CS249548B2 - Method of metalic nickel winning - Google Patents

Description

The invention relates to. a process for obtaining nickel in the form of nickel tetracarbonyl from spent catalysts from the food, pharmaceutical, nitrogen industries) and other chemical industries and other wastes containing. nickel. .

The way. according to the invention, nickel can be recovered in the form of nickel tetracarbonyl in a yield of more than 95% of spent catalysts used for the hydrogenation of oils, fatty solidification, galvanic bath sludge, Raney nickel used as the catalyst for hydrogenation of various organic compounds by hydrogenation of phenols as well as methanated catalysts which have already lost their activity.

In the chemical, pharmaceutical and food industries, nickel metal is extracted. as is well known in the literature, chemically from catalysts contaminated or toxic inactivated by organic or inorganic substances, from nickel-containing sludge formed in electroplating during electrolytic processes. '.

In terms of individual chemical processes, nickel-containing waste, spent catalyst, is treated with strong inorganic acids, the nickel salt formed precipitates and electronically or pyrometallurgically clarifies (Adamski. Z. et al .: Rudy met. Niezalaz., 1981, 26 (5)) , Burynska, L. et al .: Rudy Met Niezalaz 1981 26 (6), 325-6 (Pol), Darolin, R. et al .: Fr. Demande Fr. 2,472,620, Monolache , C. et al .: Rom. 70, 780, April 15, 1980, Goryachev, AA Ropkova, EK: USSR 831 839, May 23, 1981; Kontopoulos, A .: Fr. Demande 2,459,295, January 9, 1981; Schneider , A 3549———————————————————————————————————————————————————————— Zacheria, M., Extr. March 15, 1983, Mulak W. et al., Pol PL 113 896, May 1982; Loboiko, A. Ya et al .: USSR, SU 1011237, April 15, 1983).

According to another kind of chemical process, the complicated process starts with alkaline melting followed by acid decomposition, precipitation and fine clarification (Drule, ML et al .: Rum. RO 67 818 01, October 1979; Nihon Jiryoku Senko Inc. Jpn. Kokai Tokyo KOHO JP 81 78 431, June 27, 1981, also decomposition starting with an alkali hydroxide, carbonate or ammonia solution may be classified as: Oastraszku, R., Simionuk, G .: Powloki Ochr., 1981,9 (4-5), 53 Rokukawa, N .: Kogai Shigen Kenkyusho Iho, 1983 13 (1), 59-63 (Jap) Nickel is obtained from a combination of the above-described chemical methods from galvanic bath sludge, slag, dead stone and turbidity. chemical or decomposition-based method is that the accompanying elements - nickel and other impurities - enter the solution, the processes are not selective, the yield does not reach 90%.

An electrolysis-based process yields a near-selective and somewhat better yield: Furukawa Kinzoku Kogyo Κ. K. Jpn. Kokai Tokyo Koho JP 81 123 335 September 28, 1981; Tomlinson, D., Brown, D., Galvano.Technica 1981, 32 (4), 73-5 (Ital.). The drawback of the method is that, for electrolysis, a pure nickel salt or a solution thereof must be available in advance (which is also the most complicated process). Nickel can be recovered from the nickel solution from waste by electrodlaze:. Heller, H. C. Markovac, V .: Anal. Chem., 1983, 55 (4). 551A-552A, 556A-551 / A (UK); Galimi, G. Montalto, M., Galvanotechnica 1983, 34 (4), 67-75 (Ital).

From the impregnating solution resulting from the manufacture of the catalyst or from a solution containing. nil, - originating from other waste, nickel can be recovered using an ion exchange resin: Figurovskaya et al .: Deposited Doc. 1982 SPSTL 498 Kph — D82.5; Heu, T.J. et al .: Huan Ching Pao Hu (TAI) 1982, 5 (3), 17-25 (CH). '' I

From spent catalysts from the nitrogen industry, nickel is obtained in the form of tetracarbonyl in 80% yield. See Kasco, F. et al. Patent Rum. RO — 67, 180, May 29, 1979.. The process described herein is not suitable for treatment for wastes waste in the food, pharmaceutical and organic chemistry industries, the 20% nickel residue requires another method of recovery.

The process according to the invention can treat nickel-containing wastes either in their original state or pretreated. Under the term. pretreatment means the following operations: degreasing, centrifuging, precipitating, solvent extraction, in the case of non-pyrophoric drying materials. The pyrophoric materials are fed into the reactor - wet.

According to the invention, nickel-containing wastes are treated in two stages, but in the same plant. In the first stage of the process the waste is activated, in the second stage the activated material is carbonylated. Both operations can be carried out in a powder reactor designed by the inventors.

Waste activation is carried out at atmospheric pressure, in the presence of hydrogen or synthesis gas, in the temperature range of 250 to 450 ° C. Freshly prepared mercury sulphide, copper sulphide or a mixture thereof is used for activation.

The carbonylation of the activated charge takes place at a temperature of 60 to 125 ° C and a carbon monoxide pressure of 1.0 to 13.5 MPa. The carbon monoxide is fed to the top of the reactor upstream of the hydrogen stream and discharged along with the nickel carbonyl being formed at the bottom of the reactor. Pressure-cooled nickel carbonyl condenses from the gas stream and is collected in a pressure tank. The carbonyl leaving the gas stream system is allowed to freeze to a deep-cooled trap structure.

The reaction is carried out under a carbon monoxide pressure of 1.0 to 10.0 MPa. During four hours of carbonylization, 342 g of nickel tetracarbonyl was formed corresponding to 94.5% nickel.

The end product obtained by the process of the invention is high purity tetracarbonyl of nickel, with a boiling point of 42.2 ° C and a melting point of -17.2 ° C. The product can be stored under pressure of carbon monoxide without the risk of decomposition for many years.

Example 1

350 g of a degreased catalyst containing 36.6% of nickel, used for 36.6% nickel, was weighed into a 500 ml stainless steel reactor equipped with a heating mantle, a magnetic powder mixer, a gas inlet and outlet line, a manometer and control valves. hydrogenation of shortening. 3.5 g of freshly prepared mercuric sulfide Hgs are fed as activator. After the aeration with nitrogen, the gas-tightness of the device is checked with hydrogen at a pressure of 125 MPa.

After the pressure test, the charge was heated at a heating rate of 50 ° C / h in a 30 L / h hydrogen flow to 350 ° C, then activated at 40 ° C / h for 4 hours at this temperature. After activation, the charge is cooled back to 70-80 ° C and the reduced charge is slowly carbonylated with oxide. at a pressure of 1.0 to 11.0 MPa. The pressure is increased to such an extent that the outlet temperature is increased by a maximum of 20-25 ° C. After 15 minutes, counting from the beginning of the carbonylization, the carbonyl is discharged and carbon monoxide is removed.

The tetracarbonyl nickel liquefied in a pressurized condenser is discharged in a carbon monoxide stream into a pressure-resistant storage bottle. The carbonyl exiting the bottle, possibly together with the gas stream, is allowed to freeze in a deep-cooled collector. After five hours, 348 g of nickel tetracarbonyl was formed, corresponding to a nickel yield of 93.4 percent.

Example 2

300 g of a deactivated, degreased catalyst containing 41.5% nickel containing carrier and used for fat-hardening were weighed into the reactor described in Example 1 and 2 g of HgS + -1 g CuS were added beforehand. The charge was activated as described in Example 1. After activation, the reactor was cooled to 80 ° C. The carbonyliD of the reactor of Example 1 was weighed with 350 g of Raney nickel wet sludge used in the pharmaceutical hydrogenation industry, with a moisture content of 26.5 percent, the nickel content based on dry matter

64.3%. A mixture consisting of 2 g of mercury sulphide and 2 g of copper sulphide is added to the sludge. The cartridge is first dried in a stream of nitrogen by heating to 125 ° C, then reduced for 3 hours at 300 ° C in a syngas stream. After activation, the charge is carbonylated at a temperature of 75 to 125 ° C and at a pressure of 1.0 to 12.0 MPa (carbon monoxide pressure). After carbonylization for 6 hours, it was formed

458.8 g of nickel tetracarbonyl corresponding to a nickel yield of 95.4%.

Example 4

300 g of spent, pulverized catalyst used for the hydrogenation of phenol, to which 1% freshly produced mercury sulfide and V2 percent copper sulfide were premixed, were weighed into the reactor of Example 1. The charge is activated for 5 hours in a stream of hydrogen at 420 ° C as described in Example 1, after which the charge is carbonylated at 90 ° C and slowly from 1.0 MPa to 11.5 MPa with increasing carbon monoxide pressure for 4.5 hours. clock. From the filled, spent nickel-containing catalyst, 308.2 g of nickel carbonyl was formed, corresponding to a nickel yield of 93.7 percent.

Example 5

300 g of a pulverized, methanized catalyst, from the nitrogen industry, to which 1.5 g of HgS 4 - 1.5 g of CuS was premixed was weighed into the reactor of Example 1. The charge was activated in a stream of ammonia at 400 ° C for 4.5 hours and then carbonylized at 70-120 ° C under a carbon monoxide pressure of 1.0 to 13.0 MPa. 217 g of tetracarbonyl nickel were formed in 5 hours, corresponding to a nickel yield of 92.4%.

Claims (1)

Process for obtaining nickel metal in the form of nickel tetracarbonyl from spent powdered catalysts containing or without supported nickel, characterized in that the spent, purified catalyst is activated at a temperature of 250 to 450 ° C in a stream of hydrogen, ammonia or synthesis gas in the presence of a mixture mercury sulfide and / or copper sulfide as activator in a total amount of 0.1 to 4.0% by weight, the activated charge is carbonylated at 60 to 125 ° C at a carbon monoxide pressure of 10 to 13.5 MPa, whereupon the resulting the liquid nickel tetracarbonyl is cooled to a temperature below its boiling point and stored under a carbon monoxide pressure of 0.2 to 1.0 MPa.