CN1157756A - Nanometre grade cobalt-manganese spinel and its manufacturing method and use - Google Patents
Nanometre grade cobalt-manganese spinel and its manufacturing method and use Download PDFInfo
- Publication number
- CN1157756A CN1157756A CN96117198.7A CN96117198A CN1157756A CN 1157756 A CN1157756 A CN 1157756A CN 96117198 A CN96117198 A CN 96117198A CN 1157756 A CN1157756 A CN 1157756A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- manganese
- citric acid
- spinel
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 23
- 239000011029 spinel Substances 0.000 title claims abstract description 23
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 2
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 2
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 64
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- 239000011572 manganese Substances 0.000 claims description 19
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910020632 Co Mn Inorganic materials 0.000 abstract 2
- 229910020678 Co—Mn Inorganic materials 0.000 abstract 2
- 229910003179 MnxCo3−xO4 Inorganic materials 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Abstract
A nm-grade Co-Mn spinel, which has chemical formula MnxCo3-xO4 (where X is greater than 0 but less than or equal to 1.4), average granularity less than 80 nm and specific surface area greater than 40 sq.m/g, is prepared through adding organic ligand to aqueous soltuion of cobolt nitrate and manganese nitrate, regulating pH value to 0-1.5, heating to 50-70 deg.C to form gel, baking, and calcine. Said Co-Mn spinel can be used as catalyst for hydrotransforming CO to hydrocarbon with high catalytic activity, selectivity and transform rate of CO.
Description
The present invention relates to the cobalt manganese composite oxide, specifically a kind of nano level cobalt-manganese spinel.
Cobalt-manganese spinel can [be seen N Yanamoto with the solution co-precipitation, J.Mat.Sci.Lett., 525,2.1983 and J L Martin de Vidales, Mat.Res.Bull., 1135,28,1993] and solid phase salt powder calcination method [see PRavindranathan, J.Solid state Chem., 20,66,1987] preparation spinel-type cobalt manganese composite oxide.But the lower (Mn of its manganese content of cobalt-manganese spinel with method for preparing
xCo
3-xO
4, 0＜x≤1) and particle diameter big (micron dimension), specific area is less＜40m
2/ g) and particle diameter inhomogeneous, other dephasign is arranged, as catalyst, catalytic activity is relatively poor.
The object of the present invention is to provide a kind of nano level cobalt-manganese spinel, and easy method for making, a further object of the present invention provides its purposes as catalyst.
Technical scheme of the present invention is:
A kind of nanometre grade cobalt-manganese spinel, it consists of Mn
xCo
3-xO
4, 0＜x≤1.4 wherein, average grain diameter is less than 80nm, and specific area is greater than 40m
2/ g.
The method for making of cobalt-manganese spinel of the present invention adds organic ligand in cobalt nitrate, manganese nitrate aqueous solution, regulate PH to 0 to 1.5, forms gel at 50 to 70 ℃, oven dry, and roasting promptly gets nanometre grade cobalt-manganese spinel.
In cobalt nitrate, the manganese nitrate aqueous solution, the mol ratio of manganese ion and cobalt ions is x: 3-x, 0＜x≤1.4, and the initial concentration of total metal ion (cobalt, manganese ion sum) is 0.3 to 0.9 mole.
The amount that organic ligand adds is that to make the metal ion (cobalt, manganese) and the mol ratio of organic ligand be 1: 1.
Organic ligand can be a citric acid, also can be the mixture of citric acid and acetylacetone,2,4-pentanedione.When selecting the mixture of citric acid and acetylacetone,2,4-pentanedione for use, the mol ratio of citric acid and acetylacetone,2,4-pentanedione is not less than 2: 1.After in cobalt nitrate, manganese nitrate aqueous solution, adding organic ligand, regulate pH value and place the formation gel at 50-70 ℃ to 0-1.5, with gel 100-120 ℃ of oven dry, then can roasting between 300-700 ℃ (preferred sintering temperature is 350-400 ℃), promptly get the single average grain diameter of crystalline phase less than 80nm, specific area is greater than 40m
2The nanometre grade cobalt-manganese spinel of the present invention of/g.
Nanometre grade cobalt-manganese spinel of the present invention can be used as catalyst, and it increases significantly for the activity of the general cobalt-manganese spinel of the specific activity of carbon monoxide hydrogenation (more than the particle diameter micron dimension).The olefine selective of the cobalt-manganese spinel of high Mn content is also apparently higher than the spinelle that hangs down manganese content.
Nanometre grade cobalt-manganese spinel of the present invention, its manganese content can be higher, and manganese, cobalt ions ratio can reach 1.4: 1.6.Average grain diameter is less than 80nm, epigranular, and specific area is greater than 40m
2/ g.As catalyst, bigger catalytic activity is arranged, for carbon monoxide hydrogenation, higher olefine selective is arranged.
By the following examples, further specify the present invention.
Embodiment 1. with raw material cobalt nitrate, manganese nitrate, acetylacetone,2,4-pentanedione, citric acid by Co: Mn: acetylacetone,2,4-pentanedione: the citric acid mol ratio is 2.5: 0.5: 0.5: 2.5 wiring solution-formings, the initial concentration that makes total metal ion in the solution is at 0.6M, with nitric acid regulator solution initial p H value 0, in 60 ℃ of water-baths, form gel, gel 110 ℃ of oven dry, was got Mn in 2 hours in 350 ℃ of roastings again
0.5Co
2.5O
4Sample.Its average grain diameter is 10-15nm, specific area 74m
2/ g, epigranular.
Embodiment 2. with raw material cobalt nitrate, manganese nitrate, acetylacetone,2,4-pentanedione, citric acid by Co: Mn: acetylacetone,2,4-pentanedione: the citric acid mol ratio is 2.0: 1.0: 0.5: 2.5 wiring solution-formings, the initial concentration that makes total metal ion in the solution is at 0.6M, with nitric acid regulator solution initial p H value 0, in 60 ℃ of water-baths, form gel, gel 110 ℃ of oven dry, was got Mn in 2 hours in 350 ℃ of roastings again
1.0Co
2.0O
4Sample.Its average grain diameter is 10-15nm, specific area 71m
2/ g, epigranular.
Embodiment 3. with raw material cobalt nitrate, manganese nitrate, acetylacetone,2,4-pentanedione, citric acid by Co: Mn: acetylacetone,2,4-pentanedione: the citric acid mol ratio is 1.8: 1.2: 0.5: 2.5 wiring solution-formings, the initial concentration that makes total metal ion in the solution is at 0.6M, with ammoniacal liquor regulator solution initial p H value 1, in 60 ℃ of water-baths, form gel, gel 110 ℃ of oven dry, was got Mn in 2 hours in 350 ℃ of roastings again
1.2Co
1.8O
4Sample.Its average grain diameter is 10-15nm, specific area 78m
2/ g, epigranular.
Embodiment 4. with raw material cobalt nitrate, manganese nitrate, acetylacetone,2,4-pentanedione, citric acid by Co: Mn: acetylacetone,2,4-pentanedione: the citric acid mol ratio is 2.0: 1.0: 0.5: 2.5 wiring solution-formings, the initial concentration that makes total metal ion in the solution is at 0.4M, with ammoniacal liquor regulator solution initial p H value 1.5, in 60 ℃ of water-baths, form gel, gel 110 ℃ of oven dry, was got MnCo in 2 hours in 350 ℃ of roastings again
2O
4Sample.Its average grain diameter is 10-15nm, specific area 71m
2/ g, epigranular.
Embodiment 5. with raw material cobalt nitrate, manganese nitrate, acetylacetone,2,4-pentanedione and citric acid by Co: Mn: acetylacetone,2,4-pentanedione: the citric acid mol ratio is 2.0: 1.0: 0.5: 2.5 wiring solution-formings, the initial concentration that makes total metal ion in the solution is at 0.8M, solution initial PH value is 0.5, in 60 ℃ of water-baths, form gel, gel 110 ℃ of oven dry, was got MnCo in 2 hours in 400 ℃ of roastings again
2O
4Sample.Its average grain diameter is 10-15nm, specific area 70m
2/ g, epigranular.
Embodiment 6. with raw material cobalt nitrate, manganese nitrate, citric acid by Co: Mn: the citric acid mol ratio is 2.0: 1.0: 3.0 wiring solution-formings, the initial concentration that makes total metal ion in the solution is at 0.6M, with nitric acid regulator solution initial p H value 0, in 60 ℃ of water-baths, form gel, gel 110 ℃ of oven dry, was got MnCo in 2 hours in 350 ℃ of roastings again
2O
4Sample.Its average grain diameter is 10-15nm, specific area 40m
2/ g, epigranular.
Embodiment 7. cobalt-manganese spinel MnCo of the present invention
2O
4As the carbon monoxide hydrogenation catalyst: reaction condition: 300 ℃ of temperature, pressure 1atm, H
2/ CO (vol/vol)=2.0 GHSV 700/h, the conversion ratio of carbon monoxide is 17.4%, C
2-C
4Olefine selective is 40%.(the micron dimension MnCo of prior art
2O
4, the conversion ratio of CO is 9.6% under the similarity condition).
Embodiment 8. cobalt-manganese spinel Mn of the present invention
1.2Co
1.8O
4As the carbon monoxide hydrogenation catalyst: reaction condition: 270 ℃ of temperature, pressure 1atm, H
2/ CO (vol/vol)=2.0 GHSV 700/h, the conversion ratio of carbon monoxide is 13.2%, C
2-C
4Olefine selective is 43.2%.(prior art can't obtain Mn: Co＞1: 2 cobalt-manganese spinel).
Claims (7)
1. a nanometre grade cobalt-manganese spinel is characterized in that it consists of Mn
xCo
3-xO
4, 0＜x≤1.4 wherein, average grain diameter is less than 80nm, and specific area is greater than 40m
2/ g.
2. the method for making of cobalt-manganese spinel according to claim 1 is characterized in that adding organic ligand in cobalt nitrate, manganese nitrate aqueous solution, regulates PH to 0 to 1.5, forms gel at 50 to 70 ℃, oven dry, and roasting promptly gets nanometre grade cobalt-manganese spinel.
3. preparation method according to claim 2 is characterized in that in cobalt nitrate, the manganese nitrate aqueous solution that the mol ratio of manganese ion and cobalt ions is x: 3-x, 0＜x≤1.4, and the initial concentration of total metal ion is 0.3 to 0.9 mole.
4. preparation method according to claim 2, the mol ratio that it is characterized in that metal ion and organic ligand is 1: 1.
5. preparation method according to claim 2 is characterized in that organic ligand is the mixture of citric acid or citric acid and acetylacetone,2,4-pentanedione.
6. preparation method according to claim 5 is characterized in that the mol ratio of citric acid and acetylacetone,2,4-pentanedione is not less than 2: 1 in organic ligand citric acid and the acetylacetone,2,4-pentanedione mixture.
7. the purposes of cobalt-manganese spinel according to claim 1 is characterized in that being used as the catalyst that co hydrogenation is converted into hydrocarbon reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117198A CN1049608C (en) | 1996-12-02 | 1996-12-02 | Nanometre grade cobalt-manganese spinel and its manufacturing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117198A CN1049608C (en) | 1996-12-02 | 1996-12-02 | Nanometre grade cobalt-manganese spinel and its manufacturing method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1157756A true CN1157756A (en) | 1997-08-27 |
| CN1049608C CN1049608C (en) | 2000-02-23 |
Family
ID=5124131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96117198A Expired - Fee Related CN1049608C (en) | 1996-12-02 | 1996-12-02 | Nanometre grade cobalt-manganese spinel and its manufacturing method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049608C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427380C (en) * | 2005-06-08 | 2008-10-22 | 北京化工大学 | Process for preparing high radio surface area nano spinel by lamellar precursor body method |
| CN101670999B (en) * | 2009-09-27 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Mn-Co-doped spinel composite nanometer material and low-temperature sintering method thereof |
| CN103073072A (en) * | 2013-01-29 | 2013-05-01 | 安泰科技股份有限公司 | Manganese cobalt composite oxide (MnCo2O4) magnetic nanocrystal and preparation method thereof |
| CN103746104A (en) * | 2013-12-09 | 2014-04-23 | 中国科学院福建物质结构研究所 | Manganese cobalt oxide self-assembled micro-spheres, and preparation and applications thereof |
| CN104810518A (en) * | 2015-04-15 | 2015-07-29 | 南开大学 | Cobalt-manganese-based spinel nano material as well as preparation method and application thereof |
| CN105170158A (en) * | 2015-07-22 | 2015-12-23 | 重庆工商大学 | CoMn composite oxide catalyst for eliminating benzene-serial volatile organic compounds in air and preparation method for therefor |
| CN105555922A (en) * | 2013-07-31 | 2016-05-04 | 沙特基础工业公司 | A process for the production of olefins through fischer-tropsch based synthesis |
| CN108264093A (en) * | 2018-01-09 | 2018-07-10 | 上海应用技术大学 | A kind of preparation method of cobalt-manganese spinel microballoon |
| CN108682869A (en) * | 2018-04-10 | 2018-10-19 | 云南铝业股份有限公司 | Manganese cobalt spinel oxygen reduction catalyst and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2831745B2 (en) * | 1989-10-31 | 1998-12-02 | 富士通株式会社 | Semiconductor device and manufacturing method thereof |
| US5248701A (en) * | 1991-08-05 | 1993-09-28 | Exxon Research And Engineering Company | Substituted cobalt catalysts for Fischer-Tropsch synthesis |
| CN1029510C (en) * | 1991-11-22 | 1995-08-16 | 中国科学院山西煤炭化学研究所 | Preparing method for hydrogen refining cobalt molybdenum catalyzer. |
-
1996
- 1996-12-02 CN CN96117198A patent/CN1049608C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427380C (en) * | 2005-06-08 | 2008-10-22 | 北京化工大学 | Process for preparing high radio surface area nano spinel by lamellar precursor body method |
| CN101670999B (en) * | 2009-09-27 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Mn-Co-doped spinel composite nanometer material and low-temperature sintering method thereof |
| CN103073072A (en) * | 2013-01-29 | 2013-05-01 | 安泰科技股份有限公司 | Manganese cobalt composite oxide (MnCo2O4) magnetic nanocrystal and preparation method thereof |
| CN103073072B (en) * | 2013-01-29 | 2014-08-13 | 安泰科技股份有限公司 | Manganese cobalt composite oxide (MnCo2O4) magnetic nanocrystal and preparation method thereof |
| CN105555922A (en) * | 2013-07-31 | 2016-05-04 | 沙特基础工业公司 | A process for the production of olefins through fischer-tropsch based synthesis |
| CN103746104A (en) * | 2013-12-09 | 2014-04-23 | 中国科学院福建物质结构研究所 | Manganese cobalt oxide self-assembled micro-spheres, and preparation and applications thereof |
| CN104810518A (en) * | 2015-04-15 | 2015-07-29 | 南开大学 | Cobalt-manganese-based spinel nano material as well as preparation method and application thereof |
| CN104810518B (en) * | 2015-04-15 | 2017-03-08 | 南开大学 | A kind of cobalt manganese systems spinel nano material and its preparation method and application |
| CN105170158A (en) * | 2015-07-22 | 2015-12-23 | 重庆工商大学 | CoMn composite oxide catalyst for eliminating benzene-serial volatile organic compounds in air and preparation method for therefor |
| CN105170158B (en) * | 2015-07-22 | 2018-02-27 | 重庆工商大学 | Eliminate CoMn composite oxide catalysts of benzene in air system volatile organic matter and preparation method thereof |
| CN108264093A (en) * | 2018-01-09 | 2018-07-10 | 上海应用技术大学 | A kind of preparation method of cobalt-manganese spinel microballoon |
| CN108682869A (en) * | 2018-04-10 | 2018-10-19 | 云南铝业股份有限公司 | Manganese cobalt spinel oxygen reduction catalyst and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1049608C (en) | 2000-02-23 |
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