SU1521279A3 - Method of obtaining nickel tetracarbonyl - Google Patents

Abstract

This invention relates to a process for the production of nickel in the form of nickel tetracarbonyl from used catalysts obtained in the food, pharmaceutical, nitrogen industries. The invention makes it possible to increase the yield of the product. The essence of the method is that the spent powdered nickel-containing catalyst is treated with hydrogen, ammonia or synthesis gas at 250-450 ° C in a reactor with a magnetic stirrer in the presence of a freshly prepared mixture of mercury sulfide with copper sulfide II) in an amount of 0.2-4.0 wt. based on the nickel content, followed by carbonylation at 60-125 ° C and 10-135 bar and release of the product in a refrigerator under pressure. The yield of the product increased to 82.7-98.2%.

Description

This invention relates to the production of nickel in the form of nickel tetracarbonate from used catalysts obtained in the food, pharmaceutical, nitrogen industry.

The aim of the invention is to increase the yield of the product.

Example 1. Made from heat-resistant steel, having a volume of 500 ml, equipped with a heating arm, magnetic stirrer, supply and DETAILS pipelines For gas, pressure gauge and control valves, the reactor is charged with 350 g of defatted, used catalyst oil for hydrogenation. containing nickel

36.6%. As an activator, 3.5 g of freshly prepared HgS (2.73 wt.% LigS based on the nickel content) are added. After purging with nitrogen, the tightness of the apparatus is checked by means of a hydrogen pressure of 125 bar. After the test pressure, the loaded material is heated at a heating rate in a hydrogen stream of 30 l / h to 350 ° C, then activated at this temperature for 4 h in a hydrogen stream of 40 l / h. After the activation, the loaded material is cooled to 80 ° C and the reduced loaded material is gradually subjected to carbonylation under pressure of carbon monoxide | DM M

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yes PO bar o The pressure increase is twisted so that the initial temperature increases as much as possible. After 5 minutes of counting from the beginning, the carbonyl release and carbon monoxide release are activated. Tetracarbonyl nickel is released into liquid form in a pressurized condenser in a stream of carbon monoxide to an internal pressure resistant storage cylinder. The carbopyl leaving the can with a gas stream is allowed to freeze in a deep-cooled trap. In 5 hours, 348 g of nickel tetracarbonyl is formed, which corresponds to a nickel yield of 93.4% Approx 2o B the reactor described in Example 1 was weighed 300 g of a deactivated non-fat catalyst containing nickel 41.5% used for curing fat %, this was preceded by the addition of 2 g of HgS g CuS (2.42 wt%). The loaded material is activated as described in the example. After activation, the reactor is cooled to 80 ° C. Carbonyl carbonation is carried out at a carbon monoxide pressure of 100 bar. During the four-hour carbonylir of the I-type, 342 g of nickel tetracarbonyl are obtained, which corresponds to a yield of} 94.5%.

Example 3 Into the reactor of Example 1, 350 g of the catalyst used in the pharmaceutical industry for the hydrogenation of a René nickel-based catalyst slurry in the wet state are weighed out, the moisture content being 26.5%, the dry matter content of nickel is 64.3% A mixture of 2 g of mercury sulphide and 2 g of copper sulphide (2.42 wt.%) Is added to the slurry. The material being loaded is dried by heating only in a stream of nitrogen up to 125 ° C, then reduced in a stream of synthesis gas for 3 hours. After the activation has been carried out, the feed material is carbonated at a temperature and at a pressure of 120 bar (carbon monoxide pressure), After 6 hours, the carbonyphosphoot contains 458.8 g of tetracarbonium.

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pa nickel, which corresponds to a nickel yield of 95.4%,

Example 4c Into the reactor of Example 1, 300 g of waste is weighed.

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sprayed, applied dp hydrogenation of phenol catalyst, to which 1% of freshly prepared mercury sulphide and 1/2% copper sulphide are pre-mixed, (1.32 wt.%). The loaded material is activated as described in Example 1 in a stream of hydrogen for 5 hours at 420 ° C, after which, gradually increasing the pressure of carbon monoxide to 115 bar, the loaded material is subjected to carbonylation for 4.5 hours at a temperature of about 90 ° C. C, From the loaded spent nickel-containing catalyst, 308.2 g of nickel carbonyl is obtained, which corresponds to a nickel yield of 93.7%.

Example5. 300 g of a sprayed catalyst for the conversion of carbon monoxide and carbon dioxide to methane are weighed from the nitrogen industry, to which 1.5 g HgS + 1.5 g CuS (4 wt.%) Were mixed, are weighed into the reactor of example 1. The loaded material is activated in the flow of ammonia gas. at 400 ° C for 4.5 hours and then subjected to carbonylation at 120 ° C and at a CO pressure of 130 bar. For 5 hours, 217 g of nickel tetracarbonyl is formed, which corresponds to a nickel yield of 92.4%,

EXAMPLE 6 300 g of waste containing 33.0% by weight of nickel catalyst and a freshly formed mixture of 2.0 g of HgS and 0.5 g of CuS (2.52% by weight; HgS + CuS in terms of nickel content). After flushing the reactor with nitrogen, the temperature of the reactor is increased at a heating rate of 50 ° C / h and a hydrogen stream of 30 l / h to 250 s and maintain this temperature at a constant hydrogen flow of 5. h o After activation, the load is cooled to 60 ° C and t carbonylation in the temperature range and at a carbon monoxide pressure of 135 bar for 4 hours. Formed tetracarbonyl. nickel is continuously removed from the system.

A total of 253.3 g of nickel tetracarbonyl is formed, which corresponds to a yield by nickel of 88.0% o

Example c Into the reactor of example 1, 300 g of spent catalyst with a nickel content of 33.0 wt.% And a freshly formed mixture of 2.0 g of HgS and 0.5 g of CuS (2.52 wt.% Of HgS + CuS in terms of content

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nickel). After flushing the reactor with nitrogen, the reactor temperature is increased at a heating rate of 50 ° C / h in a hydrogen stream of 30 l / h at a pressure of 10 bar before and maintained at a constant hydrogen flow of 5 hours. After activation, the reactor is cooled to and carbonized temperature ranges of 125 ° C at a carbon monoxide pressure of 135 bar for 5 hours. The tetracarbonyl nickel formed is continuously removed from the system

A total of 280.4 g of nickel tetracarbonyl is formed, which corresponds to a nickel yield of 97.4%

Example: Into the reactor of example 1, 300 g of spent catalyst with a nickel content of 33.0 wt.% And a freshly formed mixture of 3.0 g of CuS (3.03% CuS based on nickel content) are loaded. After washing the reactor with nitrogen, the temperature of the reactor is increased heating rate of 50 ° C / h in a stream of nitrogen of 30 l / up to 450 ° C and maintain this temperature at a constant flow of hydrogen for 5 hours. After activation, the reactor is cooled to 60 ° C and carbonylation is performed in the temperature range of 20 ° C and at a carbon monoxide pressure of 135 bar for 5 hours. The resulting tetracarb nile nickel continuously removed from the system,

A total of 238.1 g of nickel tetracarbonyl was formed, which corresponds to a nickel yield of 82.7% (in terms of the nickel content in the initial catalyst).

Example E. The reactor according to Example 1 is charged with 300 g of spent catalyst with a nickel content of 33.0 wt.% And a freshly formed mixture of 2.0 g of mercury sulphide and 0.5 g of copper sulphide (2.52 wt.% HgS + CuS based on on nickel content). After flushing the reactor with nitrogen, the reactor temperature is increased at a heating rate of 50 ° C / hr in a hydrogen stream of 30 l / h to 450 ° C and maintained at a constant hydrogen flow of 5 Cho. After activation, the reactor is cooled to and carbonylation is performed at 60 ° C at 135 bar carbon monoxide pressure for 8 Cho. The resulting tetracarbonyl nickel is continuously removed from the system.

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A total of 267.1 g of nickel tetracarbonyl is formed, which corresponds to a yield of 92.8%.

Example 10. In the reactor of example 1 load 300 g of spent catalyst with a nickel content of 33.0 wt,% and a freshly formed mixture of 0.07 g of mercury sulfide and 0.03 g

Copper sulfide Q (0.10 maso% HgS + CuS based on nickel content). After flushing the reactor with nitrogen, increase the temperature of the reactor at a heating rate of 50 ° C / h in the stream

5 30 l / h before and maintain this temperature at a constant flow of hydrogen 5 h. After activation, the reactor is cooled to 60 ° C and carbonylation is carried out in the temperature range at a pressure of 135 bar of carbon monoxide for 5 hours. The resulting tetracarbonyl nickel is continuously removed from the system.

A total of 221.0 g of tetracar5 bonil nickel is formed, which corresponds to a yield of 76.0%.

Example I. In the reactor of example 1 load 300 g of spent catalyst with a nickel content of 33.0 mass%, and freshly formed

a mixture of 3.0 g of mercury sulphide and 1.0 g of copper sulphide (4.04 wt.% HgS + CuS based on the nickel content). After flushing the reactor with nitrogen, the temperature of the reactor is increased at a heating rate of 50 ° C / hr in a hydrogen stream of 30 l / hr and maintain this temperature at a constant stream. hydrogen 5 hours. After activation

0 the reactor is cooled to 60 ° C and carbonylation is carried out in a temperature range of 125 ° C at a carbon monoxide pressure of 135 bar for 5 ° C. The resulting nickel tetracarbonyl is continuously removed from the system

A total of 285.6 tetrakarsh nickel was formed, which corresponds to a yield of 98.2%.

Example 12. In the reactor according to

In Example 1, 300 g of a consumable catalyst was introduced with 33.0 wt.% Nickel content and a freshly prepared mixture of 0.14 g HgS and 0.06 g CuS (0.20 wt.% Hg and CuS relative to the content of 5

kel). After purging the reactor with nitrogen, the temperature of the reactor is increased to 450 ° C at a heating rate of 50 ° C / h in a hydrogen stream of 30 l / h and this temperature is maintained at a constant

The hydrogen stream is 5 hours. After the activation process, the reactor is cooled to 60 ° C and the carbonylation is carried out at a pressure of 135 bar of carbon monoxide for 5 hours. The resulting tatracarbonyl nickel is removed from the system continuously by cooling under pressure.

244.3 g of tetracarbonyl nickel J is formed, which corresponds to a yield of 84%.

Example 13. In the reactor according to Example 1, the experiment was carried out according to the example of this; the mixer is not operated.

300 g of consumed catalyst are introduced into the reactor with 33.0% by weight of nickel and a freshly prepared mixture of 2 g of HgS and 0.8 g of CuS (2.52% by weight of HgS and CuS relative to the nickel content). After purging the reactor with nitrogen, the temperature of the reactor is increased at a heating rate of 50 ° C / h in a hydrogen stream of 30 l / h and this temperature is maintained at a constant hydrogen flow for 5 h. After the activation process, the reactor is cooled to and carbonylated at a temperature of 60 ° C with a pressure of carbon monoxide of 135 bar for 8 hours

The resulting nickel tetracarbonyl, by applying cooling in the presence of pressure, is continuously removed from the system.

259.3 g of nickel tetracarbonyl is formed, which corresponds to a product yield of 90.1%.

Primvr14 In the reactor according to example 1, when meikals are put into operation, the experiment according to example 9 is carried out. Tetracarbonyl nickel is condensed only by cooling without pressure with a release from 135 to 1 bar.

300 g of consumed catalyst with 33.0% by weight of nickel and a freshly prepared mixture of 2 g of HgS and 0.5 g of CuS (2.52% by weight of HgS and CuS relative to the nickel content) are introduced into the reactor. After purging the reactor with nitrogen, the temperature of the reactor rises with a heating rate of 50 ° C / hr in a hydrogen stream of 30 l / hr and this temperature is maintained

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at a constant flow of hydrogen for 5 hours. After the activation process, the reactor is cooled to 60 ° C and carbonylation is carried out at a carbon dioxide pressure of 135 bar for 8 hours. The tetracarbonyl nickel thus formed and CO — the accompanying gas is released from 135 to 1 bar and the resulting tetracarbonyl nickel is condensed by cooling.

A total of 241 g of nickel tetracarbonyl is formed, which corresponds to a yield of 83.7%.

Example 15 300 g of waste containing 64.3 wt. Of nickel, a catalyst and a mixture of 2.0 g of HgS and 0.5 g of CuSc are loaded into the reactor of example 1. The mass moisture of the catalyst is 26.5 wt%. First, the loaded mass is dried in a stream of nitrogen at 125 ° C, then reduced in a stream of hydrogen at 280-320 ° C,

After activation, the charging is boiled at 10 bar carbon monoxide pressure for 18 hours. The tetracarbonyl nickel formed is continuously removed from the system.

A total of 442.5 g of nickel tetracarbonyl is formed, which corresponds to a nickel yield of 92.0%.

By a known method, the product yield is 80%.

Claims (1)

Invention Formula A method for producing nickel tetracarbonyl from a spent dust-like nickel-containing catalyst, comprising treating it at a high temperature with hydrogen, ammonia or synthesis gas in a reactor with a magnetic stirrer, subsequent carbonylation at elevated temperature and pressure, and releasing the product in a refrigerator under pressure, about replicating with that. That, in order to increase the product yield, the treatment with hydrogen, ammonia or synthesis gas is carried out at 250-450 ° C in the presence of a freshly prepared mixture of mercury sulfide with copper sulfide (II) in the amount of 0.2-4.0 wt.%, Calculated on nickel content, and carbonylation is carried out at 60-125 ° C and 10-135 bar.