CN102367177A - Method for preparing copper sulfide, cupric nitrate and sodium nitrate with residual copper sludge - Google Patents
Method for preparing copper sulfide, cupric nitrate and sodium nitrate with residual copper sludge Download PDFInfo
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- CN102367177A CN102367177A CN2011101827751A CN201110182775A CN102367177A CN 102367177 A CN102367177 A CN 102367177A CN 2011101827751 A CN2011101827751 A CN 2011101827751A CN 201110182775 A CN201110182775 A CN 201110182775A CN 102367177 A CN102367177 A CN 102367177A
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Abstract
The invention provides a method for preparing copper sulfide, cupric nitrate and sodium nitrate with residual copper sludge generated from vat grey BG production. The method comprises the steps of: turning the residual copper sludge into slurry with industrial water, conducting filtration so as to obtain copper sulfide and filtrate 1, reacting the filtrate 1 with a hydrochloric acid solution, thus obtaining a mixed solution containing cupric chloride, sodium chloride and sodium sulfate, and simultaneously a discharging hydrogen sulfide gas; filtering the mixed solution so as to obtain a very small amount of filter cake impurities and clarified filtrate; subjecting the clarified filtrate first to normal pressure distillation for distilling out organic impurities with a low boiling point, then reacting the remained filtrate with excess nitric acid so as to generate cupric nitrate, sodium nitrate and hydrogen chloride, carrying out filtration so as to remove a small number of impurities, thus obtaining filtrate 2; reacting the filtrate 2 with excess calcium nitrate so as to remove sodium sulfate, and conducting filtration, thus obtaining filtrate 3; crystallizing the filtrate mainly composed of cupric nitrate, sodium nitrate and hydrogen chloride at different temperatures according to different solubility of cupric nitrate and sodium nitrate under different temperature conditions, thus obtaining cupric nitrate and sodium nitrate respectively.
Description
Technical field:
The invention belongs to dyestuff organic chemical industry industry multipurpose use of three types of wastes technical field, particularly, relating to is a kind ofly to prepare cupric sulfide with the waste residue copper sludge, the method for cupric nitrate and SODIUMNITRATE, and said waste residue copper sludge is for producing the Vat Grey BG gained.
Background technology
The reactive brilliant bule K-NR of dyestuffs industries, purple, the production processes generation copper-containing residues such as redeem a vow to a god grey BC, methyl catechol of alkalescence; Wherein contain a large amount of organic substances, inorganic salt etc.; The general calcination process that adopts; At high temperature contain copper compound in the waste residue and be oxidized to cuprously, reclaim with the copper sulfate form after reaching sulfuric acid acidation then.Oxidative decomposition at high temperature takes place in the organism in the waste residue simultaneously, generates gases such as sulfurous gas, nitrogen oxide, carbonic acid gas, hydrochloric acid, water.
Vat grey BC is to be raw material with phthalic anhydride, ammoniacal liquor, Resorcinol and midbody RK, through reaction such as condensation, ammonification, oxidation, acidylate, solid phase condensation and filter, dry, process such as spray is done and making.By how acid anhydride and ammoniacal liquor are raw material for midbody RK system, make through process such as reaction such as ammonification, hydrolysis, bob-weight nitrogen, virtueization, cyclization bromination and filtration, drying.The RK that makes supplies vat grey BC to produce the solid phase condensation use.The filtration procedure that midbody RK produces produces a large amount of waste residue copper sludges.
Detect the waste residue copper sludge that the above-mentioned explained hereafter vat grey of certain station-service BC produces, 1 ton of grey BC that redeems a vow to a god of every production produces waste residue copper sludge 989.91kg, and vat grey BC produces 300 tons per year, and then producing the waste residue copper sludge per year is 297 tons.The waste residue copper sludge component of gained is: cupric chloride 3.44%, and cupric sulfide 13.44%, sodium sulphite 3.53%, sodium-chlor 3.26%, sodium sulfate 1.67%, water are 20.4%, organic impurity 50%.
Summary of the invention
Through detecting, the component that certain factory produces the waste residue copper sludge that produces in the vat grey BC process per year is following: cupric chloride 3.44%, cupric sulfide 13.44%, sodium sulphite 3.53%, sodium-chlor 3.26%, sodium sulfate 1.67%, water 20.4%, organic impurity 50%.This waste residue copper sludge derives from the filter residue of the filtration procedure of midbody RK production, and 1 ton of vat grey BC of every production produces waste residue copper sludge 989.91kg.
The invention provides and a kind ofly prepare cupric sulfide with the waste residue copper sludge; The method of cupric nitrate and SODIUMNITRATE; Said waste residue copper sludge is for producing the Vat Grey BG gained, and the pollution of dye industry waste residue copper sludge is effectively administered and utilized to this method, also produces various copper bearing compound products; Create considerable economic value, had well-off social benefit and abundant economic benefit simultaneously.
In order to reach above-mentioned purpose, technical scheme of the present invention is: a kind ofly prepare cupric sulfide with the waste residue copper sludge, the method for cupric nitrate and SODIUMNITRATE; Said waste residue copper sludge is for producing the Vat Grey BG gained, and the component of said waste residue copper sludge is following: cupric chloride 3.44%, cupric sulfide 13.44%; Sodium sulphite 3.53%, sodium-chlor 3.26%, sodium sulfate 1.67%; Water 20.4%, organic impurity 50%, this method comprises the steps:
Step (1), weighing waste residue copper sludge with waste residue copper sludge furnishing soup compound, through filtering, obtain cupric sulfide filter cake and filtrating one with service water; The cupric sulfide filter cake is after washing, and drying obtains copper sulphide product;
The molar content of vulcanized sodium in step (2), the calculating filtrating one; Ratio according to vulcanized sodium and the mole of the pure material of hydrogen chloride is 1: 1.6-2.4; The filtrating one of step (1) gained is dropped into corrosion resistant reactor reaction with hydrochloric acid solution; Obtain containing the mixed solution of copper chloride, sodium chloride and sodium sulphate, discharge hydrogen sulfide gas simultaneously; Hydrogen sulfide gas feeds in the alkali lye or through reclaiming and makes hydrosulphuric acid;
Step (3), the mixing solutions that contains cupric chloride, sodium-chlor and sodium sulfate of step (2) gained is filtered, obtain extremely a spot of filter cake impurity and clarifying filtrating;
Step (4), the first air distillation of the clarifying filtrating of step (3) gained is steamed low-boiling organic impurities, mainly contain sodium sulfate, sodium-chlor and three kinds of materials of cupric chloride in the surplus solution;
Step (5): the sodium-chlor in the calculating surplus solution and the molar content sum of cupric chloride, and according to the excessive rare nitric acid of this molar content sum adding, reaction generates cupric nitrate, SODIUMNITRATE and hydrogenchloride through removing by filter a spot of impurity, obtain filtrating two;
Mainly contain cupric nitrate, SODIUMNITRATE, sodium sulfate and hydrogenchloride in step (6), the filtrating two; Calculate the content of sodium sulfate, and add nitrocalcite, make sulfate ion and calcium ion be combined into calcium sulfate and precipitate; And generation SODIUMNITRATE, filtering reacting liquid obtains calcium sulfate precipitation and filtrating three; Mainly contain SODIUMNITRATE, cupric nitrate and hydrogenchloride in the filtrating three
The content of cupric nitrate, SODIUMNITRATE and hydrogenchloride in step (7), the calculating filtrating three, during according to 20 ℃, the solubleness of cupric nitrate is 125g; The solubleness of SODIUMNITRATE is 87.6g, and the 2 20 ℃ of following underpressure distillation of will filtrating make the concentration of SODIUMNITRATE reach supersaturation; And the concentration of cupric nitrate does not reach its saturation concentration; At this moment, the SODIUMNITRATE crystallization is separated out, warp filters, and obtains SODIUMNITRATE and filtrating four; To filtrate four is cooled to 0 ℃, and at this moment, the solubleness of cupric nitrate is 83.5g; The solubleness of SODIUMNITRATE is 73g, and four underpressure distillation of will filtrating make the concentration of cupric nitrate reach supersaturation; And the concentration of SODIUMNITRATE does not reach its saturation concentration, and at this moment, the cupric nitrate crystallization is separated out, warp filters; Obtain cupric nitrate and filtrating five, recycling after filtrating five is mixed also with the soup compound of next round step (1) gained.
The hydrogen sulfide that step (2) is discharged feeds in the alkali lye or through reclaiming and makes hydrosulphuric acid.
Buried or the burning of the filter cake impurity that step (3) obtains.
According to the inventionly prepare cupric sulfide with the waste residue copper sludge, the method for cupric nitrate and SODIUMNITRATE, its chemical equation is:
Na
2S+2HCl＝＝＝＝2NaCl+H
2S
CuCl
2+2HNO
3＝＝＝＝Cu(NO
3)
2+2HCl
NaCl+HNO
3＝＝＝＝NaNO
3+HCl
Na
2SO
4+Ca(NO
3)
2＝＝＝＝2NaNO
3+Ca?SO
4↓
Beneficial effect of the present invention is: saidly prepare cupric sulfide with the waste residue copper sludge, and the method for cupric nitrate and SODIUMNITRATE, simple to operate, facility investment is few, has effectively administered the pollution of dye industry waste residue copper sludge, realizes turning waste into wealth, and has created considerable economic value.
Embodiment
Embodiment 1:
A kind ofly prepare cupric sulfide with the waste residue copper sludge, the method for cupric nitrate and SODIUMNITRATE, said waste residue copper sludge is for producing the Vat Grey BG gained; The component of said waste residue copper sludge is following: cupric chloride 3.44%, cupric sulfide 13.44%, sodium sulphite 3.53%; Sodium-chlor 3.26%, sodium sulfate 1.67%, water 20.4%; Organic impurity 50%, this method comprises the steps:
Step (1), weighing 500kg waste residue copper sludge with waste residue copper sludge furnishing soup compound, through filtering, obtain cupric sulfide filter cake and filtrating one with service water; The cupric sulfide filter cake is after washing, and drying obtains the 67.2kg copper sulphide product;
The molar content of vulcanized sodium in step (2), the calculating filtrating one; Ratio according to vulcanized sodium and the mole of the pure material of hydrogen chloride is 1: 2.4; The filtrating one of step (1) gained is dropped into corrosion resistant reactor reaction with hydrochloric acid solution; Obtain containing the mixed solution of copper chloride, sodium chloride and sodium sulphate, discharge hydrogen sulfide gas simultaneously; Hydrogen sulfide gas feeds in the alkali lye or through reclaiming and makes hydrosulphuric acid;
Step (3), the mixing solutions that contains cupric chloride, sodium-chlor and sodium sulfate of step (2) gained is filtered; Obtain extremely a spot of filter cake impurity and clarifying filtrating; Buried or the burning of filter cake impurity; Contain the about 17.2kg of cupric chloride in the filtrating, the about 42.78kg of sodium-chlor, the about 8.35kg of sodium sulfate;
Step (4), the first air distillation of the clarifying filtrating of step (3) gained is steamed low-boiling organic impurities, mainly contain sodium sulfate, sodium-chlor and three kinds of materials of cupric chloride in the surplus solution;
Step (5): the sodium-chlor in the calculating surplus solution and the molar content sum of cupric chloride, and according to the excessive rare nitric acid of this molar content sum adding, reaction generates cupric nitrate, SODIUMNITRATE and hydrogenchloride through removing by filter a spot of impurity, obtain filtrating two;
Mainly contain cupric nitrate, SODIUMNITRATE, sodium sulfate and hydrogenchloride in step (6), the filtrating two; Calculate the content of sodium sulfate, and add nitrocalcite, make sulfate ion and calcium ion be combined into calcium sulfate and precipitate; And generation SODIUMNITRATE, filtering reacting liquid obtains calcium sulfate precipitation and filtrating three; Mainly contain SODIUMNITRATE, cupric nitrate and hydrogenchloride in the filtrating three
Step (7), the about 19kg of content that calculates cupric nitrate in the filtrating three, the content of SODIUMNITRATE are about 72.1kg, and during according to 20 ℃, the solubleness of cupric nitrate is 125g; The solubleness of SODIUMNITRATE is 87.6g, and the 2 20 ℃ of following underpressure distillation of will filtrating make the concentration of SODIUMNITRATE reach supersaturation; And the concentration of cupric nitrate does not reach its saturation concentration; At this moment, cupric nitrate sodium partial crystallization goes out, warp filters, and obtains SODIUMNITRATE and filtrating four; To filtrate four is cooled to 0 ℃, and at this moment, the solubleness of cupric nitrate is 83.5g; The solubleness of SODIUMNITRATE is 73g, and four underpressure distillation of will filtrating make the concentration of cupric nitrate reach supersaturation; And the concentration of SODIUMNITRATE does not reach its saturation concentration, and at this moment, the cupric nitrate crystallization is separated out, warp filters; Obtain cupric nitrate and filtrating five, recycling after filtrating five is mixed also with the soup compound of next round step (1) gained.
Embodiment 2:
A kind ofly prepare cupric sulfide with the waste residue copper sludge, the method for cupric nitrate and SODIUMNITRATE, said waste residue copper sludge is for producing the Vat Grey BG gained; The component of said waste residue copper sludge is following: cupric chloride 3.44%, cupric sulfide 13.44%, sodium sulphite 3.53%; Sodium-chlor 3.26%, sodium sulfate 1.67%, water 20.4%; Organic impurity 50%, this method comprises the steps:
Step (1), weighing 500kg waste residue copper sludge with waste residue copper sludge furnishing soup compound, through filtering, obtain cupric sulfide filter cake and filtrating one with service water; The cupric sulfide filter cake is after washing, and drying obtains the 67.2kg copper sulphide product;
The molar content of vulcanized sodium in step (2), the calculating filtrating one; Ratio according to vulcanized sodium and the mole of the pure material of hydrogen chloride is 1: 2.0; The filtrating one of step (1) gained is dropped into corrosion resistant reactor reaction with hydrochloric acid solution; Obtain containing the mixed solution of copper chloride, sodium chloride and sodium sulphate, discharge hydrogen sulfide gas simultaneously; Hydrogen sulfide gas feeds in the alkali lye or through reclaiming and makes hydrosulphuric acid;
Step (3), the mixing solutions that contains cupric chloride, sodium-chlor and sodium sulfate of step (2) gained is filtered; Obtain extremely a spot of filter cake impurity and clarifying filtrating; Buried or the burning of filter cake impurity; Contain the about 17.2kg of cupric chloride in the filtrating, the about 42.78kg of sodium-chlor, the about 8.35kg of sodium sulfate;
Step (4), the first air distillation of the clarifying filtrating of step (3) gained is steamed low-boiling organic impurities, mainly contain sodium sulfate, sodium-chlor and three kinds of materials of cupric chloride in the surplus solution;
Step (5): the sodium-chlor in the calculating surplus solution and the molar content sum of cupric chloride, and according to the excessive rare nitric acid of this molar content sum adding, reaction generates cupric nitrate, SODIUMNITRATE and hydrogenchloride through removing by filter a spot of impurity, obtain filtrating two;
Mainly contain cupric nitrate, SODIUMNITRATE, sodium sulfate and hydrogenchloride in step (6), the filtrating two; Calculate the content of sodium sulfate, and add nitrocalcite, make sulfate ion and calcium ion be combined into calcium sulfate and precipitate; And generation SODIUMNITRATE, filtering reacting liquid obtains calcium sulfate precipitation and filtrating three; Mainly contain SODIUMNITRATE, cupric nitrate and hydrogenchloride in the filtrating three
Step (7), the about 19kg of content that calculates cupric nitrate in the filtrating three, the content of SODIUMNITRATE are about 72.1kg, and during according to 20 ℃, the solubleness of cupric nitrate is 125g; The solubleness of SODIUMNITRATE is 87.6g, and the 2 20 ℃ of following underpressure distillation of will filtrating make the concentration of SODIUMNITRATE reach supersaturation; And the concentration of cupric nitrate does not reach its saturation concentration; At this moment, cupric nitrate sodium partial crystallization goes out, warp filters, and obtains SODIUMNITRATE and filtrating four; To filtrate four is cooled to 0 ℃, and at this moment, the solubleness of cupric nitrate is 83.5g; The solubleness of SODIUMNITRATE is 73g, and four underpressure distillation of will filtrating make the concentration of cupric nitrate reach supersaturation; And the concentration of SODIUMNITRATE does not reach its saturation concentration, and at this moment, the cupric nitrate crystallization is separated out, warp filters; Obtain cupric nitrate and filtrating five, recycling after filtrating five is mixed also with the soup compound of next round step (1) gained.
Embodiment 3
A kind ofly prepare cupric sulfide with the waste residue copper sludge, the method for cupric nitrate and SODIUMNITRATE, said waste residue copper sludge is for producing the Vat Grey BG gained; The component of said waste residue copper sludge is following: cupric chloride 3.44%, cupric sulfide 13.44%, sodium sulphite 3.53%; Sodium-chlor 3.26%, sodium sulfate 1.67%, water 20.4%; Organic impurity 50%, this method comprises the steps:
Step (1), weighing 500kg waste residue copper sludge with waste residue copper sludge furnishing soup compound, through filtering, obtain cupric sulfide filter cake and filtrating one with service water; The cupric sulfide filter cake is after washing, and drying obtains the 67.2kg copper sulphide product;
The molar content of vulcanized sodium in step (2), the calculating filtrating one; Ratio according to vulcanized sodium and the mole of the pure material of hydrogen chloride is 1: 1.6; The filtrating one of step (1) gained is dropped into corrosion resistant reactor reaction with hydrochloric acid solution; Obtain containing the mixed solution of copper chloride, sodium chloride and sodium sulphate, discharge hydrogen sulfide gas simultaneously; Hydrogen sulfide gas feeds in the alkali lye or through reclaiming and makes hydrosulphuric acid;
Step (3), the mixing solutions that contains cupric chloride, sodium-chlor and sodium sulfate of step (2) gained is filtered; Obtain extremely a spot of filter cake impurity and clarifying filtrating; Contain the about 113.1kg of cupric chloride in the filtrating, the about 37.5kg of sodium-chlor, the about 8.35kg of sodium sulfate;
Step (4), the first air distillation of the clarifying filtrating of step (3) gained is steamed low-boiling organic impurities, mainly contain sodium sulfate, sodium-chlor and three kinds of materials of cupric chloride in the surplus solution;
Step (5): the sodium-chlor in the calculating surplus solution and the molar content sum of cupric chloride, and according to the excessive rare nitric acid of this molar content sum adding, reaction generates cupric nitrate, SODIUMNITRATE and hydrogenchloride through removing by filter a spot of impurity, obtain filtrating two;
Mainly contain cupric nitrate, SODIUMNITRATE, sodium sulfate and hydrogenchloride in step (6), the filtrating two; Calculate the content of sodium sulfate, and add nitrocalcite, make sulfate ion and calcium ion be combined into calcium sulfate and precipitate; And generation SODIUMNITRATE, filtering reacting liquid obtains calcium sulfate precipitation and filtrating three; Mainly contain SODIUMNITRATE, cupric nitrate and hydrogenchloride in the filtrating three
Step (7), the about 19kg of content that calculates cupric nitrate in the filtrating three, the content of SODIUMNITRATE are about 64.43kg, and during according to 20 ℃, the solubleness of cupric nitrate is 125g; The solubleness of SODIUMNITRATE is 87.6g, and the 2 20 ℃ of following underpressure distillation of will filtrating make the concentration of SODIUMNITRATE reach supersaturation; And the concentration of cupric nitrate does not reach its saturation concentration; At this moment, cupric nitrate sodium partial crystallization goes out, warp filters, and obtains SODIUMNITRATE and filtrating four; To filtrate four is cooled to 0 ℃, and at this moment, the solubleness of cupric nitrate is 83.5g; The solubleness of SODIUMNITRATE is 73g, and four underpressure distillation of will filtrating make the concentration of cupric nitrate reach supersaturation; And the concentration of SODIUMNITRATE does not reach its saturation concentration, and at this moment, the cupric nitrate crystallization is separated out, warp filters; Obtain cupric nitrate and filtrating five, recycling after filtrating five is mixed also with the soup compound of next round step (1) gained.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be regarded as belonging to the scope of patent protection that the present invention is confirmed by claims of being submitted to.
Claims (3)
1. one kind prepares cupric sulfide with the waste residue copper sludge, the method for cupric nitrate and SODIUMNITRATE, and said waste residue copper sludge is for producing the Vat Grey BG gained; The component of said waste residue copper sludge is following: cupric chloride 3.44%, cupric sulfide 13.44%, sodium sulphite 3.53%; Sodium-chlor 3.26%, sodium sulfate 1.67%, water 20.4%; Organic impurity 50% is characterized in that, this method comprises the steps:
Step (1), weighing waste residue copper sludge with waste residue copper sludge furnishing soup compound, through filtering, obtain cupric sulfide filter cake and filtrating one with service water; The cupric sulfide filter cake is after washing, and drying obtains copper sulphide product;
The molar content of sodium sulphite in step (2), the calculating filtrating one; Ratio according to sodium sulphite and the molar weight of the pure substance of hydrogenchloride is 1: 1.6-2.4; The filtrating one of step (1) gained is dropped into corrosion resistant reactor reaction with hydrochloric acid soln; Obtain containing the mixing solutions of cupric chloride, sodium-chlor and sodium sulfate, discharge hydrogen sulfide simultaneously;
Step (3), the mixing solutions that contains cupric chloride, sodium-chlor and sodium sulfate of step (2) gained is filtered, obtain extremely a spot of filter cake impurity and clarifying filtrating;
Step (4), the first air distillation of the clarifying filtrating of step (3) gained is steamed low-boiling organic impurities, mainly contain sodium sulfate, sodium-chlor and three kinds of materials of cupric chloride in the surplus solution;
Step (5): the sodium-chlor in the calculating surplus solution and the molar content sum of cupric chloride, and according to the excessive rare nitric acid of this molar content sum adding, reaction generates cupric nitrate, SODIUMNITRATE and hydrogenchloride through removing by filter a spot of impurity, obtain filtrating two;
Mainly contain cupric nitrate, SODIUMNITRATE, sodium sulfate and hydrogenchloride in step (6), the filtrating two; Calculate the content of sodium sulfate, and add nitrocalcite, make sulfate ion and calcium ion be combined into calcium sulfate and precipitate; And generation SODIUMNITRATE, filtering reacting liquid obtains calcium sulfate precipitation and filtrating three; Mainly contain SODIUMNITRATE, cupric nitrate and hydrogenchloride in the filtrating three
The content of cupric nitrate, SODIUMNITRATE and hydrogenchloride in step (7), the calculating filtrating three, during according to 20 ℃, the solubleness of cupric nitrate is 125g; The solubleness of SODIUMNITRATE is 87.6g, and the 2 20 ℃ of following underpressure distillation of will filtrating make the concentration of SODIUMNITRATE reach supersaturation; And the concentration of cupric nitrate does not reach its saturation concentration; At this moment, the SODIUMNITRATE crystallization is separated out, warp filters, and obtains SODIUMNITRATE and filtrating four; To filtrate four is cooled to 0 ℃, and at this moment, the solubleness of cupric nitrate is 83.5g; The solubleness of SODIUMNITRATE is 73g, and four underpressure distillation of will filtrating make the concentration of cupric nitrate reach supersaturation; And the concentration of SODIUMNITRATE does not reach its saturation concentration, and at this moment, the cupric nitrate crystallization is separated out, warp filters; Obtain cupric nitrate and filtrating five, recycling after filtrating five is mixed also with the soup compound of next round step (1) gained.
2. as claimed in claim 1ly prepare cupric sulfide with the waste residue copper sludge, the method for cupric nitrate and SODIUMNITRATE, said waste residue copper sludge is characterized in that for producing the Vat Grey BG gained hydrogen sulfide that step (2) is discharged feeds in the alkali lye or through reclaiming and makes hydrosulphuric acid.
3. as claimed in claim 1ly prepare cupric sulfide with the waste residue copper sludge, the method for cupric nitrate and SODIUMNITRATE, said waste residue copper sludge is characterized in that for producing the Vat Grey BG gained, the filter cake impurity that step (3) obtains is buried or burn.
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|---|---|---|---|
| CN2011101827751A CN102367177A (en) | 2011-07-01 | 2011-07-01 | Method for preparing copper sulfide, cupric nitrate and sodium nitrate with residual copper sludge |
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|---|---|---|---|
| CN2011101827751A CN102367177A (en) | 2011-07-01 | 2011-07-01 | Method for preparing copper sulfide, cupric nitrate and sodium nitrate with residual copper sludge |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279293A (en) * | 2020-11-02 | 2021-01-29 | 贵州理工学院 | Preparation method of copper sulfide nano material |
-
2011
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279293A (en) * | 2020-11-02 | 2021-01-29 | 贵州理工学院 | Preparation method of copper sulfide nano material |
| CN112279293B (en) * | 2020-11-02 | 2023-08-25 | 贵州理工学院 | Preparation method of copper sulfide nano material |
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Address after: 523000, room five, building 508, Jinhai building, Dongcheng District Tong Road, Dongguan, Guangdong Applicant after: Wang Jiaxing Address before: Wushi Village Primary School in Dongguan city of Dongcheng District province Guangdong road 523000 Lane 1 No. 6 main mountain Applicant before: Wang Jiaxing |
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Application publication date: 20120307 |