CN101007656A - Waste molybdenum nickel cobalt catalyst utilization method for environmental protection - Google Patents
Waste molybdenum nickel cobalt catalyst utilization method for environmental protection Download PDFInfo
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- CN101007656A CN101007656A CN 200610097148 CN200610097148A CN101007656A CN 101007656 A CN101007656 A CN 101007656A CN 200610097148 CN200610097148 CN 200610097148 CN 200610097148 A CN200610097148 A CN 200610097148A CN 101007656 A CN101007656 A CN 101007656A
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- 239000002699 waste material Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 title claims description 20
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 title claims description 10
- 230000007613 environmental effect Effects 0.000 title description 4
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229940078494 nickel acetate Drugs 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 6
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 6
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims description 6
- -1 iron ions Chemical class 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001238 wet grinding Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910017709 Ni Co Inorganic materials 0.000 abstract 1
- 229910003267 Ni-Co Inorganic materials 0.000 abstract 1
- 229910003262 Ni‐Co Inorganic materials 0.000 abstract 1
- 239000003426 co-catalyst Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 2
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an environment protective utilizing method of waste Mo-Ni-Co catalyst, which comprises the following step: adding different reacting materials into raw material; separating different products according to different chemical properties of metal salt and different conditions step by step; making the product.
Description
Technical Field
The invention relates to an environment-friendly method for recycling waste metal, in particular to an environment-friendly method for utilizing molybdenum, nickel and cobalt in a waste molybdenum nickel cobalt catalyst used in a catalyst in the petrochemical industry.
Background
In the molybdenum-nickel-cobalt catalyst widely used in the petrochemical industry, 16-30% of molybdenum, 6-8% of nickel and about 4% of cobalt exist in the catalyst in the form of oxides, and other components mainly comprise a small amount of silicon oxides and adsorbed organic impurities, so that the catalyst can cause great pollution to the environment after being wasted, and if the catalyst can be effectively recycled, the catalyst has considerable environmental protection and economic values. But at present, a recycling method which has environmental protection value and better economic benefit does not exist.
Disclosure of Invention
The invention aims to provide an environment-friendly utilization method of a waste molybdenum nickel cobalt catalyst with environmental protection and economic value. The technical scheme for realizing the purpose is as follows:
the environment-friendly utilization method of the waste molybdenum nickel cobalt catalyst comprises the following steps:
a, roasting the waste molybdenum nickel catalyst at the temperature of 500-;
b, adding sodium hydroxide into the raw material particles, reacting at 75-90 ℃ to generate a sodium molybdate solution, and filtering;
c, adding sulfuric acid into the filtrate obtained in the step b, adjusting the pH value to 4-5, and drying the filtered precipitate to obtain a molybdenum oxide product;
d, adding sulfuric acid into the filter residue filtered in the step b, adjusting the pH value to 1-1.5 to generate a nickel sulfate solution and a cobalt sulfate solution, filtering out impurities, adding sodium carbonate into the filtrate to adjust the pH value ofthe solution to be alkaline to generate cobalt carbonate and nickel carbonate precipitates, heating the solution to more than 60 ℃, introducing air for bubbling, converting the generated cobalt carbonate precipitate into a basic cobalt carbonate precipitate, and filtering the solution;
e, adding dilute acetic acid into the filter residue obtained after the final filtration in the step d, reacting to generate a nickel acetate solution, filtering the mixed solution, obtaining a nickel acetate product after conventional treatment, wherein the filter residue is basic cobalt carbonate precipitate, drying, and calcining at 600 ℃ to obtain a cobalt oxide product.
Further, after wet grinding in the step a, the raw material particles are selected by a 300-mesh screen and then used as raw material particles.
Or after the nickel sulfate and cobalt sulfate solution is generated in the step d, adding sodium hydroxide to adjust the pH value of the solution to 4, adding hydrogen peroxide to oxidize a small amount of low-valence iron ions in the solution into high-valence iron ions, precipitating and filtering to remove impurity iron in the solution; after impurities are filtered out, sodium carbonate is added to adjust the pH value of the solution to 8; the heating temperature is 80 ℃.
In addition, after the nickel acetate product is prepared in the step e, the nickel acetate product is roasted to obtain a nickel oxide product.
The main chemical reaction equations related to the technical scheme and the technical measures are as follows:
MoO3+NaOH—→Na2MoO4+H2O
Na2MoO4+H2SO4—→MoO3↓+Na2SO4
NiO+H2SO4—→NiSO4+H2O
CoO+H2SO4—→CoSO4+H2O
NiSO4+Na2CO3—→NiCO3↓+Na2SO
CoSO4+Na2CO3—→CoCO3↓+Na2SO
CoCO3+OH-—→Co(OH)CO3↓
NiCO3+HAc—→Ni(Ac)2
the method has the advantages that the precious molybdenum, nickel and cobalt in the waste molybdenum, nickel and cobalt catalyst can be recycled, no environmental pollution is caused in the production process, and the method has higher social and economic benefits.
Detailed Description
The following are specific embodiments of the present invention:
after organic impurities (mainly generated during catalysis in the petrochemical reaction process) of the waste molybdenum-nickel catalyst are removed by roasting at 500 ℃, the waste molybdenum-nickel catalyst is humidified, ground and sieved by a 300-mesh screen to prepare raw material particles; adding sodium hydroxide into the raw material particles, reacting at 80 ℃ to generate a sodium molybdate solution, adding sulfuric acid into the filtered filtrate, adjusting the pH value to 4 to generate a molybdenum oxide precipitate, filtering the precipitate, and drying to obtain a molybdenum oxide product; adding sodium hydroxide into raw material particles, reacting and filtering the obtained product at 80 ℃, adding sulfuric acid into the obtained filter residue, adjusting the pH value to 1 to generate a nickel sulfate and cobalt sulfate solution, adding sodium hydroxide to adjust the pH value of the solution to 4, adding hydrogen peroxide to oxidize a small amount of low-valence iron ions in the solution into high-valence iron ions for precipitation, and filtering to remove impurity iron in the solution; filtering to remove impurities, adding sodium carbonate into the filtrate to adjust the pH of the solution to 8 to generate cobalt carbonate and nickel carbonate precipitates, heating the solution to 80 ℃, introducing air for bubbling to convert the generated cobalt carbonate precipitates into basic cobalt carbonate precipitates, and filtering the solution; adding dilute acetic acid into the filter residue, reacting to generate nickel acetate solution, filtering the mixed solution, obtaining nickel acetate product after conventional treatment by using the filtrate as nickel acetate, and roasting the nickel acetate product to obtain the nickel oxide product. The filter residue is basic cobalt carbonate precipitate, and is calcined into a cobalt oxide product at 600 ℃ after being dried.
Claims (4)
1. The environment-friendly utilization method of the waste molybdenum nickel cobalt catalyst is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
a, roasting the waste molybdenum nickel catalyst at the temperature of 500-;
b, adding sodium hydroxide into the raw material particles, reacting at 75-90 ℃ to generate a sodium molybdate solution, and filtering;
c, adding sulfuric acid into the filtrate obtained in the step b, adjusting the pH value to 4-5, and drying the filtered precipitate to obtain a molybdenum oxide product;
d, adding sulfuric acid into the filter residue filtered in the step b, adjusting the pH value to 1-1.5 to generate a nickel sulfate solution and a cobalt sulfate solution, filtering out impurities, adding sodium carbonate into the filtrate to adjust the pH value of the solution to be alkaline to generate cobalt carbonate and nickel carbonate precipitates, heating the solution to more than 60 ℃, introducing air for bubbling, converting the generated cobalt carbonate precipitate into a basic cobalt carbonate precipitate, and filtering the solution;
e, adding dilute acetic acid into the filter residue obtained after the final filtration in the step d, reacting to generate a nickel acetate solution, filtering the mixed solution, obtaining a nickel acetate product after conventional treatment, wherein the filter residue is basic cobalt carbonate precipitate, drying, and calcining at 600 ℃ to obtain a cobalt oxide product.
2. The method for environmentally utilizing a waste molybdenum nickel cobalt catalyst as claimed in claim 1, wherein: and in the step a, after wet grinding, selecting materials by a 300-mesh screen to serve as raw material particles.
3. The method for environmentally utilizing a waste molybdenum nickel cobalt catalyst as claimed in claim 1, wherein: after the nickel sulfate and cobalt sulfate solution is generated in the step d, adding sodium hydroxide to adjust the pH value of the solution to 4, adding hydrogen peroxide to oxidize a small amount of low-valence iron ions in the solution into high-valence iron ions, precipitating and filtering to remove impurity iron in the solution; after impurities are filtered out, sodium carbonate is added to adjust the pH value of the solution to 8; the heating temperature is 80 ℃.
4. The method for environmentally utilizing a waste molybdenum nickel cobalt catalyst as claimed in claim 1, wherein: and e, roasting the nickel acetate product to obtain a nickel oxide product after the nickel acetate product is prepared in the step e.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100971487A CN100427406C (en) | 2006-10-25 | 2006-10-25 | Waste molybdenum nickel cobalt catalyst utilization method for environmental protection |
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| CNB2006100971487A CN100427406C (en) | 2006-10-25 | 2006-10-25 | Waste molybdenum nickel cobalt catalyst utilization method for environmental protection |
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| CN101007656A true CN101007656A (en) | 2007-08-01 |
| CN100427406C CN100427406C (en) | 2008-10-22 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101435027B (en) * | 2007-11-15 | 2010-06-02 | 中国石油化工股份有限公司 | Method for recycling high purity molybdenum from molybdenum-containing spent catalyst |
| CN101724758B (en) * | 2008-10-29 | 2011-04-06 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method for recycling molybdenum of molybdenum-contained waste catalyst |
| CN103343232A (en) * | 2013-07-11 | 2013-10-09 | 岳阳鼎格云天环保科技有限公司 | Method for recycling Ni from waste FCC (Fluid Catalytic Cracking) catalyst |
| CN103849772A (en) * | 2012-11-28 | 2014-06-11 | 大连东泰产业废弃物处理有限公司 | Method for recovering metal cobalt by N,N'-1,2-ethanediylbis-1-aspartic acid |
| CN103906709A (en) * | 2011-08-26 | 2014-07-02 | 环保金属有限公司 | Method for recovering technical-grade molybdenum from diluted acid leacing solutions (PLS) that have a high arsenic concentration and originate from metallurgical waste |
| CN105603195A (en) * | 2016-02-03 | 2016-05-25 | 华东理工大学 | Method for extracting molybdenum and nickel from acrylonitrile waste catalyst |
| CN107585789A (en) * | 2017-09-26 | 2018-01-16 | 河南科技大学 | A kind of method that high-purity molybdenum trioxide is prepared using hydrometallurgy molybdenum concntrate |
| CN108728653A (en) * | 2018-06-11 | 2018-11-02 | 江苏北矿金属循环利用科技有限公司 | A method of extracting molybdenum from useless nickel molybdenum catalyst |
| CN110937991A (en) * | 2018-09-21 | 2020-03-31 | 荆门市格林美新材料有限公司 | Preparation method of green synthetic nickel acetate crystal |
| CN114763585A (en) * | 2021-01-14 | 2022-07-19 | 万华化学集团股份有限公司 | Method for preparing cobalt iso-octoate by using waste Raney cobalt catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09235628A (en) * | 1996-02-29 | 1997-09-09 | Catalysts & Chem Ind Co Ltd | Separation and recovery of useful metal from used desulfurization catalyst |
| CN1257292C (en) * | 2003-11-14 | 2006-05-24 | 沈阳嘉禾冶金炉料有限公司 | Method for recovering nickel and aluminum from waste aluminum based nickel-containing catalyst |
| CN100347318C (en) * | 2005-04-30 | 2007-11-07 | 李翔 | Method for separating and recovering cobalt and molybdic from waste cobalt-molybdic catalyst |
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- 2006-10-25 CN CNB2006100971487A patent/CN100427406C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101435027B (en) * | 2007-11-15 | 2010-06-02 | 中国石油化工股份有限公司 | Method for recycling high purity molybdenum from molybdenum-containing spent catalyst |
| CN101724758B (en) * | 2008-10-29 | 2011-04-06 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method for recycling molybdenum of molybdenum-contained waste catalyst |
| CN103906709A (en) * | 2011-08-26 | 2014-07-02 | 环保金属有限公司 | Method for recovering technical-grade molybdenum from diluted acid leacing solutions (PLS) that have a high arsenic concentration and originate from metallurgical waste |
| CN103906709B (en) * | 2011-08-26 | 2015-11-25 | 环保金属有限公司 | The method of technical grade molybdenum is reclaimed from the rare acid dip solution of the metallurgical slag containing High Concentration of Arsenic (PLS) |
| CN103849772A (en) * | 2012-11-28 | 2014-06-11 | 大连东泰产业废弃物处理有限公司 | Method for recovering metal cobalt by N,N'-1,2-ethanediylbis-1-aspartic acid |
| CN103343232A (en) * | 2013-07-11 | 2013-10-09 | 岳阳鼎格云天环保科技有限公司 | Method for recycling Ni from waste FCC (Fluid Catalytic Cracking) catalyst |
| CN105603195A (en) * | 2016-02-03 | 2016-05-25 | 华东理工大学 | Method for extracting molybdenum and nickel from acrylonitrile waste catalyst |
| CN107585789A (en) * | 2017-09-26 | 2018-01-16 | 河南科技大学 | A kind of method that high-purity molybdenum trioxide is prepared using hydrometallurgy molybdenum concntrate |
| CN107585789B (en) * | 2017-09-26 | 2019-08-23 | 河南科技大学 | A method of high-purity molybdenum trioxide is prepared using hydrometallurgy molybdenum concentrate |
| CN108728653A (en) * | 2018-06-11 | 2018-11-02 | 江苏北矿金属循环利用科技有限公司 | A method of extracting molybdenum from useless nickel molybdenum catalyst |
| CN108728653B (en) * | 2018-06-11 | 2019-11-22 | 江苏北矿金属循环利用科技有限公司 | A method of extracting molybdenum from useless nickel molybdenum catalyst |
| CN110937991A (en) * | 2018-09-21 | 2020-03-31 | 荆门市格林美新材料有限公司 | Preparation method of green synthetic nickel acetate crystal |
| CN114763585A (en) * | 2021-01-14 | 2022-07-19 | 万华化学集团股份有限公司 | Method for preparing cobalt iso-octoate by using waste Raney cobalt catalyst |
| CN114763585B (en) * | 2021-01-14 | 2024-04-09 | 万华化学集团股份有限公司 | Method for preparing cobalt iso-octoate by using waste Raney cobalt catalyst |
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| CN100427406C (en) | 2008-10-22 |
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