 Erickson ................................ 423/60 3, 197,284 7/1965 Hoekstra .............................. 252/419 18 Claims, No Drawings 4,182,747 1. 2. PROCESS FOR PREPARATION OF ANHYDROUS THE INVENTION METALLIC CHLORDES FROM WASTE The process of the invention solves the above prob CATALYSTS lems in obtaining metallic chlorides of high purity from waste catalysts containing compounds of these metals BACKGROUND OF THE INVENTION along with volatile materials and various impurities. This process, essentially using dry, i.e., anhydrous treat It is generally known that it is possible to treat waste ment steps, has as a significant aspect the recovery of catalysts such as those used in oil refining to recover the activated alumina support material for the catalysts valuable compounds or elements contained therein. 10 by transforming them into a very pure anhydrous alumi U.S. Pat, No. 2,367,506 describes a process for recov num chloride fixed on the alumina in the form of chlo ery of the molybdenum present in spent hydroforming ride mixtures of NaCl.Allclis. It also permits simple and catalysts having an activated alumina support. The efficient separation of the molybdenum and vanadium process impregnates the catalyst with a sodium carbon chlorides from each other and also from the aluminum ate solution, then heats the impregnated catalyst to 15 chloride. It is also possible in this process to recover the 1150' C. The sodium molybdate which is thus formed is hydrocarbons and the carbon contained in the waste dissolved in water, and the solution is treated to recover catalysts. a molybdenum compound. This process, in which the It is generally preferable to use waste catalysts as they final treatment is effected by wet means, is practical are withdrawn from the petroleum treatment installa only for the recovery of an oxide or a salt of molybde 20 tions and without subjecting them to any treatment for separation of the volatile materials which they contain. Dutch (Netherlands) Application No. 74-16155 con These catalysts are generally in the form of small rods cerns a process for treatment of waste desulfurization or pellets. The largest dimensions are generally less than catalysts of molybdenum-cobalt alumina type, to re one centimeter. They are constituted of an activated cover, on the one hand, vanadium and molybdenum, 25 alumina support, or gamma alumina, which is porous and to recover, on the other hand, cobalt and/or nickel. and which is impregnated with compounds containing In this process, the catalyst is treated such that, without certain metals, particularly molybdenum, most often previous roasting in the presence of soda or carbonate associated with cobalt or nickel. In the course of use of of soda, the catalyst is air heated to between 650 and these catalysts, they fix vanadium compounds, carbon 850 C. The sodium molybdates and vanadates formed 30 resulting from the partial decomposition of hydrocar are extracted with water, and ammonium vanadate is bons, and sulfur, at least partially in the form of sulfides prepared, and then the ammonium tetramolybdate is and also a certain number of other metallic or nonmetal precipitated by hydrochloric acidification. The solid lic impurities, generally in combined form, such as for residue can be treated separately for extraction of alu 35 example nickel. Finally, in their raw state, these waste mina, nickel and cobalt. This method is for extraction of catalysts are of course still impregnated with a certain molybdenum and vanadium, and not for simultaneous quantity of hydrocarbons. - extraction of alumina. As in the preceding method of The first step of the present process is the elimination the U.S. patent, this method does not permit collection of the hydrocarbons by a sufficiently selective process of these metals in an anhydrous chloride state. In addi 40 to avoid elimination of the carbon which is present in tion, the process requires direct treatment of the waste noncombined state in the pores of the waste catalyst. catalysts by alkaline compounds, which prevents recov This can be obtained for example by the action of a ering the hydrocarbons for subsequent use. solvent, for instance an organic solvent, as is conven French Pat. No. 724,905 describes a process of treat tional in the art, for elimination of the major part of the ment by hydrochloric acid or chlorine of materials 45 hydrocarbons contained in the pores of the catalyst. containing molybdenum, tungsten and vanadium, in This solvent is then eliminated by distillation at a suit which it is possible to obtain these metals in chloride able temperature. The hydrocarbons can also be form if they are found in oxide state in the starting burned, in a strictly limited quantity of air so as to stop material. The chlorination is accomplished at a temper the combustion before the noncombined carbon is also 50 oxidized. This is obtained by heating a mass of catalyst ature on the order of 300 to 400 C. The carbon neces to a temperature on the order of 400° C. for approxi sary for the reaction can be found in the starting mate mately one half hour in a furnace in the presence of air rial, which is the case with catalysts used for the hydro but without forced circulation of the air. Then a com genation of coal. The carbon necessary can also be bustion of the hydrocarbons is carried out, which is added in the form of coke, lignite, wood charcoal, etc. 55 practically complete, but the major part of the noncom The chlorides formed in a gaseous state can be recov bined carbon is not oxidized. ered by condensation and dissolution in water. The Alternatively a bed of spent hydrocarbon containing process does not permit separation of the vanadium and catalyst can be heated from the outside while contained molybdenum chlorides. Also, the process conditions are in a closed treatment vessel with a flow of nitrogen such that there is practically no formation of aluminum through it, which engages the bed at a temperature on chloride. the order of 400 C., or better yet, passes through the The processes just described do not permit direct bed. The nitrogen effluent becomes charged with vola preparation of anhydrous metallic chlorides from waste tile materials which distill slowly, a little at a time, and catalysts. it is thus possible to recover them by a condensation Moreover, the prior art processes do not provide 65 procedure. A part of the hydrocarbons which are thus means for efficiently separating the aluminum chloride recovered can be used for heating the treatment fur from at least one of the molybdenum and vanadium nace, and the other part is used otherwise. Tests have chlorides. shown that the quantity of hydrocarbons thus extracted 4,182,747 3 4. from the catalysts was on the order of from 10 to 20% molybdenum chloride from the other compounds con by weight of these catalysts. tained in the gaseous mixture is possible by passing it After the hydrocarbon extraction, the waste catalyst through a column containing granules of potassium can be directly subjected to the action of the gaseous chloride, prepared by crystallization from an aqueous chlorine at a temperature of between 500 and 600 C. 5 solution, brought to a temperature between approxi This operation can be effected for example in a vertical mately 100 and 500 C. According to prior art litera nickel column heated from the exterior and partially ture, the vanadium chloride VCl4 becomes fixed to the filled with spent catalyst, with a gaseous chlorine cur potassium chloride, producing a double chloride rent injected at the base of the column while the volatile VCl3.3ClK (see Pascal Volume XII pages 132-133). In compounds which are formed are discharged at the top.