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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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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| CNB2006100971487A CN100427406C (en) | 2006-10-25 | 2006-10-25 | Waste molybdenum nickel cobalt catalyst utilization method for environmental protection |
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Cited By (10)
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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 |
| 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
- 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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