CN103626240B - Lower concentration complexity prepares the method for ruthenium trichloride containing ruthenium waste liquid - Google Patents
Lower concentration complexity prepares the method for ruthenium trichloride containing ruthenium waste liquid Download PDFInfo
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Abstract
The invention provides a kind of lower concentration complexity prepares ruthenium trichloride method containing ruthenium waste liquid, the method is complicated containing ruthenium waste liquid carries out acidifying, selectivity sinks ruthenium, the ruthenium slag of conventional washing dry acquisition enrichment to lower concentration; Ruthenium slag adopts chlorine to add alkali distillation, absorption by Hydrochloric Acid, concentrate the ruthenium trichloride that baking is prepared into SILVER REAGENT.The inventive method has that technique is simple, energy consumption is low, ruthenium accumulation rate is high, impurity element is up to standard, distillation number of times is few, the reaction times is short, quality product is easily controlled, product yield high.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of lower concentration complexity prepares ruthenium trichloride method containing ruthenium waste liquid.
Background technology
Ruthenium trichloride is one of most important compound of ruthenium, is the important industrial chemicals in the fields such as heterogeneous catalyst, homogeneous catalysis, plating, coating.Ruthenium trichloride is the main raw material of electric tank metal anode coating, more than 20 year has been produced in China, China has family more than 30 of electrolyzer manufacturing enterprise, metal anode is in electrochemical field widespread uses such as chlorine industry, inorganic electrosynthesis, Organic electro-synthesis, metallurgy, and wherein 95% of chlorine industry septation method caustic soda is that applied metal anode electrolytic tank is produced.
China's ruthenium natural resources shortage, producing ruthenium amount per year only has tens kilograms, and less than 1% of demand, therefore, the secondary resource regeneration of ruthenium is recycled significant.From secondary resource, how to extract the focus that ruthenium becomes China practitioner concern, from electrolyzer, reclaiming ruthenium, to prepare ruthenium trichloride be also one of emphasis, at present, lower concentration complexity adopts the method for common neutralization--charcoal absorption-burning enrichment usually containing ruthenium waste liquid, or use strong reductant direct-reduction, these two kinds of methods all have complex process, energy consumption is high, ruthenium accumulation rate is low, the shortcomings such as the many and contaminate environment of impurity element, simultaneously sodium chlorate is usually adopted to add sulfuric acid system preparing ruthenium trichloride, there is distillation often, long reaction time, the control of quality product difficulty, the problems such as product yield is low.
Summary of the invention
The object of this invention is to provide a kind of lower concentration complexity prepares ruthenium trichloride method containing ruthenium waste liquid.Wherein lower concentration complexity containing ruthenium waste liquid enrichment ruthenium process solves complex process, energy consumption is high, ruthenium accumulation rate is low, impurity element is many and the shortcoming such as contaminate environment, the preparation of ruthenium trichloride adopts the production technique of chlorine hydro-oxidation sodium to improve quality product, shortens the reaction times.
In order to achieve the above object, Technical Design of the present invention is as follows:
Lower concentration complexity prepares the method for ruthenium trichloride containing ruthenium waste liquid, it is characterized in that: lower concentration complexity containing ruthenium waste liquid through acidifying, selectivity sink ruthenium, through the dry ruthenium slag obtaining enrichment of routine washing; Ruthenium slag adds alkali distillation, absorption by Hydrochloric Acid through chlorine, concentrates the ruthenium trichloride that baking is prepared into SILVER REAGENT.
Lower concentration complexity prepares the method for ruthenium trichloride containing ruthenium waste liquid, it is characterized in that, lower concentration complexity is that concentration is the 1-15% of waste liquid to lower concentration complexity containing one or both mixing acid added in ruthenium waste liquid in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid containing the acidifying of ruthenium waste liquid.
Lower concentration complexity prepares ruthenium trichloride containing ruthenium waste liquid, it is characterized in that, it is a kind of precipitation agent added in solution in ammonium sulfide, hydrazine hydrate, thiocarbamide, sodium borohydride, sodium hydroxide that selectivity sinks ruthenium, be heated to 1h stopping heating of boiling, thin up 1 times, the consumption of precipitation agent is 0.5-10 times of ruthenium quality.
Lower concentration complexity prepares the method for ruthenium trichloride containing ruthenium waste liquid, it is characterized in that, the ruthenium trichloride that ruthenium slag adds alkali distillation through chlorine, absorption by Hydrochloric Acid, concentrated baking are prepared into SILVER REAGENT follows these steps to carry out: 1. under air-tight state, negative pressure adds the NaOH solution that massfraction is 20-40%, and the material proportion of thick ruthenium powder and sodium hydroxide solution is 1:10 – 100; 2. be heated to 80 DEG C, to step 1. in pass into chlorine, passing into chlorine flowrate is 50 – 120mL/min, controls temperature of reaction at 105 DEG C, generates yellow RuO
4gas; 3. the RuO 2. step generated
4gas is through deionized water purifying, pass into multistage absorption by Hydrochloric Acid liquid to absorb, concentration of hydrochloric acid is 2-10mol/L, temperature control is 25-40 DEG C, reductive agent is added in absorption by Hydrochloric Acid liquid, reductive agent is methyl alcohol, ethanol, n-propyl alcohol, the one of Virahol or two kinds of mixtures, and the massfraction of reductive agent is 0.01 – 6%, and reaction generates red-brown H
2ruCl
5solution, the NaOH solution that tail gas passes into 15% through negative pressure absorbs; 4. the H 3. step generated
2ruCl
5concentrate through conventional heating, RuCl that crystallization and infrared drying obtain chocolate
3crystal.
The inventive method, ruthenium waste liquid is contained for raw material with lower concentration complexity, acidifying, selective precipitation, ruthenium slag prepares ruthenium trichloride in homemade reaction unit, has that technique is simple, energy consumption is low, ruthenium accumulation rate is high, impurity element is up to standard, distillation number of times is few, the reaction times is short, quality product is easily controlled, product yield high.
Accompanying drawing explanation
Fig. 1 is the production equipment schema of best mode for carrying out the invention.
Embodiment
Following examples are intended to be further elaborated the present invention, instead of limitation of the present invention.Under the prerequisite not departing from State Intellectual property right protection, also may have various changes and modifications, these changes and improvements all belong to the scope of protection of present invention.
Embodiment 1
Measure lower concentration complexity and add (ruthenium content is 9.53 ‰ by analysis) in the Porcelain Jar of 500L containing ruthenium waste liquid 100Kg, one or both mixing acid in 5Kg hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid are slowly added under stirring, then a kind of precipitation agent in 1906g ammonium sulfide, hydrazine hydrate, thiocarbamide, sodium borohydride, sodium hydroxide is added, be heated to 1h stopping heating of boiling, be diluted with water to 200L, unload still, conventional filtration, washing, dry acquisition 1115g ruthenium slag (by analysis ruthenium content 84.29%), in waste liquid, the yield of ruthenium is 98.62%.
Get 300g ruthenium slag to drop in reactor a, and to add 1.5L massfraction be 20 – 40%NaOH solution, in b and c, add 2L deionized water, to RuO
4adding the hydrochloric acid of 2.5L2 – 10mol/L and methyl alcohol, ethanol, n-propyl alcohol, the one of Virahol or two kinds of mixtures in absorption bottle d, e, f keeps massfractions to be 0.01 – 6%, and in tail gas absorption bottle g, add 3L massfraction is 15%NaOH solution.First open vacuum pump h, close purging valve i, after checking the stopping property of whole preparation system, adjustment negative pressure is 0.08MPa.After feeding intake, heating a reactor, pass into chlorine after being warming up to 80 DEG C, controlling temperature of reaction is 105 DEG C, and in reactor a, solution is brownish black, and produces a large amount of yellow RuO
4gas, enters in absorption bottle d, e, f, generates henna H after removal of impurities bottle b and c
2ruC1
5solution, approximately after reaction 20min, system reaction starts to slow down.Again add equivalent NaOH solution, continue to pass into chlorine, and produce yellow RuO
4gas, so repeats 2-3 time to reaction solution without reddish-brown, and after having reacted, slowly unlatching blow-off valve i, closes vacuum pump h, sucking-off H
2ruC1
5solution through heating concentrated, crystallization, infrared drying obtains the crystallization of 673.12g ruthenium trichloride; Ruthenium trichloride quality meets HG/3679 – 2000 standard after testing, RuCl
3xH
2o crystallization ruthenium content is 36.95%, has good solubility property, ruthenium trichloride product yield 98.36%.
Embodiment 2
Measure lower concentration complexity and add (ruthenium content is 7.79 ‰ by analysis) in the Porcelain Jar of 500L containing ruthenium waste liquid 200Kg, one or both mixing acid in 22Kg hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid are slowly added under stirring, then a kind of precipitation agent in 4674g ammonium sulfide, hydrazine hydrate, thiocarbamide, sodium borohydride, sodium hydroxide is added, be heated to 1h stopping heating of boiling, be diluted with water to 400L, unload still, conventional filtration, washing, dry acquisition 1797g ruthenium slag (by analysis ruthenium content 86.32%), in waste liquid, the yield of ruthenium is 98.62%.
Get 300g ruthenium slag to drop in reactor a, and to add 1.8L massfraction be 30%NaOH solution, in b and c, add 2L deionized water, to RuO
4adding the hydrochloric acid of 2.5L4mol/L and methyl alcohol, ethanol, n-propyl alcohol, the one of Virahol or two kinds of mixtures in absorption bottle d, e, f keeps massfractions to be 0.5%, and in tail gas absorption bottle g, add 3L massfraction is 15%NaOH solution.First open vacuum pump h, close purging valve i, after checking the stopping property of whole preparation system, adjustment negative pressure is 0.08MPa.After feeding intake, heating a reactor, pass into chlorine after being warming up to 80 DEG C, controlling temperature of reaction is 105 DEG C, and in reactor a, solution is brownish black, and produces a large amount of yellow RuO
4gas, enters in absorption bottle d, e, f, generates henna H after removal of impurities bottle b and c
2ruC1
5solution, approximately after reaction 20min, system reaction starts to slow down.Again add equivalent NaOH solution, continue to pass into chlorine, and produce yellow RuO
4gas, so repeats 2-3 time to reaction solution without reddish-brown, and after having reacted, slowly unlatching blow-off valve i, closes vacuum pump h, sucking-off H
2ruC1
5solution through heating concentrated, crystallization, infrared drying obtains the crystallization of 694.05g ruthenium trichloride; Ruthenium trichloride quality meets HG/3679 – 2000 standard after testing, RuCl
3xH
2o crystallization ruthenium content is 36.91%, has good solubility property, ruthenium trichloride product yield 98.92%.
Embodiment 3
Measure lower concentration complexity and add (ruthenium content is 1.06% by analysis) in the Porcelain Jar of 500L containing ruthenium waste liquid 150Kg, one or both mixing acid in 18Kg hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid are slowly added under stirring, then a kind of precipitation agent in 3975g ammonium sulfide, hydrazine hydrate, thiocarbamide, sodium borohydride, sodium hydroxide is added, be heated to 1h stopping heating of boiling, be diluted with water to 300L, unload still, conventional filtration, washing, dry acquisition 1783g ruthenium slag (by analysis ruthenium content 88.39%), in waste liquid, the yield of ruthenium is 99.12%.
Get 300g ruthenium slag to drop in reactor a, and to add 2L massfraction be 25%NaOH solution, add 2.5L deionized water, to RuO to b
4adding the hydrochloric acid of 2.5L4mol/L and methyl alcohol, ethanol, n-propyl alcohol, the one of Virahol or two kinds of mixtures in absorption bottle c, d, e, f keeps massfractions to be 0.5%, and in tail gas absorption bottle g, add 3L massfraction is 15%NaOH solution.First open vacuum pump h, close purging valve i, after checking the stopping property of whole preparation system, adjustment negative pressure is 0.08MPa.After feeding intake, heating a reactor, pass into chlorine after being warming up to 80 DEG C, controlling temperature of reaction is 105 DEG C, and in reactor a, solution is brownish black, and produces a large amount of yellow RuO
4gas, enters in absorption bottle d, e, f, generates henna H after removal of impurities bottle b and c
2ruC1
5solution, approximately after reaction 20min, system reaction starts to slow down.Again add equivalent NaOH solution, continue to pass into chlorine, and produce yellow RuO
4gas, so repeats 2-3 time to reaction solution without reddish-brown, and after having reacted, slowly unlatching blow-off valve i, closes vacuum pump h, sucking-off H
2ruC1
5solution through heating concentrated, crystallization, infrared drying obtains the crystallization of 707.19g ruthenium trichloride; Ruthenium trichloride quality meets HG/3679 – 2000 standard after testing, RuCl
3xH
2o crystallization ruthenium content is 37.02%, has good solubility property, ruthenium trichloride product yield 98.73%.
Embodiment 4
Measure lower concentration complexity and add (ruthenium content is 1.13% by analysis) in the Porcelain Jar of 500L containing ruthenium waste liquid 250Kg, one or both mixing acid in 30Kg hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid are slowly added under stirring, then a kind of precipitation agent in 5650g ammonium sulfide, hydrazine hydrate, thiocarbamide, sodium borohydride, sodium hydroxide is added, be heated to 1h stopping heating of boiling, be diluted with water to 450L, unload still, conventional filtration, washing, dry acquisition 3112g ruthenium slag (by analysis ruthenium content 90.07%), in waste liquid, the yield of ruthenium is 99.22%.28252802
Get 300g ruthenium slag to drop in reactor a, and to add 2L massfraction be 25%NaOH solution, add 2.5L deionized water, to RuO to b
4adding the hydrochloric acid of 2.5L6mol/L and methyl alcohol, ethanol, n-propyl alcohol, the one of Virahol or two kinds of mixtures in absorption bottle c, d, e, f keeps massfractions to be 1%, and in tail gas absorption bottle g, add 3L massfraction is 15%NaOH solution.First open vacuum pump h, close purging valve i, after checking the stopping property of whole preparation system, adjustment negative pressure is 0.08MPa.After feeding intake, heating a reactor, pass into chlorine after being warming up to 80 DEG C, controlling temperature of reaction is 105 DEG C, and in reactor a, solution is brownish black, and produces a large amount of yellow RuO
4gas, enters in absorption bottle d, e, f, generates henna H after removal of impurities bottle b and c
2ruC1
5solution, approximately after reaction 20min, system reaction starts to slow down.Again add equivalent NaOH solution, continue to pass into chlorine, and produce yellow RuO
4gas, so repeats 2-3 time to reaction solution without reddish-brown, and after having reacted, slowly unlatching blow-off valve i, closes vacuum pump h, sucking-off H
2ruC1
5solution through heating concentrated, crystallization, infrared drying obtains the crystallization of 721.85g ruthenium trichloride; Ruthenium trichloride quality meets HG/3679 – 2000 standard after testing, RuCl
3xH
2o crystallization ruthenium content is 36.89%, has good solubility property, ruthenium trichloride product yield 98.55%.
Claims (1)
1. the complicated method preparing ruthenium trichloride containing ruthenium waste liquid of lower concentration, comprise lower concentration complexity containing ruthenium waste liquid through acidifying, selectivity sink ruthenium, through the dry ruthenium slag obtaining enrichment of routine washing, add alkali distillation, absorption by Hydrochloric Acid with chlorine, concentrate the ruthenium trichloride that baking is prepared into SILVER REAGENT, it is characterized in that, lower concentration complexity is that concentration is the 1-15% of waste liquid to lower concentration complexity containing one or both mixing acid added in ruthenium waste liquid in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid containing the acidifying of ruthenium waste liquid; It is a kind of precipitation agent added in solution in ammonium sulfide, hydrazine hydrate, thiocarbamide, sodium borohydride, sodium hydroxide that selectivity sinks ruthenium, and the 1h that is heated to boil stops heating, thin up 1 times, the consumption of precipitation agent be the 0.5-10 of ruthenium quality doubly; The ruthenium trichloride that ruthenium slag is prepared into SILVER REAGENT through chlorine distillation, absorption by Hydrochloric Acid, concentrated baking follows these steps to carry out:
1. under air-tight state, negative pressure adds the NaOH solution that massfraction is 20-40%, and the material proportion of thick ruthenium powder and sodium hydroxide solution is 1:10 – 100;
2. be heated to 80 DEG C, to step 1. in pass into chlorine, passing into chlorine flowrate is 50 – 120mL/min, controls temperature of reaction at 105 DEG C, generates yellow RuO
4gas;
3. the RuO 2. step generated
4gas is through deionized water purifying, pass into multistage absorption by Hydrochloric Acid liquid to absorb, concentration of hydrochloric acid is 2-10mol/L, temperature control is 25-40 DEG C, reductive agent is added in absorption by Hydrochloric Acid liquid, reductive agent is methyl alcohol, ethanol, n-propyl alcohol, the one of Virahol or two kinds of mixtures, and the massfraction of reductive agent is 0.01 – 6%, and reaction generates red-brown H
2ruCl
5solution, the NaOH solution that tail gas passes into 15% through negative pressure absorbs;
4. the H 3. step generated
2ruCl
5concentrate through conventional heating, RuCl that crystallization and infrared drying obtain chocolate
3crystal.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110255632A (en) * | 2019-07-17 | 2019-09-20 | 江西省汉高新材料有限公司 | The method for preparing ruthenium trichloride with waste material containing ruthenium |
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| CN106335932B (en) * | 2016-08-30 | 2018-02-23 | 昆明铂磊科技有限公司 | A kind of production technology of ruthenium trichloride |
| CN107162069B (en) * | 2017-05-12 | 2018-10-19 | 常州大学 | The recovery process of ruthenium trichloride catalyst in a kind of trimethyl pyruvic acid synthesis procedure |
| CN109136533A (en) * | 2018-10-19 | 2019-01-04 | 郴州高鑫铂业有限公司 | The method that quick separating extracts ruthenium from low content waste material containing ruthenium |
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| CN115074537A (en) * | 2022-07-06 | 2022-09-20 | 山东海科创新研究院有限公司 | Ruthenium ion recovery method |
| CN115636445B (en) * | 2022-11-02 | 2024-04-12 | 金川集团股份有限公司 | Method for preparing high-purity ruthenium trichloride from low-concentration ruthenium-containing waste liquid |
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Application publication date: 20140312 Assignee: CHENZHOU GAOXIN MATERIAL Co.,Ltd. Assignor: CHENZHOU GAOXIN PLATINUM Co.,Ltd. Contract record no.: X2021990000618 Denomination of invention: Preparation of ruthenium trichloride from low concentration complex ruthenium containing waste liquid Granted publication date: 20160330 License type: Exclusive License Record date: 20211012 |
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