Method for comprehensively recovering metallic cobalt, ruthenium and aluminum from Fischer-Tropsch synthesis dead catalyst Co-Ru/Al2O3

A waste catalyst, Fischer-Tropsch synthesis technology, applied in chemical instruments and methods, cobalt oxide/cobalt hydroxide, ruthenium/rhodium/palladium/osmium/iridium/platinum oxide/hydroxide, etc., can solve filtration difficulties, The cobalt recovery rate is reduced, and it cannot be directly used to prepare cobalt catalysts, etc.

Active Publication Date: 2012-11-28
SUNSHINE KAIDI NEW ENERGY GROUP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Co(NO 3 ) 2 ·6H 2 The purity of O is lower than 99%, and it cannot be directly used to prepare cobalt catalysts
Chinese patent 101700913A grinds the spent cobalt-based catalyst loaded on alumina, dissolves it in concentrated hydrochloric acid, precipitates cobalt with sodium sulfide, precipitates cobalt with oxalic acid, calcines, dissolves with nitric acid, evaporates and crystallizes, and finally obtains high-purity Co with a purity of more than 99% ( NO 3 ) 2 ·6H 2 O, but because the waste catalyst is not reduced, and the intermediate product CoS produced in the recovery process has very fine grains, it is difficult to filter, and it is easy to lose cobalt, which leads to a decrease in the recovery rate of cobalt, which is about 92%.
[0009] The above patents are all dedicated to the recovery of a single metal, and the patents for the comprehensive recovery of cobalt, ruthenium and aluminum have not yet been published.

Method used

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  • Method for comprehensively recovering metallic cobalt, ruthenium and aluminum from Fischer-Tropsch synthesis dead catalyst Co-Ru/Al2O3
  • Method for comprehensively recovering metallic cobalt, ruthenium and aluminum from Fischer-Tropsch synthesis dead catalyst Co-Ru/Al2O3
  • Method for comprehensively recovering metallic cobalt, ruthenium and aluminum from Fischer-Tropsch synthesis dead catalyst Co-Ru/Al2O3

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0066] 1) Take loose Co-Ru / Al 2 o 3 Spent catalyst 20.23g, elemental analysis result is: contain Co30.05%, contain Ru 4.83%, contain Al 27.90%; Spent catalyst particle is packed in the muffle furnace, feeds air, roasts 3 hours at 500 ℃, with Remove the heavy hydrocarbons on the surface of the catalyst particles, and then cool to room temperature;

[0067] 2) the spent catalyst in step 1) is ground into uniform powder, then transfers to in the fluidized bed reactor, in H 2 :N 2 The volume ratio of the mixed gas is 4:1, and the space velocity is 1000h -1 , the pressure is 1MPa, and the temperature is 800°C for 10 hours;

[0068]3) Put the spent catalyst and alkali flux reduced in step 2) into the crucible in layers, and put KOH 21.31g, spent catalyst, KOH 10.65g, KNO 3 7.32g, then put it into the muffle furnace, first raise the temperature of the muffle furnace to 200°C for 1 hour, then program the temperature at 3°C / min to 950°C for alkali fusion reaction for 3 hours, cool...

Embodiment 2

[0079] 1) Take loose Co-Ru / Al 2 o 3 Spent catalyst 20.74g, elemental analysis result is: contain Co25.33%, contain Ru 3.07%, contain Al 32.53%; Spent catalyst particle is packed in the muffle furnace, feeds air, roasts at 350 ℃ for 6 hours, with Remove the heavy hydrocarbons on the surface of the catalyst particles, and then cool to room temperature;

[0080] 2) the spent catalyst in step 1) is ground into uniform powder, then transfers to in the fluidized bed reactor, in H 2 :N 2 The volume ratio of the mixed gas is 2:1, and the space velocity is 3000h -1 , the pressure is 0.8MPa, and the temperature is 700°C for 11 hours;

[0081] 3) Add the spent catalyst and alkali flux reduced in step 2) into the crucible in layers, and put in 17.50g of NaOH, spent catalyst, 8.75g of NaOH, NaNO 3 4.02g, then put it into the muffle furnace, first raise the temperature of the muffle furnace to 200°C for 1 hour, then program the temperature at 3°C / min to 900°C for alkali fusion reaction...

Embodiment 3

[0092] 1) Take loose Co-Ru / Al 2 o 3 Spent catalyst 19.96g, element analysis result is: contain Co18.94%, contain Ru 2.11%, contain Al 37.80%; Spent catalyst particle is packed in the muffle furnace, feeds air, roasts 5 hours at 400 ℃, with Remove the heavy hydrocarbons on the surface of the catalyst particles, and then cool to room temperature;

[0093] 2) the spent catalyst in step 1) is ground into uniform powder, then transfers to in the fluidized bed reactor, in H 2 :N 2 The volume ratio of the mixed gas is 3:1, and the space velocity is 2000h -1 , the pressure is 0.5MPa, and the temperature is 350°C for 12 hours;

[0094] 3) Add the spent catalyst and alkali flux reduced in step 2) into the crucible in layers, and put NaOH 19.19g, spent catalyst, NaOH 9.59g, NaNO 32.66g, then put it into the muffle furnace, first raise the temperature of the muffle furnace to 200°C for 1 hour, then program the temperature at 3°C / min to 1000°C for alkali fusion reaction for 2 hours, c...

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Abstract

The invention discloses a method for comprehensively recovering metallic cobalt, ruthenium and aluminum from a Fischer-Tropsch synthesis dead catalyst Co-Ru / Al2O3, and the method can be used for effectively separating and comprehensively recovering valuable metallic cobalt, ruthenium and aluminum from the Fischer-Tropsch synthesis dead catalyst Co-Ru / Al2O3. The method comprises the steps of: firstly carrying out hydrocarbon removal and reductive treatment on the dead catalyst; effectively separating cobalt slag in an alkali fusion step; and carrying out acid leaching on the cobalt slag, oxalate or oxalate deposited cobalt, reducing cobalt oxalate, dissolving the metallic cobalt via nitric acid and the like to obtain Co(NO3)2.6H2O. Ruthenate is obtained by the steps of alkali fusion and deionized water leaching; and steps of ethanol reduction, concentrated hydrochloric acid dissolution, reduced pressure distillation and the like are carried out on the ruthenate to obtain a beta-RuCl1.xH2O product which is high in purity. By using a CO2 carbon dioxide decomposition method, the parameters such as reaction temperature, CO2 flow velocity, pH value of reaction destination and the like are controlled and aluminum hydroxide is prepared from meta-aluminate solution; high-temperature calcination is carried out to obtain aluminum oxide; and the product quality meets the quality requirement of first-level aluminum oxide of national standard and the process is economic and environment-friendly. According to the invention, the metallic recovery rate is high, wherein the recovery rate of cobalt is greater than or equal to 97%, the recovery rate of ruthenium is greater than or equal to 95% and the recovery rate of aluminum is greater than or equal to 92%.

Description

technical field [0001] The present invention relates to a kind of spent catalyst Co-Ru / Al from Fischer-Tropsch synthesis 2 o 3 The invention discloses a method for comprehensively recovering metal cobalt, ruthenium and aluminum, which belongs to the technical field of catalyst and metal recovery from waste catalyst. Background technique [0002] In recent years, with the depletion of world petroleum resources and the gradual aggravation of environmental pollution, it has become an urgent problem to find clean and renewable alternative liquid fuels. The Fischer-Tropsch synthesis reaction can convert the synthesis gas obtained through the gasification process of carbonaceous substances such as natural gas, coal, and biomass into liquid fuel (also called synthetic oil) under the action of a Fischer-Tropsch synthesis catalyst. After subsequent processing, rectification and other post-treatment processes, the synthetic oil can obtain gasoline and diesel oil superior to the Euro...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C22B7/00C22B1/02C22B3/04C22B11/00C22B21/00C22B23/00
CPCC22B7/00C22B7/009C22B11/026C22B21/003C22B11/048C22B23/00C22B23/026C01G51/00C01G51/04C01G55/004C01G55/005Y02P20/129C01F7/142C01P2006/80C22B23/0446Y02P10/20Y02P20/141C22B11/04C22B11/06C22B21/02
Inventor 刘倩倩韩奕铭宋德臣许莉赖波
Owner SUNSHINE KAIDI NEW ENERGY GROUP CO LTD
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