CN100567528C - A kind of method that from waste palladium carbon catalyst, reclaims precious metal palladium - Google Patents
A kind of method that from waste palladium carbon catalyst, reclaims precious metal palladium Download PDFInfo
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- CN100567528C CN100567528C CNB200610097872XA CN200610097872A CN100567528C CN 100567528 C CN100567528 C CN 100567528C CN B200610097872X A CNB200610097872X A CN B200610097872XA CN 200610097872 A CN200610097872 A CN 200610097872A CN 100567528 C CN100567528 C CN 100567528C
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Abstract
The invention belongs to solid waste recovery and utilization technology field, be specifically related to reclaim the method for the precious metal palladium in the waste palladium carbon catalyst.This method comprises that roasting, reduction, leaching, ion-exchange removal of impurities, ammino close, acidifying, roasting, hydrogen reduction, obtains palladium metal.Technology of the present invention is simple, production cost is low, and palladium recovery rate is greater than 99%, and palladium metal purity is greater than 99.9%.
Description
Technical field:
The invention belongs to solid waste recovery and utilization technology field, be specifically related to reclaim the method for the precious metal palladium in the waste palladium carbon catalyst.
Background technology:
Palladium-carbon catalyst is widely used in Chemical Manufacture, for example synthesizes reactions such as reaching caprolactam refining, terephthalic acid hydrofining at droperiodol, tolylene diisocyanate and all adopts palladium-carbon catalyst.Through behind the life-time service, the palladium in the catalyzer is lost activity by contaminating impurity, becomes spent catalyst.Because palladium is a precious metal, resource scarcity costs an arm and a leg, and reclaims significant to its regeneration.
Palladium-carbon catalyst is to be carrier with the gac, contains palladium about 0.1～10%.The relative live catalyst of waste palladium carbon catalyst palladium content descends to some extent, and spent catalyst surface coverage large amount of organic contains impurity such as Fe, Ni, Cu simultaneously.The method that reclaims palladium from waste palladium carbon catalyst mainly is divided into pyrometallurgy and hydrometallurgy two classes.Pyrometallurgical method is that the spent catalyst that will contain palladium reclaims with traditional method after the high melt enrichment again; Hydrometallurgical mainly adopts art breading such as ion-exchange, electrolysis, displacement.The most long flow path of these methods, cost height, palladium recovery rate are low.
Summary of the invention:
The invention provides a kind of method that from waste palladium carbon catalyst, reclaims precious metal palladium, advantage such as this method has rate of recovery height, and technology is simple, and cost is low, and environmental pollution is little.
Method of the present invention comprises that waste palladium carbon catalyst roasting, reductive agent reduction, inorganic acid and the leaching of oxygenant mixing solutions, Zeo-karb and ammino set up the inferior palladium roasting of removal of impurities, hcl acidifying, dichloro two amminos and six processes of reducing jointly, makes the resultant metal palladium.
A preferred embodiment of the present invention is:
1) roasting process: use the stoving oven roasting, maturing temperature 500-800 ℃, preferably use the tube furnace roasting, maturing temperature 550-750 ℃, abundant air feed.
2) reduction process: the roasting ash reduces with reductive agent, reductive agent can be formic acid, sodium formiate or hydrazine hydrate, preferable formic acid is as reductive agent, the palladium ash is 1 with the formic acid weight ratio: 0.1-1 (preferred 1: 0.2-0.8), reduction temperature 50-90 ℃ (preferred 60-80 ℃), recovery time 2-6 hour (preferred 3-5 hour).
3) leaching process: used inorganic acid can be hydrochloric acid, sulfuric acid or nitric acid, preferred hydrochloric acid, used oxygenant can be one or both the mixing solutions in clorox, hydrogen peroxide, sodium chlorate or the perchloric acid, be preferably the mixing solutions of clorox and hydrogen peroxide or sodium chlorate and hydrogen peroxide, wherein the weight ratio of clorox and hydrogen peroxide is 1: 0.5-3, and the weight ratio of sodium chlorate and hydrogen peroxide is 1: 1-4; The weight ratio of inorganic acid and oxygenant is 1: (1-8), extraction temperature is 60-100 ℃ (preferred 70-90 a ℃), and extraction time is 3-8 hour (preferred 4-7 hour).
4) ion-exchange, ammino close the removal of impurities process: will contain palladium solution and exchange removal of impurities with Zeo-karb, preferred D001 type Zeo-karb, again with ion exchange liquid with the abundant complexing of ammoniacal liquor, control pH=8-11 (preferred pH=9-10), filtering and impurity removing.
5) acidization: the ammonia complex liquid hcl acidifying after will filtering, control pH=1-4 (preferred 1.5-3) obtains the inferior palladium yellow mercury oxide of dichloro two amminos, filters washing.
6) roasting, reduction process: the inferior palladium yellow mercury oxide of dichloro two amminos is put into the stoving oven roasting, maturing temperature 400-800 ℃ (preferred 500-700 ℃), roasting time is 2-7 hour (preferred 3-5 hour), uses hydrogen reducing again, obtains palladium metal.
1), technology is simple, easy handling the present invention has the following advantages:; 2), the palladium recovery rate height, can reach more than 99%; 3), " three wastes " few, handles simply, environmental pollution is little; 4), good product quality, palladium metal purity is more than 99.9%; 5), production cost is low.
Embodiment:
With reference to the following embodiment that only provides for explanation, further details of the present invention and advantage will become clearer.Need to prove that these embodiment are used to limit protection scope of the present invention.
The catalyzer that adopts among the embodiment is the terephthalic acid hydrofining palladium-carbon catalyst after the industrial use, and the fresh palladium-carbon catalyst palladium of this type content about 0.5% uses back palladium content about 0.3～0.4%.Result of implementation sees Table 1.
Embodiment 1:
Get waste palladium carbon catalyst 10kg (doing), palladium content is 0.33% (wt), puts into tube furnace and carries out roasting, maturing temperature is 600 ℃, abundant air feed, and the roasting ash adds the formic acid reduction, add-on is that every kilogram of palladium ash adds 300 milliliters of formic acid, be heated to 70 ℃, kept 3 hours, filter, filter residue hydrochloric acid, clorox, the aqueous solution of hydrogen peroxide leaches, palladium ash wherein: hydrochloric acid: clorox: hydrogen peroxide: water=1: 5: 5: 5: 3,75 ℃ of temperature, 4 hours time, filter, filter residue reclaims, and filtrate is carried out ion-exchange, and ammino closes, filter, the complexing slag reclaims, the complex liquid acidifying, and the acidifying tail washings is collected, put into stoving oven after the acid precipitation oven dry, hydrogen reducing is used in 600 ℃ of following roastings 4 hours, obtains resultant metal palladium 32.71g.
Embodiment 2:
Get spent catalyst 10kg (doing), palladium content is 0.33% (wt), puts into tube furnace and carries out roasting, maturing temperature is 650 ℃, abundant air feed, and the roasting ash adds the formic acid reduction, add-on is that every kilogram of palladium ash adds 400 milliliters of formic acid, be heated to 75 ℃, kept 4 hours, filter, filter residue hydrochloric acid, clorox, the aqueous solution of hydrogen peroxide leaches, palladium ash wherein: hydrochloric acid: clorox: hydrogen peroxide: water=1: 6: 5: 8: 4,80 ℃ of temperature, 5 hours time, filter, filter residue reclaims, and filtrate is carried out ion-exchange, and ammino closes, filter, the complexing slag reclaims, the complex liquid acidifying, and the acidifying tail washings is collected, put into stoving oven after the acid precipitation oven dry, hydrogen reducing is used in 550 ℃ of following roastings 4.5 hours, obtains resultant metal palladium 32.79g.
Embodiment 3:
Get spent catalyst 10kg (doing), palladium content is 0.33% (wt), puts into tube furnace and carries out roasting, maturing temperature is 700 ℃, abundant air feed, and the roasting ash adds the formic acid reduction, add-on is that every kilogram of palladium ash adds 500 milliliters of formic acid, be heated to 80 ℃, kept 5 hours, filter, filter residue hydrochloric acid, clorox, the aqueous solution of hydrogen peroxide leaches, palladium ash wherein: hydrochloric acid: sodium chlorate: hydrogen peroxide: water=1: 7: 5: 10: 3,85 ℃ of temperature, 6 hours time, filter, filter residue reclaims, and filtrate is carried out ion-exchange, and ammino closes, filter, the complexing slag reclaims, the complex liquid acidifying, and the acidifying tail washings is collected, put into stoving oven after the acid precipitation oven dry, hydrogen reducing is used in 550 ℃ of following roastings 4 hours, obtains resultant metal palladium 32.75g.
Table 1 test-results
Claims (8)
1, a kind of method that reclaims precious metal palladium from waste palladium carbon catalyst is characterized in that comprising following consecutive steps:
A), with the waste palladium carbon catalyst roasting, maturing temperature is 500-800 ℃;
B), the palladium ash reduces with reductive agent, reductive agent is formic acid, sodium formiate or hydrazine hydrate; The palladium ash is 1 with the reductive agent weight ratio: 0.1-1, and reduction temperature 50-90 ℃, the time is 2-6 hour;
C), leach with inorganic acid and oxygenant; The weight ratio of inorganic acid and oxygenant is 1: 1-8, extraction temperature are 60-100 ℃, and extraction time is 3-8 hour; Used oxygenant is the mixing solutions of clorox and hydrogen peroxide or sodium chlorate and hydrogen peroxide, and wherein the weight ratio of clorox and hydrogen peroxide is 1: 0.5-3, and the weight ratio of sodium chlorate and hydrogen peroxide is 1: 1-4;
D), leach liquor is through removal of impurities, carries out ammino again and closes, control pH value is 8-10;
E), ammino closes filtrate and uses acidifying, control pH value be 1-4, obtains dichloro two amminos Asia palladium yellow mercury oxide, precipitates and carries out roasting, maturing temperature 300-800 ℃, time 2-7 hour, obtains the resultant metal palladium through reduction then.
2, the method for claim 1 is characterized in that waste palladium carbon catalyst at the tubular type kiln roasting, maturing temperature 550-750 ℃, and abundant air feed.
3, the method for claim 1 is characterized in that the palladium ash is 1 with the reductive agent weight ratio: 0.2-0.8, reduction temperature 60-80 ℃, recovery time 3-5 hour.
4, the method for claim 1 is characterized in that used inorganic acid is hydrochloric acid, sulfuric acid or nitric acid.
5. the method for claim 1 is characterized in that used inorganic acid is a hydrochloric acid.
6. the method for claim 1, the weight ratio that it is characterized in that inorganic acid and oxygenant is 1: 2-8, extraction temperature are 70-90 ℃, extraction time 4-7 hour.
7. the method for claim 1 is characterized in that leach liquor is exchanged removal of impurities with Zeo-karb, again with ion exchange liquid with the abundant complexing of ammoniacal liquor, control preferred pH=9-10, filtering and impurity removing.
8. the method for claim 1, it is characterized in that ammonia complex liquid hcl acidifying, control PH 1.5-3, obtain the inferior palladium yellow mercury oxide of dichloro two amminos, filter, after the washing the inferior palladium precipitation of dichloro two amminos is put into the stoving oven roasting, maturing temperature 400-700 ℃, time 3-5 hour, obtain the resultant metal palladium with hydrogen reducing again.
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| WO2024023055A1 (en) * | 2022-07-26 | 2024-02-01 | Solvay Sa | Hydrometallurgical process for recovering palladium from a spent catalyst |
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| CN103122412B (en) * | 2011-11-18 | 2014-10-15 | 中国石油化工股份有限公司 | Recovery method for waste palladium carbon catalyst metal palladium |
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| CN102978409A (en) * | 2012-12-26 | 2013-03-20 | 安徽工业大学 | Method for recovering heavy metal palladium from waste carbon-based catalytic agent |
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| CN104032143A (en) * | 2014-05-15 | 2014-09-10 | 浙江省冶金研究院有限公司 | Recycling and purifying method of waste palladium-carbon catalyst |
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| WO2024023055A1 (en) * | 2022-07-26 | 2024-02-01 | Solvay Sa | Hydrometallurgical process for recovering palladium from a spent catalyst |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: Nanhua Group Research Institute |
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