CN101462056B - Method for preparing porous nickel metal integral type catalyst - Google Patents
Method for preparing porous nickel metal integral type catalyst Download PDFInfo
- Publication number
- CN101462056B CN101462056B CN200910067662XA CN200910067662A CN101462056B CN 101462056 B CN101462056 B CN 101462056B CN 200910067662X A CN200910067662X A CN 200910067662XA CN 200910067662 A CN200910067662 A CN 200910067662A CN 101462056 B CN101462056 B CN 101462056B
- Authority
- CN
- China
- Prior art keywords
- room temperature
- hours
- minute
- warming
- keeps
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a method for preparing a monolithic porous nickel metal catalyst, which is characterized by comprising the steps of: (1) preparing a monolithic porous carbon template; (2) placing the monolithic porous carbon template into a container, using a saturated nickel nitrate water solution for incipient impregnation, heating, and keeping for 8 to 16 hours; (3) repeating the step (2) for 2 to 4 times; and (4) heating a solid prepared in step (3) in N2 atmosphere to between 100 and 1,000 DEG C, keeping for 1 to 100 hours, reducing to room temperature, introducing the air, increasing the temperature to between 500 and 1,000 DEG C, keeping for 1 to 100 hours, reducing to room temperature, introducing hydrogen, increasing the temperature to between 100 and 1,000 DEG C, keepingfor 1 to 100 hours, and reducing to room temperature to obtain the monolithic porous nickel metal catalyst. The porosity of the monolithic porous nickel metal catalyst is between 90 and 95 percent, the specific surface area reaches between 10 and 50m<2>/g, and the catalyst has good activity and stability as well as broad application.
Description
Technical field
The present invention relates to a kind of preparation method of porous nickel metal integral type catalyst, belong to the nickel-metal catalyst preparing technical field.
Background technology
Along with the development of World Economics, the rare metal mineral resources are rare day by day, as rhodium, ruthenium, platinum, palladium etc.Because cheap and numerous reactions are had extraordinary catalytic action, nickel-metal catalyst more and more is subject to people's attention.Can have much with of the reaction of nickel metal as catalyst, mainly comprise the reaction of preparing synthetic gas by natural gas partial oxidation, the reaction of gas renormalizing preparing synthetic gas, methyl alcohol, alcohol steam reformed reaction, F-T synthetic reactions such as carbon monoxide and hydrogen synthesizing formaldehyde, methyl alcohol, methanol oxidation reaction, and multiple polymerisation.
Existing Raney nickel mainly contains granular pattern, support type and monolithic devices.Document (Applied Catalysis A:General, 2004,272:157) reported working load type Raney nickel, as Ni/Al
2O
3And Ni/TiO
2, the reaction result of catalyzing natural gas portion oxidation synthesis gas.When using fixed bed reactors, nickel catalyst carriedly under high-speed show very high activity, but inactivation very easily, and main cause is that carbon distribution has covered the supported catalyst activated centre.
Professor Schmidt of Univ Minnesota-Twin Cities USA has invented the integral catalyst of metal coating, and (Science 1993,259:343; U.S.P 5648582; AIChE Journal, 2005,51 (1): 247), thereby reaction can self-heating be carried out, need not use externally heated oven; Structure of reactor is simple, is easy to industrialization; Because the integral catalyst porosity is big, can makes to be reflected under the big air speed (short contacting time) and carry out simultaneously, reactor volume is little, and pressure falls little, and the production capacity height; If be fuel cell hydrogen-feeding, the toggle speed of this process is also fast.This is that the hydro carbons partial oxidation is the optimal reaction system of fuel cell hydrogen-feeding.
Professor Schmidt adopts ceramic oxide as carrier, and the coated with metal layer is as catalyst.Discover, use the activity of such catalysts and the selectivity of noble metal Rh and Pt coating all very high; Also all very high for industrial significant Ni activity of such catalysts and selectivity, but poor stability, inactivation rapidly, the reason of inactivation mainly be the sintering of active component or loss (Schmidt, J.Catal., 1994,146:1).In addition, use ceramic oxide as carrier, its heat conduction is also bad, can not effectively eliminate focus, for the Ni coated catalysts, can not solve the inactivation problem.Ceramic oxide is as also poor, the easy fragmentation of thermal shock resistance (variations in temperature is fast) (WO 2002013225) of carrier.
United States Patent (USP) (US 6254807) has been reported the result who uses nickel integral catalyst catalytic methane partial oxidation reaction, and the porosity of its catalyst and specific surface are all lower, and methane conversion is low.Chinese patent (CN 03101191.8) reported adopt single porosity more than 90%, specific area 1.0m
2The monolithic devices foamed nickel catalyst agent catalytic methane partial oxidation that/g is above, catalyst stability is good, is difficult for inactivation.Its shortcoming also is that the specific surface and the porosity of catalyst is lower, and conversion ratio is lower.
For problems such as the specific area of the poor stability that solves the monolithic devices loaded catalyst, easily inactivation and heat conductivity difference etc. and the agent of monolithic devices foamed nickel catalyst and porosity are lower, need research and development that good heat and mechanical stability are arranged, require to have the voidage height simultaneously, and the big integral catalyst of specific area.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of preparation method of porous nickel metal integral type catalyst is provided, porous nickel metal integral type catalyst porosity height, specific area that method of the present invention makes are big, good stability.
Technical scheme of the present invention is summarized as follows:
A kind of preparation method of porous nickel metal integral type catalyst comprises the steps:
(1) preparation of monolithic devices porous carbon template: in room temperature, rotating speed is under 300～1000 rev/mins of stirring condition, get in the magnesium hydroxide aqueous solution that resorcinol and formaldehyde is dissolved in 0.0018M and make mixed solution, the mol ratio of described resorcinol and formaldehyde is 1/2, the mass concentration of formaldehyde is 25% in the described mixed solution, described mixed solution is poured in the mould, 15～35 ℃ of polymerizations 1～100 hour, 40～60 ℃ of following polymerizations 1～100 hour, obtained wet gel in 1～100 hour 70～100 ℃ of following polymerizations, be cooled to 15～35 ℃, described wet gel is put in the acetone, with the water in the acetone-exchanged wet gel framework, the mass ratio of described wet gel and acetone is 1: 3～6, exchanges 2～4 times, and 15～35 ℃ of dryings became solid in 8～16 hours; Behind the mold removal with described solid at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 100～1000 ℃ from room temperature, keeps 1～100 hour, reduces to room temperature, obtains monolithic devices porous carbon template;
(2) monolithic devices porous carbon template is put into container, carry out incipient impregnation, be heated to 100～120 ℃, kept 8～16 hours with the nickel nitrate saturated aqueous solution;
(3) repeating step is (2) 2～4 times;
(4) solid that step (3) is prepared is at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 100～1000 ℃ from room temperature, keeps 1～100 hour, reduces to room temperature; Bubbling air is warming up to 500～1000 ℃ with 1 ℃/minute speed, keeps 1～100 hour, reduces to room temperature; The feeding flow velocity is 1～1000ml/ minute a hydrogen, is warming up to 100～1000 ℃ with 1 ℃/minute speed, keeps 1～100 hour, reduces to room temperature, makes porous nickel metal integral type catalyst.
The preparation of described step (1) monolithic devices porous carbon template is preferably: in room temperature, rotating speed is under 700 rev/mins of stirring condition, get in the magnesium hydroxide aqueous solution that resorcinol and formaldehyde is dissolved in 0.0018M and make mixed solution, the mol ratio of described resorcinol and formaldehyde is 1/2, the mass concentration of formaldehyde is 25% in the described mixed solution, described mixed solution is poured in the mould, 20～25 ℃ of polymerizations 20～30 hours, 50 ℃ of following polymerizations 60～72 hours, obtained wet gel in 60～72 hours 90 ℃ of following polymerizations, be cooled to 20～25 ℃, described wet gel is put in the acetone, with the water in the acetone-exchanged wet gel framework, the mass ratio of described wet gel and acetone is 1: 6, exchanges 3 times, and 20～25 ℃ of dryings became solid in 12 hours; Behind the mold removal with described solid, at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 800 ℃ from room temperature, keeps 5 hours, reduces to room temperature, obtains monolithic devices porous carbon template.
Described step (4) is preferably: with the solid of step (3) preparation, at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 800 ℃ from room temperature, keeps 8 hours, reduces to room temperature; Bubbling air is warming up to 500 ℃ with 1 ℃/minute speed, keeps 6 hours, reduces to room temperature; The feeding flow velocity is 200ml/ minute a hydrogen, is warming up to 800 ℃ with 1 ℃/minute speed, keeps 5 hours, reduces to room temperature, makes porous nickel metal integral type catalyst.
The invention has the advantages that: the porous nickel metal integral type catalyst porosity that the present invention makes 90～95%, specific area reaches 10～50m
2/ g, active, good stability are difficult for inactivation, are easy to industrialization, are widely used.
The specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
A kind of preparation method of porous nickel metal integral type catalyst comprises the steps:
(1) in room temperature, rotating speed is under 700 rev/mins of stirring condition, get 110.11 the gram resorcinols and 60.06 the gram formaldehyde be dissolved in 70 the gram 0.0018M magnesium hydroxide aqueous solution in make mixed solution, pour mixed solution into glass mold (20 millimeters of diameters, high 10 millimeters) in, 20 ℃ of polyase 13s 0 hour, 50 ℃ of following polymerase 17s 2 hours, obtained the wet gel of cross-linked structure in 2 hours at 90 ℃ of following polymerase 17s, be cooled to 20 ℃, at room temperature this wet gel is put in the acetone, with the water in the acetone-exchanged wet gel framework, the mass ratio of wet gel and acetone is 1: 4 times, exchanges 3 times, became solid (20 millimeters of diameters in 12 hours 20 ℃ of dryings, high 10 millimeters), behind the mold removal solid is put in the quartz tube reactor, at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 800 ℃ from room temperature, keeps 5 hours, reduces to room temperature, obtains monolithic devices porous carbon template; The size and the shape of monolithic devices porous carbon template can be controlled by glass mold;
(2) weighing 0.5 gram monolithic devices porous carbon template is placed in the container; 6 milliliters of nickel nitrate saturated aqueous solutions slowly are added drop-wise on the monolithic devices porous carbon template, solution are absorbed fully, at 120 ℃, kept 12 hours, with the naked eye can be observed water vapour during beginning and distributed, when waiting until perusal, thought that moisture evaporates fully less than water vapour;
(3) repeating step is (2) 3 times;
(4) solid that step (3) is prepared is at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 800 ℃ from room temperature, keeps 8 hours, reduces to room temperature; Bubbling air is warming up to 500 ℃ with 1 ℃/minute speed, keeps 6 hours, reduces to room temperature; The feeding flow velocity is 200ml/ minute a hydrogen, is warming up to 800 ℃ with 1 ℃/minute speed, keeps 5 hours, reduces to room temperature, makes porous nickel metal integral type catalyst (20 millimeters of diameters, high 10 millimeters), and porosity is 95%, and specific area is 50 meters squared per gram.
Embodiment 2
A kind of preparation method of porous nickel metal integral type catalyst comprises the steps:
(1) preparation of monolithic devices porous carbon template: in room temperature, rotating speed is under 300 rev/mins of stirring condition, get in the magnesium hydroxide aqueous solution that resorcinol and formaldehyde is dissolved in 0.0018M and make mixed solution, the mol ratio of described resorcinol and formaldehyde is 1/2, the mass concentration of formaldehyde is 25% in the described mixed solution, described mixed solution is poured in the mould, 35 ℃ of polymerizations 1 hour, 60 ℃ of following polymerizations 1 hour, obtained wet gel in 1 hour 100 ℃ of following polymerizations, be cooled to 35 ℃, described wet gel is put in the acetone, with the water in the acetone-exchanged wet gel framework, the mass ratio of described wet gel and acetone is 1: 3 times, exchanges 4 times, and 35 ℃ of dryings became solid in 8 hours; Behind the mold removal with described solid at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 1000 ℃ from room temperature, keeps 1 hour, reduces to room temperature, obtains monolithic devices porous carbon template;
(2) monolithic devices porous carbon template is put into container, carry out incipient impregnation, be heated to 120 ℃, kept 8 hours with the nickel nitrate saturated aqueous solution;
(3) repeating step is (2) 2 times;
(4) solid that step (3) is prepared is at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 1000 ℃ from room temperature, keeps 1 hour, reduces to room temperature; Bubbling air is warming up to 1000 ℃ with 1 ℃/minute speed, keeps 1 hour, reduces to room temperature; The feeding flow velocity is 1000ml/ minute a hydrogen, is warming up to 100 ℃ with 1 ℃/minute speed, keeps 100 hours, reduces to room temperature, makes porous nickel metal integral type catalyst.Porosity is 93%, and specific area is 40 meters squared per gram.
Embodiment 3
A kind of preparation method of porous nickel metal integral type catalyst comprises the steps:
(1) preparation of monolithic devices porous carbon template: in room temperature, rotating speed is under 1000 rev/mins of stirring condition, get in the magnesium hydroxide aqueous solution that resorcinol and formaldehyde is dissolved in 0.0018M and make mixed solution, the mol ratio of described resorcinol and formaldehyde is 1/2, the mass concentration of formaldehyde is 25% in the described mixed solution, described mixed solution is poured in the mould, 25 ℃ of polymerizations 20 hours, 50 ℃ of following polymerizations 60 hours, obtained wet gel in 60 hours 90 ℃ of following polymerizations, be cooled to 25 ℃, described wet gel is put in the acetone, with the water in the acetone-exchanged wet gel framework, the mass ratio of described wet gel and acetone is 1: 6 times, exchanges 2 times, and 25 ℃ of dryings became solid in 12 hours; Behind the mold removal with described solid at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 800 ℃ from room temperature, keeps 5 hours, reduces to room temperature, obtains monolithic devices porous carbon template;
(2) monolithic devices porous carbon template is put into container, carry out incipient impregnation, be heated to 110 ℃, kept 12 hours with the nickel nitrate saturated aqueous solution;
(3) repeating step is (2) 3 times;
(4) solid that step (3) is prepared is at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 800 ℃ from room temperature, keeps 10 hours, reduces to room temperature; Bubbling air is warming up to 800 ℃ with 1 ℃/minute speed, keeps 2 hours, reduces to room temperature; The feeding flow velocity is 500ml/ minute a hydrogen, is warming up to 500 ℃ with 1 ℃/minute speed, keeps 10 hours, reduces to room temperature, makes porous nickel metal integral type catalyst.Porosity is 92%, and specific area is 35 meters squared per gram.
Embodiment 4
A kind of preparation method of porous nickel metal integral type catalyst comprises the steps:
(1) preparation of monolithic devices porous carbon template: in room temperature, rotating speed is under 600 rev/mins of stirring condition, get in the magnesium hydroxide aqueous solution that resorcinol and formaldehyde is dissolved in 0.0018M and make mixed solution, the mol ratio of described resorcinol and formaldehyde is 1/2, the mass concentration of formaldehyde is 25% in the described mixed solution, described mixed solution is poured in the mould, 15 ℃ of polymerizations 100 hours, 40 ℃ of following polymerizations 100 hours, obtained wet gel in 100 hours 70 ℃ of following polymerizations, be cooled to 15 ℃, described wet gel is put in the acetone, with the water in the acetone-exchanged wet gel framework, the mass ratio of described wet gel and acetone is 1: 5 times, exchanges 3 times, and 15 ℃ of dryings became solid in 16 hours; Behind the mold removal with described solid at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 100 ℃ from room temperature, keeps 100 hours, reduces to room temperature, obtains monolithic devices porous carbon template; (2) monolithic devices porous carbon template is put into container, carry out incipient impregnation, be heated to 100 ℃, kept 16 hours with the nickel nitrate saturated aqueous solution;
(3) repeating step is (2) 4 times;
(4) solid that step (3) is prepared is at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 100 ℃ from room temperature, keeps 100 hours, reduces to room temperature; Bubbling air is warming up to 500 ℃ with 1 ℃/minute speed, keeps 100 hours, reduces to room temperature; The feeding flow velocity is 1ml/ minute a hydrogen, is warming up to 1000 ℃ with 1 ℃/minute speed, keeps 1 hour, reduces to room temperature, makes porous nickel metal integral type catalyst.Porosity is 90%, and specific area is 10 meters squared per gram.
Porous nickel metal integral type catalyst of the present invention since porosity 90～95%, specific area reaches 10～50m
2/ g, active, good stability, be difficult for inactivation, be easy to industrialization, be widely used as: can be used for the reaction of catalyzing natural gas self-heating portion oxidation synthesis gas, also can be used for the reaction of catalyzing natural gas preparing synthetic gas by reforming, methyl alcohol, alcohol steam reformed reaction, F-T synthetic reactions such as carbon monoxide and hydrogen synthesizing formaldehyde, methyl alcohol, the methanol oxidation reaction, and multiple polymerisation etc.
Claims (3)
1. the preparation method of a porous nickel metal integral type catalyst is characterized in that comprising the steps:
(1) preparation of monolithic devices porous carbon template: in room temperature, rotating speed is under 300～1000 rev/mins of stirring condition, get in the magnesium hydroxide aqueous solution that resorcinol and formaldehyde is dissolved in 0.0018M and make mixed solution, the mol ratio of described resorcinol and formaldehyde is 1/2, the mass concentration of formaldehyde is 25% in the described mixed solution, described mixed solution is poured in the mould, 15～35 ℃ of polymerizations 1～100 hour, 40～60 ℃ of following polymerizations 1～100 hour, obtained wet gel in 1～100 hour 70～100 ℃ of following polymerizations, be cooled to 15～35 ℃, described wet gel is put in the acetone, with the water in the acetone-exchanged wet gel framework, the mass ratio of described wet gel and acetone is 1: 3～6, exchanges 2～4 times, and 15～35 ℃ of dryings became solid in 8～16 hours; Behind the mold removal with described solid at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 100～1000 ℃ from room temperature, keeps 1～100 hour, reduces to room temperature, obtains monolithic devices porous carbon template;
(2) monolithic devices porous carbon template is put into container, carry out incipient impregnation, be heated to 100～120 ℃, kept 8～16 hours with the nickel nitrate saturated aqueous solution;
(3) repeating step is (2) 2～4 times;
(4) solid that step (3) is prepared is at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 100～1000 ℃ from room temperature, keeps 1～100 hour, reduces to room temperature; Bubbling air is warming up to 500～1000 ℃ with 1 ℃/minute speed, keeps 1～100 hour, reduces to room temperature; The feeding flow velocity is 1～1000ml/ minute a hydrogen, is warming up to 100～1000 ℃ with 1 ℃/minute speed, keeps 1～100 hour, reduces to room temperature, makes porous nickel metal integral type catalyst.
2. the preparation method of a kind of porous nickel metal integral type catalyst according to claim 1, it is characterized in that being prepared as of described step (1) monolithic devices porous carbon template: in room temperature, rotating speed is under 700 rev/mins of stirring condition, get in the magnesium hydroxide aqueous solution that resorcinol and formaldehyde is dissolved in 0.0018M and make mixed solution, the mol ratio of described resorcinol and formaldehyde is 1/2, the mass concentration of formaldehyde is 25% in the described mixed solution, described mixed solution is poured in the mould, 20～25 ℃ of polymerizations 20～30 hours, 50 ℃ of following polymerizations 60～72 hours, obtained wet gel in 60～72 hours 90 ℃ of following polymerizations, be cooled to 20～25 ℃, described wet gel is put in the acetone, with the water in the acetone-exchanged wet gel framework, the mass ratio of described wet gel and acetone is 1: 6, exchange 3 times, 20～25 ℃ of dryings became solid in 12 hours; Behind the mold removal with described solid, at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 800 ℃ from room temperature, keeps 5 hours, reduces to room temperature, obtains monolithic devices porous carbon template.
3. the preparation method of a kind of porous nickel metal integral type catalyst according to claim 1 is characterized in that described step (4) is: with the solid of step (3) preparation, at N
2Speed with 1 ℃/minute in the atmosphere is warming up to 800 ℃ from room temperature, keeps 8 hours, reduces to room temperature; Bubbling air is warming up to 500 ℃ with 1 ℃/minute speed, keeps 6 hours, reduces to room temperature; The feeding flow velocity is 200ml/ minute a hydrogen, is warming up to 800 ℃ with 1 ℃/minute speed, keeps 5 hours, reduces to room temperature, makes porous nickel metal integral type catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910067662XA CN101462056B (en) | 2009-01-13 | 2009-01-13 | Method for preparing porous nickel metal integral type catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910067662XA CN101462056B (en) | 2009-01-13 | 2009-01-13 | Method for preparing porous nickel metal integral type catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101462056A CN101462056A (en) | 2009-06-24 |
| CN101462056B true CN101462056B (en) | 2010-09-15 |
Family
ID=40802986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910067662XA Expired - Fee Related CN101462056B (en) | 2009-01-13 | 2009-01-13 | Method for preparing porous nickel metal integral type catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101462056B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107096380B (en) * | 2017-05-31 | 2023-04-21 | 华南理工大学 | Method and device for treating formaldehyde in air by catalytic oxidation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4208339A (en) * | 1977-06-27 | 1980-06-17 | Rhone-Poulenc Industries | Process for the preparation of para-benzoquinone |
| CN1491744A (en) * | 2003-08-27 | 2004-04-28 | 天津大学 | Process for preparing carbon nano fiber knitting macro-particles containing high active nickel catalyst |
| CN1958157A (en) * | 2006-12-06 | 2007-05-09 | 北京化工大学 | Method for preparing high-dispersed nickel bases catalyst from hydrotalcite / Nano carbon composite precursor |
| CN101058073A (en) * | 2007-06-06 | 2007-10-24 | 天津大学 | Method for preparing nickel nanometer line network particle catalyst |
| CN101227973A (en) * | 2005-06-16 | 2008-07-23 | 约翰森·马瑟公开有限公司 | Catalyst and process for its manufacture |
-
2009
- 2009-01-13 CN CN200910067662XA patent/CN101462056B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4208339A (en) * | 1977-06-27 | 1980-06-17 | Rhone-Poulenc Industries | Process for the preparation of para-benzoquinone |
| CN1491744A (en) * | 2003-08-27 | 2004-04-28 | 天津大学 | Process for preparing carbon nano fiber knitting macro-particles containing high active nickel catalyst |
| CN101227973A (en) * | 2005-06-16 | 2008-07-23 | 约翰森·马瑟公开有限公司 | Catalyst and process for its manufacture |
| CN1958157A (en) * | 2006-12-06 | 2007-05-09 | 北京化工大学 | Method for preparing high-dispersed nickel bases catalyst from hydrotalcite / Nano carbon composite precursor |
| CN101058073A (en) * | 2007-06-06 | 2007-10-24 | 天津大学 | Method for preparing nickel nanometer line network particle catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101462056A (en) | 2009-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101320388B1 (en) | Hydrocarbon reforming catalyst, method for manufacturing the same and a fuel treatment device comprising the same | |
| CN102275963B (en) | Preparation method of aluminium oxide material | |
| EP1433745A2 (en) | Catalyst for the removal of carbon monoxide, its method of manufacture and its uses | |
| KR20090119766A (en) | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide | |
| CN111604045B (en) | Nickel-based oxygen vacancy carrier catalyst and preparation method and application thereof | |
| CN101185904B (en) | Selectivity liquid phase hydrogenation catalyst and preparation method and use thereof | |
| TWI294413B (en) | Method for converting co and hydrogen into methane and water | |
| CN1672789A (en) | Catalyst for autothermal reformation of methanol to prepared hydrogen and its prepn process and application | |
| Sun et al. | Yolk-shell structured Pt-CeO2@ Ni-SiO2 as an efficient catalyst for enhanced hydrogen production from ethanol steam reforming | |
| CN114308042B (en) | Attapulgite-based ordered microporous zeolite catalyst and preparation method and application thereof | |
| CN113996293B (en) | Cerium lanthanum solid solution supported iridium catalyst, preparation method and application thereof | |
| CN100478071C (en) | Catalyst for making synthetic gas from methane by catalyzing partly oxidation and its preparation method | |
| CN101462051B (en) | Catalyst for generating crotonyl alcohol by selective hydrogenation of gas-phase crotonaldehyde and preparation method thereof | |
| CN100557050C (en) | A kind of preparation method of nickel-aluminum base alloy porous material | |
| CN101462056B (en) | Method for preparing porous nickel metal integral type catalyst | |
| KR101342605B1 (en) | Hydrocarbon reforming catalyst, method for manufacturing the same and a fuel treatment device comprising the same | |
| CN113332933A (en) | Vehicle-mounted organic liquid hydride dehydrogenation reactor | |
| CN105233815B (en) | A kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen and application | |
| WO2014182020A1 (en) | Monolith catalyst for carbon dioxide reforming reaction, production method for same, and production method for synthesis gas using same | |
| CN101537374B (en) | Method for protecting reforming catalyst of molten carbonate fuel cell and applications thereof | |
| CN104383927B (en) | The Catalysts and its preparation method of a kind of methane and CO 2 reformation preparing synthetic gas | |
| CN100431696C (en) | Method for preparing nickel nanometer line network particle catalyst | |
| CN110329992A (en) | Low-temperature methanol steam reforming catalyst for preparing hydrogen and preparation method thereof | |
| CN100488628C (en) | Improved catalyzer of methane catalysis and partial oxidation for synthesizing gas and method of manufacturing the same | |
| CN102600853B (en) | Integral catalyst as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100915 Termination date: 20110113 |