CN1480541A - Method for extracting cobalt from industrial waste residue - Google Patents
Method for extracting cobalt from industrial waste residue Download PDFInfo
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- CN1480541A CN1480541A CNA021323976A CN02132397A CN1480541A CN 1480541 A CN1480541 A CN 1480541A CN A021323976 A CNA021323976 A CN A021323976A CN 02132397 A CN02132397 A CN 02132397A CN 1480541 A CN1480541 A CN 1480541A
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Abstract
A process for extracting cobalt from industrial waste dregs includes immersing in the solution of sodium hydroxide, pulverizing, oxidizing calcine, filtering to obtain Co dregs, immersing in the mixture of sulfuric acid, nitric acid and hydrochloric acid, adding calcium carbide dregs or lime solution for neutralidizing the extracted suspension, filtering, washing and using sodium carbonate to neutralize the Co contained filtrate to obtain cobalt carbonate.
Description
Technical field the present invention relates to a kind of simple and energy-efficient method of extracting cobalt from industrial residue, particularly extracts the method for cobalt from industrial spent catalyst.
Need in background technology petrochemical complex and the petroleum refining industry to use a large amount of cobalt molybdenum catalyst series, form by active ingredient molybdenum, nickel, cobalt and alumina catalyst support as Hydrobon catalyst; Use sulfur-resisting transformation cobalt-molybdenum catalyst etc. in petroleum hydrocarbon and the coal hydrogen production process.In ammonia synthesizing industry, cobalt molybdenum catalyst series is subjected to favoring widely with its good sulfur tolerance and low temperature active, and consumption is increasing, and in the carbon monoxide transformation catalyst that the nitrogen throughout industry is used quite a few being arranged is cobalt molybdenum catalyst series.China is that the large, medium and small type synthesis ammonia plant of raw material almost all uses co-mo antisulphuric transforming catalyst with coal and residual oil.
Be substantially 3～5 years the work-ing life of cobalt molybdenum catalyst series, and its essentially consist is to contain 1%～10% cobalt oxide and 4%～20% molybdenum oxide, and all the other are alumina catalyst support or silicon oxide etc.
Cobalt molybdenum resource scarcity costs an arm and a leg in the world, if the cobalt molybdenum spent catalyst that changes is thrown away, then not only causes financial loss, but also contaminate environment.Spent catalyst is as a kind of solid waste, and the whole world is annual to produce 50～700,000 tons.Reclaiming useful metal from spent catalyst, is to the making full use of of precious resources, and also is the needs of environment protection simultaneously.Therefore, the noble dilute metal that reclaims in the spent catalyst has remarkable economic efficiency and social benefit.
At present more for the report of the comprehensive utilization of cobalt molybdenum spent catalyst, roughly can reduce following several:
1. ammonia leaching process: be mainly used in the leftover bits that produce when producing cobalt-molybdenum catalyst.Because this waste material is without use, so inherent composition is only with MoO
3, CoO and skeleton Al
2O
3Be main.Therefore, can be liquid-solid ratio 4: 1 o'clock, with 4mol/L left and right sides ammoniacal liquor, leaching is 2～3 hours when temperature is 60～65 ℃, uses this method to the MoO in the spent catalyst
3Be respectively 92% and 17% with the rate of recovery of CoO, the leach liquor that contains molybdenum and cobalt then is directly used in pickling process and produces cobalt molybdenum low temperature shift catalyst.The point of the main deficiency of this method is that the rate of recovery of cobalt is low excessively.
2. chlorinating roasting: this method is reported by preceding West Germany, it be the spent catalyst that will pulverize in the presence of sodium-chlor through after the chloridizing roasting, the water logging product of roasting obtains containing the leach liquor of molybdenum and vanadium, after the liquid-solid separation, with molybdenum and the vanadium in traditional method recovery solution, the nickel and the cobalt that remain in the filter cake then utilize the method leaching that adds caustic soda to separate, this method is called multistage absorption method again, owing to consume more in the reaction, cost is higher, and the skeleton composition aluminum oxide in the spent catalyst must be through several secondary responses before separating.Gu this, a large amount of sedimentary several steps handle, and make recovery process tediously long.
3. alkali leaches method: this method is reported by the U.S., is about to spent catalyst and sneaks into Na
2CO
3After carry out roasting, molybdenum and vanadium enter solution after the water logging, remain in cobalt in the filter cake, nickel and aluminium and add caustic soda and handle and reclaim, the shortcoming and the chlorinating roasting of this method are basic identical.
4. High Temperature High Pressure diluted acid lixiviation process: the principal character of this technology is to adopt single process to make molybdenum, cobalt, nickel and vanadium in the spent catalyst enter solution, and makes Al
2O
3Precipitate with the solid form.The noble dilute metal that enters in the solution then reclaims with well-known method, and the main drawback of this method is because of High Temperature High Pressure, so appointed condition is required high.
5. roasting-acidolysis-organic solvent extraction method: after spent catalyst roasting, acidolysis, select appropriate organic solvent respectively wherein one or more elements selectively to be extracted.Its advantage is to extract whole useful metal aluminium, vanadium, nickel, molybdenum and cobalt from spent catalyst, but extraction process complexity, solvent recuperation expense height.Need to select suitable extraction agent in addition, guaranteeing good selectivity and high extraction yield, this also is a developing direction of organic extraction method from now on.
6. chloridized method: be divided into two kinds again, wherein a kind of is to be lower than under 600 ℃ the temperature, with chlorine and Air mixing gas disposal spent catalyst.Gas phase is selectively condensed, can obtain the muriate or the oxychlorination thing of aluminium and vanadium respectively.The water logging chloride residue can obtain the muriate of nickel and cobalt.Another kind is chlorine and the carbon mono oxide mixture with 1: 1, and chlorination is 90 minutes under 623K, and leaching obtains the muriate or the oxychlorination thing of molybdenum, then under 973K with residue chlorination 3 hours, leaching obtains the muriate of cobalt; Or with spent catalyst in chlorination water logging after 2 hours under the 798K, make cobalt and molybdenum leach out simultaneously, can cobalt be precipitated and isolated by transferring pH.The flow process of chloridized method is very simple, but the required equipment complexity.
The technology of extracting molybdenum from industrial residue (as spent catalyst) is comparative maturity, but extracts the Technology of cobalt the cobalt slag after carrying molybdenum, then also has many work to await further further investigation.
Summary of the invention the object of the present invention is to provide a kind of simple and energy-efficient processing method of extracting cobalt from industrial residue in the residue (being the cobalt slag) behind the extraction molybdenum.
Above-mentioned purpose of the present invention is reached by following concrete technical scheme.
The technology method of extraction cobalt of the present invention comprises the steps:
1.. to the cobalt molybdenum that exists with sulphided form is that industrial residue (as spent catalyst etc.) carries out the crushing screening pre-treatment;
2.. the powder material after the above-mentioned pre-treatment is carried out oxidizing roasting;
3.. with the powder material after the sodium hydroxide solution leaching oxidizing roasting:
4.. filter the suspension after alkali leaches, mainly contain Sodium orthomolybdate in the gained filtrate, filter cake is the cobalt slag.In filtrate, add the nitric acid neutralization and can get molybdic acid product (perhaps continue to add ammoniacal liquor, then can obtain the ammonium molybdate product);
5.. in the filter cake cobalt slag that 4. step obtains, add the nitration mixture leaching agent of being made up of sulfuric acid, nitric acid and hydrochloric acid, leaching cobalt wherein obtains acidleach and gets mixed solution under boiling;
6.. with main component is Ca (OH)
2Carbide slag (or lime) give neutralizing acid leaching mixed solution;
7.. filter the above-mentioned suspension that neutralization obtains that gives, filter cake is sent to and is fired composition brick or cement etc., and filtrate is then for containing cobalt liquid;
8.. contain cobalt filtrate with the yellow soda ash neutralization, filter also and obtain cobaltous carbonate product (perhaps further roasting obtains the cobalt oxide product) after the drying.
In cobalt recovery method of the present invention, wherein said oxidizing roasting is carried out in rotary kiln, and maturing temperature is 550～650C, and roasting time is 2～4 hours; Described crushing screening pre-treatment is meant that the material before the roasting is crushed to 80～120 orders: described sodium hydroxide solution leaching is meant the NaOH with 1.0～2.0N, solid-to-liquid ratio is 1: 3～4, stir leaching 1.5～2.5 hours under boiling, three circulation dippings: described being filtered into through 200～300 purpose filter clothes filtered; Described nitration mixture leaching agent is the mixed solution of sulfuric acid, nitric acid and hydrochloric acid, three's volume ratio is 1: 0～0.5: 0～0.5, and solid-to-liquid ratio is 1: 2～5, and stirring reaction is after 0.5～15 hour under the boiling, thin up continued boiling reaction 2～4 hours to 1.5～2.5 times of original volume; Described carbide slag is that calcium carbide route is produced the industrial residue of being produced in the polyvinyl chloride process, can't obtain the area of carbide slag, and available lime replaces, but the latter's cost is the former tens times.
The present invention is about extracting the simple and energy-efficient method of cobalt from industrial residue, its advantage is:
1. the industrial residue that contains the cobalt molybdenum just can successfully therefrom extract the cobalt molybdenum through described step.Technology is simple, and flow process is short, and is pollution-free;
2. making full use of calcium carbide route and produce industrial residue---the carbide slag of being produced in the polyvinyl chloride process, acid extraction liquid is given neutralization, can save a large amount of alkaline consumptions, so cost is very cheap, is the most energy-efficient up to now a kind of cobalt technology of carrying;
3. rate of recovery height, molybdenum 〉=94% wherein, cobalt 〉=91%;
4. based on above-mentioned 3 points, present method has remarkable economic efficiency and social benefit.
Simple and the energy-efficient method of description of drawings extraction cobalt of the present invention, its whole process flow as shown in Figure 1.
Describe a specific embodiment of the present invention below the embodiment in detail:
1. get petroleum industry and contain Co-Mo/Al
2O
3Spent catalyst, earlier after pulverizing 120 orders, again through 580 ℃ of oxidizing roastings 4 hours, wherein Co content is 1.48%, Mo content is 8.50%, Al content is 35.0%;
2. take by weighing above-mentioned powder material 200 grams, 800 milliliters of the NaOH solution of adding 1.5N, heated and stirred is to boiling in 2000 ml beakers, reaction leaching 2 hours is filtered then, adds nitric acid in filtrate, adjust pH to 1.0 filters once more, washs and dry cake, can make the molybdic acid product.Quality product meets the requirements, and wherein contains molybdenum 16.1 grams, and the rate of recovery of molybdenum reaches 94.7%;
3. carrying filter cake (being the cobalt slag) behind the molybdenum, to contain cobalt be 2.75%, takes by weighing 100 grams, adds 200 milliliters in water, stirs, and adds nitration mixture (H again
2SO
4: HNO
3: HCl=1: 0.2: 0.05, volume ratio) 100 milliliters, stirring reaction after 1 hour under boiling, thin up to 700 milliliter continued boiling reaction 3 hours, gave being neutralized to about pH=5.2 with carbide slag suspension.Filter then and washing leaching cake, obtain containing cobalt filtrate;
4. use Na
2CO
3Neutralizing above-mentionedly contains cobalt filtrate to the pH=8.0, filters and dry cake, can obtain the cobaltous carbonate product.Quality product meets the requirements, and wherein contains cobalt 2.55 grams, and the rate of recovery of cobalt is 92.7%.
Claims (4)
1. a simple and energy-efficient method of extracting cobalt from industrial residue is characterized in that this method comprises the steps:
1.. to the cobalt molybdenum that exists with sulphided form is that industrial residue (as spent catalyst etc.) carries out the crushing screening pre-treatment;
2.. the powder material after the above-mentioned pre-treatment is carried out oxidizing roasting;
3.. with the powder material after the sodium hydroxide solution leaching oxidizing roasting;
4.. filter the suspension after alkali leaches, mainly contain Sodium orthomolybdate in the gained filtrate, filter cake is the cobalt slag.Add the nitric acid neutralization in the filtrate and can obtain the molybdic acid product, perhaps continue to add ammoniacal liquor, then can obtain the ammonium molybdate product;
5.. in the filter cake cobalt slag that 4. step obtains, add the nitration mixture leaching agent, leaching cobalt wherein obtains acidleach and gets mixed solution under boiling;
6.. with main component is Ca (OH)
2Carbide slag give neutralizing acid leaching mixed solution;
7.. filter the above-mentioned suspension that neutralization obtains that gives, filter cake is sent to and is fired composition brick or cement etc., and filtrate is then for containing cobalt liquid;
8.. contain cobalt filtrate with the yellow soda ash neutralization, filter also and obtain the cobaltous carbonate product behind the dry cake, perhaps further roasting obtains the cobalt oxide product.
2. method according to claim 1 is characterized in that described method also comprises the steps: to get in the mixed solution in the acidleach that obtains, and gives being neutralized to pH=5.0～5.2 earlier with carbide slag suspension, and then filters and washing leaching cake.
3. method according to claim 1, it is characterized in that described method comprises the steps: that also the acidleach stage of getting of the filter cake (being the cobalt slag) after carrying molybdenum comprises two processes, i.e. first boiling stirring reaction 0.5～1.5 hour under the concentrated acid condition, and then (being thin up 1.5～2.5 times to original volume) continued the boiling stirring reaction 2～4 hours under the diluted acid condition.
4. according to claim 1 or 3 described methods, it is characterized in that: the used nitration mixture leaching agent of leaching filter cake cobalt slag is the mixed solution of sulfuric acid, nitric acid and hydrochloric acid, and three's volume ratio is 1: 0～0.5: 0～0.5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021323976A CN1232662C (en) | 2002-09-03 | 2002-09-03 | Method for extracting cobalt from industrial waste residue |
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|---|---|---|---|
| CNB021323976A CN1232662C (en) | 2002-09-03 | 2002-09-03 | Method for extracting cobalt from industrial waste residue |
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| CN1480541A true CN1480541A (en) | 2004-03-10 |
| CN1232662C CN1232662C (en) | 2005-12-21 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974691A (en) * | 2010-11-10 | 2011-02-16 | 白银有色集团股份有限公司 | Method for recovering cobalt in cobalt-containing waste residues from zinc smelting |
| CN102438741A (en) * | 2009-04-01 | 2012-05-02 | 大地更新集团有限责任公司 | Improved aqueous phase oxidation process |
| CN103253920A (en) * | 2013-06-09 | 2013-08-21 | 赣州腾远钴业有限公司 | Method for preparing concrete block by utilizing wet smelting leached waste residues of cobalt |
| CN106747321A (en) * | 2017-03-12 | 2017-05-31 | 江西理工大学 | A kind of fired brick of cobalt melting waste slag base and preparation method thereof |
| CN110735041A (en) * | 2019-08-28 | 2020-01-31 | 广西银亿高新技术研发有限公司 | process method for leaching insoluble metal waste by cyclic catalytic oxidation acid leaching |
-
2002
- 2002-09-03 CN CNB021323976A patent/CN1232662C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102438741A (en) * | 2009-04-01 | 2012-05-02 | 大地更新集团有限责任公司 | Improved aqueous phase oxidation process |
| CN101974691A (en) * | 2010-11-10 | 2011-02-16 | 白银有色集团股份有限公司 | Method for recovering cobalt in cobalt-containing waste residues from zinc smelting |
| CN101974691B (en) * | 2010-11-10 | 2012-10-03 | 白银有色集团股份有限公司 | Method for recovering cobalt in cobalt-containing waste residues from zinc smelting |
| CN103253920A (en) * | 2013-06-09 | 2013-08-21 | 赣州腾远钴业有限公司 | Method for preparing concrete block by utilizing wet smelting leached waste residues of cobalt |
| CN106747321A (en) * | 2017-03-12 | 2017-05-31 | 江西理工大学 | A kind of fired brick of cobalt melting waste slag base and preparation method thereof |
| CN106747321B (en) * | 2017-03-12 | 2019-10-11 | 江西理工大学 | A kind of fired brick and preparation method thereof of cobalt melting waste slag base |
| CN110735041A (en) * | 2019-08-28 | 2020-01-31 | 广西银亿高新技术研发有限公司 | process method for leaching insoluble metal waste by cyclic catalytic oxidation acid leaching |
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|---|---|
| CN1232662C (en) | 2005-12-21 |
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