CN102795653A - Method for recycling copper oxide and zinc oxide from organosilicon spent contact mass - Google Patents
Method for recycling copper oxide and zinc oxide from organosilicon spent contact mass Download PDFInfo
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- CN102795653A CN102795653A CN2011101360918A CN201110136091A CN102795653A CN 102795653 A CN102795653 A CN 102795653A CN 2011101360918 A CN2011101360918 A CN 2011101360918A CN 201110136091 A CN201110136091 A CN 201110136091A CN 102795653 A CN102795653 A CN 102795653A
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- waste catalyst
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- ammonium salt
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Abstract
The invention relates to the field of recycling of organosilicon spent contact masses, particularly a method for recycling copper oxide and zinc oxide from an organosilicon spent contact mass, which comprises the following steps: 1) extracting a spent contact mass with an oxidizer-containing ammonia-ammonium salt mixed solution at 20-100 DEG C for 1-8 hours, separating to obtain a copper-ammonia zinc-ammonia complex solution and a solid, and washing and drying the solid to obtain silicon powder; 2) evaporating ammonia from the copper-ammonia zinc-ammonia complex solution at 40-100 DEG C for 1-10 hours to precipitate a copper compound precipitate, separating to obtain the precipitate and a zinc-containing mother solution, washing the precipitate, drying and roasting to obtain copper oxide powder; and 3) adding an ammonium salt into the zinc-containing mother solution obtained in the step 2), regulating the temperature to 20-80 DEG C and the pH value to 4-8 to obtain a basic zinc carbonate precipitate, separating, washing, drying and roasting to obtain zinc oxide powder. The yield and purity of the copper oxide obtained by treating the spent contact mass with an ammonia process are respectively higher than 95%.
Description
Technical field
The present invention relates to the organosilicon waste catalyst and reclaim the field, particularly, the present invention relates to the method that a kind of organosilicon waste catalyst reclaims cupric oxide and zinc oxide.
Background technology
In organic silicon production process, silicon and methyl chloride are as raw materials for production, and ternary copper catalyst (Primary Catalysts) and zinc (auxiliary agent) are commonly used to promote the synthetic of an organosilane monomer such as dimethyl-methylene dichloride.After silica flour transformation efficiency and methyl chlorosilane monomer selectivity acquire a certain degree, need react residue silica flour and spent catalyst discharge reactor drum, the formation industrial residue is called the organosilicon waste catalyst.The waste catalyst staple is a silicon, copper, and carbon, zinc etc., their weight contents in waste catalyst are respectively 65%～80%, and 3%～20%, 1%～10%, 0.05%～2.0%.Waste catalyst is because particle is tiny, and copper powder is active higher, meets air oxidizing reaction takes place easily, makes wherein organic substance and the carbon burning pungent white cigarette of emerging, difficult storage, and environmental pollution is serious, has serious " three wastes " problem.Abroad as far back as last century the fifties just carried out the recycling research (US5306328 of organosilicon waste catalyst; US4758352); The treatment process that adopts is mainly acid oxidation dipping bond replacement(metathesis)reaction and reclaims copper; Promptly through oxidizing acid such as nitric acid, the vitriol oil or contain the acid solution dipping waste catalyst of oxygenants such as ydrogen peroxide 50, Youxiaolin; The bivalent cupric ion that copper catalyst in the waste catalyst is changed into solubility enters into acid solution, adds reductive agent such as reduced iron powder then or zinc dust precipitation copper obtains copper powder.Yet the acid solution that has oxidisability in the above-mentioned technology is to the treatment facility seriously corroded, and the sour discharge of wastewater that forms in the treating processes is difficult; Cause easily second environmental pollution; And reductive agent also iron powder or zinc powder needs to reclaim, and treatment process is comparatively loaded down with trivial details, and cost is higher.Present domestic organosilicon enterprise generally is through burying or sell to small business at a low price, not carrying out the recycling of waste catalyst to the processing mode of waste catalyst.Domestic each scientific research institution then mainly adopts external treatment process to reclaim copper to the research of waste catalyst processing recovery copper, and (CN1083418A CN1844422A), does not also have other more environmental protection, more economical related process to study.Along with the expansion of China's methyl chlorosilane throughput in recent years; This monomer output had broken through 1,500,000 tons in 2010; Expect 2012 annual capacities and will reach 2,500,000 tons; The waste catalyst that produces reaches 90,000 tons, causes serious environmental issue and safety-problems, has become the bottleneck of restriction organosilicon enterprise development.Therefore; Solve " three wastes " problem of waste catalyst; Carrying out the research of environment-friendly type and Eco-power waste catalyst harmless treatment process recovery copper is the technical barrier that current field of organic silicon must solve; It reduces cost, reduces pollution to organosilicon enterprise, and the sound development that promotes China's organosilicon industry is extremely important.
Summary of the invention
The objective of the invention is to for overcome in the present field of organic silicon waste catalyst handle reclaim process for copper exist technical process complicated, be prone to environment is caused secondary pollution and the high problem of processing cost, provide a kind of organosilicon waste catalyst to reclaim the method for cupric oxide and zinc oxide.
Method according to organosilicon waste catalyst recovery cupric oxide of the present invention and zinc oxide said method comprising the steps of:
1) under 20～100 ℃, adopt the ammonia-ammonium salt mixing solutions contain oxygenant that waste catalyst is leached, leaching time 1～8h obtains the complex solution and the solid of cuprammonium, zinc ammonia after the separation, solids wash is dry, obtains silica flour;
The complex solution of the cuprammonium that 2) step 1) is obtained, zinc ammonia is at 40～100 ℃ of following ammonia still process 1～10h; Separate out the compound precipitation of copper; Separate and obtain deposition and zinciferous mother liquor; With obtaining cupric oxide powder after washing of precipitate, drying, the roasting, the ammonia that steams simultaneously absorbs with ammoniacal liquor, returns in the step 1) to recycle;
3) to step 2) in add ammonium salt in the zinciferous mother liquor that obtains; 20～80 ℃ of attemperation, pH value 4～8; Obtain zinc subcarbonate deposition,, simultaneously the mother liquor that obtains ammonium salt-containing after the spinning turned back to 1 through separating, obtaining Zinc oxide powder after the washing, drying, roasting) in recycle.
According to the method for organosilicon waste catalyst recovery cupric oxide of the present invention and zinc oxide, described oxygenant is air, oxygen or ydrogen peroxide 50.
Reclaim the method for cupric oxide and zinc oxide according to organosilicon waste catalyst of the present invention, ammonia is commercialization ammoniacal liquor in described ammonia-ammonium salt mixed solution, and ammonium salt is a kind of in ammonium chloride, volatile salt or the bicarbonate of ammonia.
According to the method for organosilicon waste catalyst recovery cupric oxide of the present invention and zinc oxide, the mol ratio of ammonia and ammonium salt is 1: 1.5～5 in described ammonia-ammonium salt mixed solution, and the mass ratio of ammonia-ammonium salt mixture and waste catalyst is 1: 1～2.
According to the method for organosilicon waste catalyst recovery cupric oxide of the present invention and zinc oxide, described maturing temperature is 200～800 ℃.
The principal reaction that each step of the present invention takes place is following:
1)Cu+1/2O
2+(NH
4)
2CO
3+2NH
3→[Cu(NH
3)
4]
2++CO
3 2-+H
2O
CuO+(NH
4)
2CO
3+2NH
3→[Cu(NH
3)
4]
2++CO
3 2-+H
2O
Cu
2O+1/2O
2+2(NH
4)
2CO
3+4NH
3→2[Cu(NH
3)
4]
2++2CO
3 2-+2H
2O
Zn+1/2O
2+(NH
4)
2CO
3+2NH
3→[Zn(NH
3)
4]
2++CO
3 2-+H
2O
2)[Cu(NH
3)
4]
2+→Cu
2++4NH
3
2Cu
2++CO
3 2-+2OH
-→Cu
2(OH)
2CO
3(s)↓
Cu
2(OH)
2CO
3(s)→2CuO+CO
2↑+H
2O
3)3Zn(NH
3)
4CO
3+2H
2O→ZnCO
3·2Zn(OH)
2(s)↓+12NH
3+2CO
2↑
ZnCO
3·2Zn(OH)
2→3ZnO+CO
2↑+2H
2O
In the present invention, through ammonia process handle waste catalyst and control metals ion and complexing ion between ratio, make copper and the zinc oxidation in the waste catalyst and form complex compound entering solution; Different according to cupric ammine complex and zinc ammonia complex stability then, controlled temperature decomposes cupric ammine complex, is precipitated out; Realize separating of cupric ion and zine ion; Calcining at last obtains zinc oxide and cupric oxide, has realized ammonia in the method simultaneously and has contained recycling of ammonium mother liquor, and flow process is short, efficient is high, be beneficial to mass-producing handles; While entire treatment process material reusable edible; Three-waste free discharge is avoided environment is produced secondary pollution, thereby the green that realizes waste catalyst is handled.
The waste catalyst treatment process that the present invention proposes is compared with existing method and is had the following advantages:
1, the present invention adopts ammonia process processing waste catalyst to compare with the acid technological process that extensively adopts at present; Flow process is short, efficient is high, be beneficial to mass-producing handles, while entire treatment process material reusable edible, three-waste free discharge; Avoid environment is produced secondary pollution, thereby the green that realizes waste catalyst is handled.
2, the present invention adopts ammonia process processing waste catalyst lower to the corrodibility of operational outfit than acid technological process, and the material reusable edible reduces processing cost greatly, has high economic benefit.
3, the present invention adopts ammonia process to handle cupric oxide yield and the purity that waste catalyst obtains all to be higher than 95%.
Description of drawings
Fig. 1 is the schema that ammonia leaching process of the present invention is handled organosilicon waste catalyst method;
Fig. 2 is the XRD spectra of organosilicon waste catalyst of the present invention;
Fig. 3 handles the XRD spectra that the organosilicon waste catalyst reclaims silica flour for ammonia leaching process of the present invention;
Fig. 4 handles the XRD spectra that the organosilicon waste catalyst reclaims cupric oxide for ammonia leaching process of the present invention;
Fig. 5 handles the XRD spectra that the organosilicon waste catalyst reclaims by product zinc oxide for ammonia leaching process of the present invention.
Embodiment
Following examples further specify the present invention, but the present invention is not limited to following examples.
Embodiment 1.
72.0kg ammoniacal liquor (25.0wt%) and 34.0kg volatile salt joined be made into mixed solution (mol ratio of ammonia and volatile salt is 3.0) in the 250.0kg water; Add 100.0kg waste catalyst (cupric 15.0wt%, zinc 1.5wt% then; Ammonia-ammonium salt and waste catalyst mass ratio are 1.06), stir 8h at 20 ℃ of blowing airs, after filtration or spinning; With solid slag washing, drying, obtain silica flour 80.0kg.Mother liquor after the spinning is warming up to 40 ℃, and insulation 10h produces a large amount of blue-greenish colour depositions in the solution, and the ammonia of overflowing simultaneously absorbs the raw material that can be used as the dipping waste catalyst with 10wt% ammoniacal liquor and recycles.After filtration or the spinning, with throw out washing, drying, at 450 ℃ of roasting 5h, obtain 18.0kg finished product cupric oxide, purity is 97%, and total yield is 96%.Add the 2.5kg volatile salt in the mother liquor after separating, 20 ℃ of temperature of reaction, pH value are 4.0; Separate out white precipitate in the solution, after filtration or the spinning, with throw out washing, drying; Obtain 1.80kg zinc oxide at 600 ℃ of roasting 4h, total yield 96%, purity is 97%.The raw material that mother liquor after the separation returns as the dipping waste catalyst recycles.
Above-mentioned cupric oxide that from waste catalyst, extracts and zinc oxide are carried out the XRD test at the X ' Pert PRO MPD type multi-functional X-ray diffractometer of Dutch Panalytical company (PANalytical) production.
Fig. 2 is the XRD spectra of organosilicon waste catalyst, and wherein 2 θ are the diffraction peak characteristic diffraction peak of corresponding silicon, copper and zinc respectively of 28.4 °, 36.4 ° and 43.3 °, show and mainly contain silicon, copper and zinc in the waste catalyst.
Fig. 3 is the XRD spectra that reclaims silica flour among the embodiment 1 behind the ammonia leaching process processing waste catalyst; Wherein 2 θ are that 28.4 ° diffraction peak is the characteristic diffraction peak of silicon; The diffraction peak that other copper catalyst and zinc are not arranged shows and adopts ammonia process dipping waste catalyst to realize that copper, zinc separate with silicon.
Fig. 4 is the XRD spectra of the cupric oxide powder that obtains after waste catalyst being handled among the embodiment 1; Wherein the 2 θ diffraction peak that is respectively 35.5 ° and 38.9 ° is the characteristic diffraction peak of cupric oxide; The diffraction peak that other material is not arranged shows that the present invention adopts ammonia leaching process to handle waste catalyst technology and can access pure zirconia copper.
Fig. 5 is the XRD spectra of the by product zinc oxide that obtains after handling in 1 pair of waste catalyst of embodiment; Wherein the 2 θ diffraction peak that is respectively 31.9 °, 34.6 ° and 36.4 ° is the characteristic diffraction peak of zinc oxide; The diffraction peak that other material is not arranged shows that the by product that adopts ammonia leaching process processing waste catalyst technology to obtain is a pure zinc oxide.
Embodiment 2.
80.0kg ammoniacal liquor (25.0wt%) and 45.0kg volatile salt joined be made into mixed solution (mol ratio of ammonia and volatile salt is 2.5) in the 200kg water; Add 100.0kg waste catalyst (cupric 15.0wt%, zinc 1.5wt% then; Ammonia-ammonium salt and waste catalyst mass ratio are 1.25), stir 6h at 70 ℃ of blowing airs, after filtration or spinning; With solid slag washing, drying, obtain silica flour 78.0kg.Mother liquor after separating is warming up to 80 ℃, and insulation 5h produces a large amount of blue-greenish colour depositions in the solution, and the ammonia of overflowing simultaneously absorbs the raw material that can be used as the dipping waste catalyst with 10wt% ammoniacal liquor and recycles.After filtration or the spinning, with throw out washing, drying, at 500 ℃ of roasting 4h, obtain 18.5kg finished product cupric oxide, purity is 96%, and total yield is 98%.Add the 3.5kg volatile salt in the mother liquor after separating, 60 ℃ of temperature of reaction, pH value are 7.0; Separate out white precipitate in the solution, after filtration or the spinning, with throw out washing, drying; Obtain 1.83kg zinc oxide at 500 ℃ of roasting 5h, total yield 98%, purity is 96%.The raw material that mother liquor after the separation returns as the dipping waste catalyst recycles.
Embodiment 3.
91.0kg ammoniacal liquor (25.0wt%) and 40.0kg volatile salt joined be made into mixed solution (mol ratio of ammonia and volatile salt is 3.2) in the 200kg water; Add 100.0kg waste catalyst (cupric 15.0wt%, zinc 1.5wt% then; Ammonia-ammonium salt and waste catalyst mass ratio are 1.31), stir 1h at 100 ℃ of blowing airs, after filtration or spinning; With solid slag washing, drying, obtain silica flour 79.5kg.Mother liquor after the spinning is warming up to 100 ℃, and insulation 1h produces a large amount of blue-greenish colour depositions in the solution, and the ammonia of overflowing simultaneously absorbs the raw material that can be used as the dipping waste catalyst with 10wt% ammoniacal liquor and recycles.After filtration or the spinning, with throw out washing, drying, at 500 ℃ of roasting 6h, obtain 18.2kg finished product cupric oxide, purity is 96%, and total yield is 97%.Add the 4.0kg volatile salt in the mother liquor after separating, 80 ℃ of temperature of reaction, pH value are 8.0; Separate out deposition in the solution, after filtration or the spinning, with throw out washing, drying; Obtain 1.80kg zinc oxide at 500 ℃ of roasting 5h, total yield 96%, purity is 95%.The raw material that mother liquor after the separation returns as the dipping waste catalyst recycles.
Embodiment 4.
107.0kg ammoniacal liquor (25.0wt%) and 50.0kg bicarbonate of ammonia joined be made into mixed solution (mol ratio of ammonia and bicarbonate of ammonia is 2.5) in the 200kg water; Add 100.0kg waste catalyst (cupric 15.0wt%, zinc 1.5wt% then; Ammonia-ammonium salt and waste catalyst mass ratio are 1.57), stir 5h at 80 ℃ of blowing airs, after filtration or spinning; With solid slag washing, drying, obtain silica flour 79.0kg.Mother liquor after separating is warming up to 80 ℃, and insulation 5h produces a large amount of blue-greenish colour depositions in the solution, and the ammonia of overflowing simultaneously absorbs the raw material that can be used as the dipping waste catalyst with 10wt% ammoniacal liquor and recycles.After filtration or the spinning, with throw out washing, drying, at 500 ℃ of roasting 5h, obtain 17.8kg finished product cupric oxide, purity is 96%, and total yield is 95%.Add the 3.5kg volatile salt in the mother liquor after separating, 60 ℃ of temperature of reaction, pH value are 7.0; Separate out deposition in the solution, after filtration or the spinning, with throw out washing, drying; Obtain 1.79kg zinc oxide at 500 ℃ of roasting 5h, total yield 96%, purity is 98%.The raw material that mother liquor after the separation returns as the dipping waste catalyst recycles.
Embodiment 5.
117.0kg ammoniacal liquor (25.0wt%) and 45.5kg bicarbonate of ammonia joined be made into mixed solution (mol ratio of ammonia and bicarbonate of ammonia is 3.0) in the 230kg water; Add 100.0kg waste catalyst (cupric 15.0wt%, zinc 1.5wt% then; Ammonia-ammonium salt and waste catalyst mass ratio are 1.62), stir 6h at 70 ℃ of blowing airs, after filtration or spinning; With solid slag washing, drying, obtain silica flour 78.8kg.Mother liquor after separating is warming up to 80 ℃, and insulation 6h produces a large amount of blue-greenish colour depositions in the solution, and the ammonia of overflowing simultaneously absorbs the raw material that can be used as the dipping waste catalyst with 10wt% ammoniacal liquor and recycles.After filtration or the spinning, with throw out washing, drying, at 500 ℃ of roasting 5h, obtain 18.2kg finished product cupric oxide, purity is 95%, and total yield is 96%.Add the 3.0kg volatile salt in the mother liquor after separating, 70 ℃ of temperature of reaction, pH value are 6.5; Separate out deposition in the solution, after filtration or the spinning, with throw out washing, drying; Obtain 1.8kg zinc oxide at 500 ℃ of roasting 5h, total yield 96%, purity is 96%.The raw material that mother liquor after the separation returns as the dipping waste catalyst recycles.
Embodiment 6.
71.0kg ammoniacal liquor (25.0wt%) and 50.0kg volatile salt joined be made into mixed solution (mol ratio of ammonia and volatile salt is 2) in the 200kg water; Add 100.0kg waste catalyst (cupric 15.0wt%, zinc 1.5wt% then; Ammonia-ammonium salt and waste catalyst mass ratio are 1.21), stir 6h at 80 ℃ of blowing airs, after filtration or spinning; With solid slag washing, drying, obtain silica flour 80.5kg.Mother liquor after separating is warming up to 80 ℃, and insulation 5h produces a large amount of blue-greenish colour depositions in the solution, and the ammonia of overflowing simultaneously absorbs the raw material that can be used as the dipping waste catalyst with 10wt% ammoniacal liquor and recycles.After filtration or the spinning, with throw out washing, drying, at 500 ℃ of roasting 6h, obtain 18.5kg finished product cupric oxide, purity is 96%, and total yield is 99%.Add the 4.0kg volatile salt in the mother liquor after separating, 60 ℃ of temperature of reaction, pH value are 7.5; Separate out deposition in the solution, after filtration or the spinning, with throw out washing, drying; Obtain 1.82kg zinc oxide at 500 ℃ of roasting 5h, total yield 97%, purity is 97%.The raw material that mother liquor after the separation returns as the dipping waste catalyst recycles.
Claims (5)
1. an organosilicon waste catalyst reclaims the method for cupric oxide and zinc oxide, it is characterized in that, said method comprising the steps of:
1) under 20～100 ℃, adopt the ammonia-ammonium salt mixing solutions that contains oxygenant that waste catalyst is leached, leaching time is 1～8h, obtains the complex solution and the solid of cuprammonium, zinc ammonia after the separation, and solids wash is dry, obtains silica flour;
The complex solution of the cuprammonium that 2) step 1) is obtained, zinc ammonia is at 40～100 ℃ of following ammonia still process 1～10h; Separate out the compound precipitation of copper; Separate and obtain deposition and zinciferous mother liquor; With obtaining cupric oxide powder after washing of precipitate, drying, the roasting, the ammonia that steams simultaneously absorbs with ammoniacal liquor, returns in the step 1) to recycle;
3) to step 2) add ammonium salt in the zinciferous mother liquor that obtains; Regulate 20～80 ℃ of pH value 4～8, temperature; Obtain zinc subcarbonate deposition,, simultaneously the mother liquor that obtains ammonium salt-containing after the spinning turned back to 1 through separating, obtaining Zinc oxide powder after the washing, drying, roasting) in recycle.
2. organosilicon waste catalyst according to claim 1 reclaims the method for cupric oxide and zinc oxide, it is characterized in that the oxygenant in the said step 1) is air, oxygen or ydrogen peroxide 50.
3. organosilicon waste catalyst according to claim 1 reclaims the method for cupric oxide and zinc oxide, it is characterized in that ammonia is ammoniacal liquor in ammonia in the said step 1)-ammonium salt mixed solution, and ammonium salt is ammonium chloride, volatile salt or bicarbonate of ammonia.
4. organosilicon waste catalyst according to claim 1 reclaims the method for cupric oxide and zinc oxide; It is characterized in that; In described step 1), the mol ratio of ammonia and ammonium salt is 1: 1.5～5 in ammonia-ammonium salt mixed solution, and the mass ratio of ammonia-ammonium salt mixture and waste catalyst is 1: 1～2.0.
5. organosilicon waste catalyst according to claim 1 reclaims the method for cupric oxide and zinc oxide, it is characterized in that said step 2) and 3) in maturing temperature be 200～800 ℃.
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Cited By (6)
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| CN104843721A (en) * | 2015-04-30 | 2015-08-19 | 中国科学院过程工程研究所 | Organic silicon waste contact recovery method |
| CN106082302A (en) * | 2016-06-12 | 2016-11-09 | 上海大学 | A kind of method directly being prepared Cu-lyt. by copper oxide |
| CN109319790A (en) * | 2018-11-09 | 2019-02-12 | 成都蜀菱科技发展有限公司 | A kind of method and chlorosilane product using fine silica powder production chlorosilane |
| CN112210669A (en) * | 2020-09-04 | 2021-01-12 | 鲁西化工集团股份有限公司硅化工分公司 | Continuous purification device and process for organic silicon copper-containing contact |
| CN114644339A (en) * | 2022-04-29 | 2022-06-21 | 成都理工大学 | Method for removing impurities in silicon by adopting inorganic zinc salt |
| CN114787083A (en) * | 2019-12-06 | 2022-07-22 | 三菱综合材料株式会社 | Method for producing copper oxide powder and copper oxide powder |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843721A (en) * | 2015-04-30 | 2015-08-19 | 中国科学院过程工程研究所 | Organic silicon waste contact recovery method |
| CN106082302A (en) * | 2016-06-12 | 2016-11-09 | 上海大学 | A kind of method directly being prepared Cu-lyt. by copper oxide |
| CN109319790A (en) * | 2018-11-09 | 2019-02-12 | 成都蜀菱科技发展有限公司 | A kind of method and chlorosilane product using fine silica powder production chlorosilane |
| CN114787083A (en) * | 2019-12-06 | 2022-07-22 | 三菱综合材料株式会社 | Method for producing copper oxide powder and copper oxide powder |
| CN112210669A (en) * | 2020-09-04 | 2021-01-12 | 鲁西化工集团股份有限公司硅化工分公司 | Continuous purification device and process for organic silicon copper-containing contact |
| CN112210669B (en) * | 2020-09-04 | 2022-03-04 | 鲁西化工集团股份有限公司硅化工分公司 | Continuous purification device and process for organic silicon copper-containing contact |
| CN114644339A (en) * | 2022-04-29 | 2022-06-21 | 成都理工大学 | Method for removing impurities in silicon by adopting inorganic zinc salt |
| CN114644339B (en) * | 2022-04-29 | 2023-04-25 | 成都理工大学 | Method for removing impurities in silicon by adopting inorganic zinc salt |
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| CN102795653B (en) | 2014-09-24 |
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