CN103977801A - A high-thermal-conductivity cobalt-based Fischer-Tropsch synthesis catalyst, a preparing method thereof and applications thereof - Google Patents
A high-thermal-conductivity cobalt-based Fischer-Tropsch synthesis catalyst, a preparing method thereof and applications thereof Download PDFInfo
- Publication number
- CN103977801A CN103977801A CN201410199499.3A CN201410199499A CN103977801A CN 103977801 A CN103977801 A CN 103977801A CN 201410199499 A CN201410199499 A CN 201410199499A CN 103977801 A CN103977801 A CN 103977801A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- powder
- tropsch synthesis
- based fischer
- synthesis catalyst
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A high-thermal-conductivity cobalt-based Fischer-Tropsch synthesis catalyst comprises active components and a carrier. The catalyst comprises 5-35% by weight of cobaltous oxide, with the balance being the metal carrier. By adoption of metal powder as the catalyst carrier, the heat transfer efficiency of a catalyst bed layer is largely increased, thus effectively preventing generation of "temperature runaway" of "hot spots" of a stationary bed layer.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method and application, is a kind of high-termal conductivity Metal Supported Co catalysts and preparation method and the application in Fischer-Tropsch is synthetic specifically.
Technical background
The synthetic process that coal, natural gas or living beings is converted under catalyst action to hydro carbons through synthesis gas that refers to of Fischer-Tropsch.The catalyst adopting in Fischer-Tropsch compound probability is divided into iron-based and cobalt-based two classes, and wherein cobalt-base catalyst has active highly, and methane selectively is low, C
5+the selective high and low advantage of water gas reaction and become Fischer-Tropsch synthesize in the catalyst of competitive superiority.Therefore the Co based Fischer-Tropsch synthesis catalyst that designs high-performance, low price has great importance.
Co-based fischer-tropsch synthesis reactor mainly contains paste state bed reactor and fixed bed reactors.Wherein fixed bed reactors have easy and simple to handle, the segregative advantage of product.But due to the high exothermic character of fischer-tropsch reaction, in course of reaction, be easy in fixed bed bed, form " focus ", when serious, even cause " temperature runaway ".In order to overcome this problem, shell company has carried out many transformations with enhanced reactor internal heat transfer to structure in reactor, but this has caused the increase of reactor design with processing charges.US2011135543 discloses a kind of MFEC technique of augmentation of heat transfer.Adopting micron order metallic fiber is matrix, above catalyst granules is attached to, utilizes the high thermal conduction characteristic of metallic fiber, increases the heat conductivility of bed.The shortcomings such as but this technology has behaviour does complexity, and catalyst utilization is low, the easy loss of catalyst granules.
Summary of the invention
The object of this invention is to provide a kind of Metal Supported Co catalysts and preparation method and the application in Fischer-Tropsch is synthetic of high thermal conductivity.
Metal material has high heat conductivility, has the nanoscale oxide-film of intact at some metal material surface simultaneously, and this oxide-film at high temperature can stable existence, avoids interior metal oxidation.Based on above characteristic, metal material is as co-based fischer-tropsch catalyst carrier, and the heat transfer efficiency of its high thermal conduction characteristic energy fortifying catalytic agent bed, avoids bed " focus " to emerge; The oxide-film on surface energy " grappling " active component, promotes the dispersion of active component simultaneously; Metal material also has its cheap market price, the sufficient advantage of raw material sources in addition.Therefore prepare Co based Fischer-Tropsch synthesis catalyst using metal material as carrier and there is greatly actual application value and great commercial promise.
Catalyst of the present invention is made up of active component and carrier, and its percentage by weight consists of: cobalt oxide: 5-35%, all the other are metallic carrier.
Metallic carrier as above is magnesium powder, copper powder, aluminium powder, zinc powder, iron powder, magnesium aluminum-alloy powder or SiCuAl alloyed powder.
Metallic carrier average grain scope 10～50 μ m as above, specific surface is 70～650m
2/ g, mesoporous aperture 2～30nm, macropore diameter 50～90nm, pore volume is 0.25～3.00cm
3/ g.
The preparation method of catalyst of the present invention is as follows:
(1) be that the metal powder of 10～50 μ m is put into distilled water and boiled 6～10h by particle diameter, filter, by filter cake dry 10～20h at 60～100 DEG C;
(2) configuration 1.0 × 10
-6～1.0 × 10
-2mol/L acid or aqueous slkali;
(3) in the time that metal powder is aluminium powder, magnesium aluminum-alloy powder or SiCuAl alloyed powder, press metal powder: acid or aqueous slkali=5g:2-5L, the metal powder of step (1) is joined in the solution of step (2), and electromagnetic agitation is processed after 10～30h, filter, washing is to neutral, and filter cake is dry 10～30h at 60～100 DEG C;
In the time that metal powder is magnesium, copper, iron or zinc, press metal powder: acid solution=5g:2-5L, the metal powder of step (1) is joined in the solution of step (2), and electromagnetic agitation is processed after 10～30h, filter, washing is to neutral, and filter cake is dry 10～30h at 60～100 DEG C;
(4) by the material of step (3) gained roasting 6～10h under 300～600 DEG C of nitrogen atmospheres, obtain metal powder carrier.
(5) adopt equi-volume impregnating, solubility cobalt salt is dissolved in deionized water, flood with step (4) gained metallic carrier at ambient temperature, dip time is 6～10h, after dipping, at 60～100 DEG C, be dried 10～20h, after dry, under nitrogen atmosphere, carry out roasting, sintering temperature is 200～400 DEG C, and roasting time is 3～8h.
Acid as above is acetic acid, nitric acid or hydrochloric acid, and alkali is potassium hydroxide or NaOH.
Cobalt salt as above is cobalt nitrate or cobalt acetate.
The catalyst specific surface that the present invention makes is 50～600m
2/ g.
The application process of catalyst of the present invention is as follows:
(1) catalyst reduces in fixed bed reactors in the hydrogen of 300～600 DEG C, and reducing gas volume space velocity is 500～2000h
-1, reduction pressure is 0.1～1.0Mpa, the recovery time is 5～20h.
(2) reaction is carried out in fixed bed reactors, and reaction condition is: H
2the mol ratio of/CO is between 1～3, and reaction temperature is 190 DEG C～240 DEG C, and pressure is 1.0～3.0Mpa, and volume space velocity is 500～2000h
-1.
The present invention compared with prior art tool has the following advantages:
1, legacy cellular shape woven wire integrated catalyst carrier, voidage is too high, aperture is excessive (grade), causes fixed bed reactors utilization rate low; The coat on top layer easily departs from reaction, causes loss of active component.And catalyst prepared by the present invention, reactor utilization ratio is high, and active component is difficult for running off.
2, by adopting metal powder as catalyst carrier, greatly improve the heat transfer efficiency of beds, effectively prevented the generation that emerges " temperature runaway " of fixed bed " focus ".
3, catalyst preparation process is simple, cheap.
Detailed description of the invention
The present invention will be further described for embodiment below, and protection scope of the present invention is not subject to the restriction of these embodiment.
Embodiment 1:
Catalyst preparation: (particle diameter 10～15 μ m) put into distilled water and boil 6h, filter, by filter cake dry 20h at 60 DEG C by metallic aluminium powder.Gained material is joined to 2L1.0 × 10
-6in mol/L sodium hydroxide solution, electromagnetic agitation is processed after 10h, filters, and washing is to neutral, and filter cake is dry 10h at 60 DEG C, dry after under nitrogen atmosphere 300 DEG C of roasting 6h, obtain catalyst carrier, carrier specific surface is 72m
2/ g, mesoporous aperture 4nm, macropore diameter 52nm, pore volume is 0.26cm
3/ g.15 (wt) % that accounts for final catalyst by cobalt oxide takes Co (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, and dip time is 6h, is dried 10h after dipping at 60 DEG C, after being dried, carries out roasting under nitrogen atmosphere, and sintering temperature is 300 DEG C, and roasting time is 4h.The catalyst weight percentage obtaining: cobalt oxide 15%, all the other are metallic aluminium powder carrier.Catalyst specific surface is 50m
2/ g.
In fixed bed reactors, (Ф 10 × 500mm) do not dilute the above-mentioned catalyst of filling 2ml, in the hydrogen of 400 DEG C, reduces, and reducing gas volume space velocity is 1500h-
1, reduction pressure is 1.0Mpa, the recovery time is 5h.Reaction is carried out in fixed bed reactors, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 220 DEG C, and pressure is 2.0Mpa, and volume space velocity is 1000h
-1.Reaction result is in table 1.
Embodiment 2:
Catalyst preparation: (particle diameter 40～45 μ m) put into distilled water and boil 6h, filter, by filter cake dry 20h at 60 DEG C by copper powder.Gained material is joined to 2L1.0 × 10
-5in mol/L salpeter solution, electromagnetic agitation is processed after 10h, filters, and washing is to neutral, and filter cake is dry 10h at 60 DEG C, dry after under nitrogen atmosphere 300 DEG C of roasting 6h, obtain catalyst carrier.Carrier specific surface is 98m
2/ g, mesoporous aperture 8nm, macropore diameter 55nm, pore volume is 0.41cm
3/ g.15 (wt) % that accounts for final catalyst by cobalt oxide takes Co (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, and dip time is 6h, is dried 10h after dipping at 60 DEG C, after being dried, carries out roasting under nitrogen atmosphere, and sintering temperature is 300 DEG C, and roasting time is 4h.The catalyst weight percentage obtaining is: cobalt oxide 15%, all the other are copper powder carrier.Catalyst specific surface is 125m
2/ g.
In fixed bed reactors, (Ф 10 × 500mm) do not dilute the above-mentioned catalyst of filling 2ml, in the hydrogen of 400 DEG C, reduces, and reducing gas volume space velocity is 1500h
-1, reduction pressure is 1.0Mpa, the recovery time is 5h.Reaction is carried out in fixed bed reactors, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 220 DEG C, and pressure is 2.0Mpa, and volume space velocity is 1000h
-1.Reaction result is in table 2.
Embodiment 3:
Catalyst preparation: (particle diameter 25～30 μ m) put into distilled water and boil 6h, filter, by filter cake dry 20h at 60 DEG C by metal magnesium powder.Gained material is joined to 2L1.0 × 10
-3in mol/L acetic acid solution, electromagnetic agitation is processed after 10h, filters, and washing is to neutral, and filter cake is dry 10h at 60 DEG C, dry after under nitrogen atmosphere 300 DEG C of roasting 6h, obtain catalyst carrier.Carrier specific surface is 190m
2/ g, mesoporous aperture 6nm, macropore diameter 60nm, pore volume is 0.9cm
3/ g.15 (wt) % that accounts for final catalyst by cobalt oxide takes Co (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, and dip time is 6h, is dried 10h after dipping at 60 DEG C, after being dried, carries out roasting under nitrogen atmosphere, and sintering temperature is 300 DEG C, and roasting time is 4h.The catalyst weight percentage obtaining is: cobalt oxide 15%, all the other are metal magnesium powder carrier.Catalyst specific surface is 416m
2/ g.
In fixed bed reactors, (Ф 10 × 500mm) do not dilute the above-mentioned catalyst of filling 2ml, in the hydrogen of 400 DEG C, reduces, and reducing gas volume space velocity is 1500h
-1, reduction pressure is 1.0Mpa, the recovery time is 5h.Reaction is carried out in fixed bed reactors, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 220 DEG C, and pressure is 2.0Mpa, and volume space velocity is 1000h
-1.Reaction result is in table 3.
Embodiment 4:
Catalyst preparation: (mass percent Si12%Cu2%Al86%, particle diameter 30～35 μ m) put into distilled water and boil 6h, filter, by filter cake dry 20h at 60 DEG C by SiCuAl alloy.Gained material is joined to 2L1.0 × 10
-2in mol/L hydrochloric acid solution, electromagnetic agitation is processed after 10h, filters, and washing is to neutral, and filter cake is dry 10h at 60 DEG C, dry after under nitrogen atmosphere 300 DEG C of roasting 6h, obtain catalyst carrier.Carrier specific surface is 320m
2/ g, mesoporous aperture 5nm, macropore diameter 53nm, pore volume is 1.25cm
3/ g.15 (wt) % that accounts for final catalyst by cobalt oxide takes Co (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, and dip time is 6h, is dried 10h after dipping at 60 DEG C, after being dried, carries out roasting under nitrogen atmosphere, and sintering temperature is 300 DEG C, and roasting time is 4h.The catalyst weight percentage obtaining is: cobalt oxide 15%, all the other are SiCuAl alloyed powder carrier.Catalyst specific surface is 599m
2/ g.
In fixed bed reactors, (Ф 10 × 500mm) do not dilute the above-mentioned catalyst of filling 2ml, in the hydrogen of 400 DEG C, reduces, and reducing gas volume space velocity is 1500h
-1, reduction pressure is 1.0Mpa, the recovery time is 5h.Reaction is carried out in fixed bed reactors, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 230 DEG C, and pressure is 2.0Mpa, and volume space velocity is 1500h
-1.Reaction result is in table 4.
Embodiment 5:
Catalyst preparation: (particle diameter 45～50 μ m) and put into distilled water and boil 6h, filter, by filter cake dry 20h at 60 DEG C by metallic aluminium powder.Gained material is joined to 2L1.0 × 10
-3in mol/L acetic acid solution, electromagnetic agitation is processed after 10h, filters, and washing is to neutral, and filter cake is dry 10h at 60 DEG C, dry after under nitrogen atmosphere 300 DEG C of roasting 6h, obtain catalyst carrier.Carrier specific surface is 190m
2/ g, mesoporous aperture 6nm, macropore diameter 60nm, pore volume is 0.9cm
3/ g.30 (wt) % that accounts for final catalyst by cobalt oxide takes Co (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, and dip time is 6h, is dried 10h after dipping at 60 DEG C, after being dried, carries out roasting under nitrogen atmosphere, and sintering temperature is 300 DEG C, and roasting time is 4h.The catalyst weight percentage obtaining: cobalt oxide 30%, all the other are metallic aluminium powder carrier.Catalyst specific surface is 398m
2/ g.
In fixed bed reactors, (Ф 10 × 500mm) do not dilute the above-mentioned catalyst of filling 2ml, in the hydrogen of 400 DEG C, reduces, and reducing gas volume space velocity is 1500h
-1, reduction pressure is 1.0Mpa, the recovery time is 5h.Reaction is carried out in fixed bed reactors, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 200 DEG C, and pressure is 2.0Mpa, and volume space velocity is 1500h
-1.Reaction result is in table 5.
Embodiment 6:
Catalyst preparation: (mass percent Mg5%Al95%, particle diameter 10～15 μ m) put into distilled water and boil 6h, filter, by filter cake dry 20h at 60 DEG C by MgAl alloyed powder.Gained material is joined to 2L1.0 × 10
-2in mol/L potassium hydroxide solution, electromagnetic agitation is processed after 10h, filters, and washing is to neutral, and filter cake is dry 10h at 60 DEG C, dry after under nitrogen atmosphere 300 DEG C of roasting 6h, obtain catalyst carrier.Carrier vector specific surface is 430m
2/ g, mesoporous aperture 12nm, macropore diameter 60nm, pore volume is 1.6cm
3/ g.30 (wt) % that accounts for final catalyst by cobalt oxide takes Co (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, and dip time is 6h, is dried 10h after dipping at 60 DEG C, after being dried, carries out roasting under nitrogen atmosphere, and sintering temperature is 300 DEG C, and roasting time is 4h.The catalyst weight percentage obtaining is: cobalt oxide 30%, all the other are MgAl alloyed powder carrier.Catalyst specific surface is 586m
2/ g.
In fixed bed reactors, (Ф 10 × 500mm) do not dilute the above-mentioned catalyst of filling 2ml, in the hydrogen of 400 DEG C, reduces, and reducing gas volume space velocity is 1500h
-1, reduction pressure is 1.0Mpa, the recovery time is 5h.Reaction is carried out in fixed bed reactors, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 240 DEG C, and pressure is 2.0Mpa, and volume space velocity is 2000h
-1.Reaction result is in table 6.
Embodiment 7:
Catalyst preparation: (mass percent Mg5%Al95%, particle diameter 15～20 μ m) put into distilled water and boil 6h, filter, by filter cake dry 20h at 60 DEG C by MgAl alloyed powder.Gained material is joined to 2L1.0 × 10
-3in mol/L salpeter solution, electromagnetic agitation is processed after 10h, filters, and washing is to neutral, and filter cake is dry 10h at 60 DEG C, dry after under nitrogen atmosphere 300 DEG C of roasting 6h, obtain catalyst carrier.Carrier specific surface is 260m
2/ g, mesoporous aperture 13nm, macropore diameter 65nm, pore volume is 1.1cm
3/ g.30 (wt) % that accounts for final catalyst by cobalt oxide takes Co (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, and dip time is 6h, is dried 10h after dipping at 60 DEG C, after being dried, carries out roasting under nitrogen atmosphere, and sintering temperature is 300 DEG C, and roasting time is 4h.The catalyst weight percentage obtaining: cobalt oxide 30%, all the other are MgAl alloyed powder carrier.Catalyst specific surface is 150m
2/ g.
In fixed bed reactors, (Ф 10 × 500mm) do not dilute the above-mentioned catalyst of filling 2ml, in the hydrogen of 400 DEG C, reduces, and reducing gas volume space velocity is 1500h
-1, reduction pressure is 1.0Mpa, the recovery time is 5h.Reaction is carried out in fixed bed reactors, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 210 DEG C, and pressure is 2.0Mpa, and volume space velocity is 1500h
-1.Reaction result is in table 7.
Table 1 catalyst test condition and reaction result
| Catalyst | Reaction condition | CO conversion ratio % | C 1Selective % | C 5+Selective % |
| Embodiment 1 | 220℃,1000h -1 | 31.2 | 7.2 | 85.3 |
| Embodiment 2 | 220℃,1000h -1 | 38.9 | 6.8 | 86.4 |
| Embodiment 3 | 220℃,1000h -1 | 45.2 | 6.6 | 88.2 |
| Embodiment 4 | 230℃,1500h -1 | 56.3 | 8.6 | 84.9 |
| Embodiment 5 | 200℃,1500h -1 | 53.2 | 5.8 | 91.2 |
| Embodiment 6 | 240℃,2000h -1 | 71.2 | 9.6 | 83.7 |
| Embodiment 7 | 210℃,1500h -1 | 67.9 | 6.2 | 87.9 |
Claims (9)
1. a high-termal conductivity Co based Fischer-Tropsch synthesis catalyst, is characterized in that catalyst is made up of active component and carrier, and its percentage by weight consists of cobalt oxide: 5-35%, all the other are metallic carrier.
2. a kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst as claimed in claim 1, is characterized in that described metallic carrier is magnesium powder, copper powder, aluminium powder, zinc powder, iron powder, magnesium aluminum-alloy powder or SiCuAl alloyed powder.
3. a kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst as claimed in claim 1, is characterized in that described metallic carrier average grain scope 10～50 μ m, and specific surface is 70～650m
2/ g, mesoporous aperture 2～30nm, macropore diameter 50～90nm, pore volume is 0.25～3.00cm
3/ g.
4. a kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst as described in claim 1-3 any one, is characterized in that catalyst specific surface is 50～600m
2/ g.
5. the preparation method of a kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst as described in claim 1-4 any one, is characterized in that comprising the steps:
(1) be that the metal powder of 10～50 μ m is put into distilled water and boiled 6～10h by particle diameter, filter, by filter cake dry 10～20h at 60～100 DEG C;
(2) configuration 1.0 × 10
-6～1.0 × 10
-2mol/L acid or aqueous slkali;
(3) in the time that metal powder is aluminium powder, magnesium aluminum-alloy powder or SiCuAl alloyed powder, press metal powder: acid or aqueous slkali=5g:2-5L, the metal powder of step (1) is joined in the solution of step (2), and electromagnetic agitation is processed after 10～30h, filter, washing is to neutral, and filter cake is dry 10～30h at 60～100 DEG C;
In the time that metal powder is magnesium, copper, iron or zinc, press metal powder: acid solution=5g:2-5L, the metal powder of step (1) is joined in the solution of step (2), and electromagnetic agitation is processed after 10～30h, filter, washing is to neutral, and filter cake is dry 10～30h at 60～100 DEG C;
(4) by the material of step (3) gained roasting 6～10h under 300～600 DEG C of nitrogen atmospheres, obtain metal powder carrier.
(5) adopt equi-volume impregnating, solubility cobalt salt is dissolved in deionized water, flood with step (4) gained metallic carrier at ambient temperature, dip time is 6～10h, after dipping, at 60～100 DEG C, be dried 10～20h, after dry, under nitrogen atmosphere, carry out roasting, sintering temperature is 200～400 DEG C, and roasting time is 3～8h.
6. the preparation method of a kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst as claimed in claim 5, is characterized in that described acid is acetic acid, nitric acid or hydrochloric acid.
7. the preparation method of a kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst as claimed in claim 5, is characterized in that described alkali is potassium hydroxide or NaOH.
8. the preparation method of a kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst as claimed in claim 5, is characterized in that described cobalt salt is cobalt nitrate or cobalt acetate.
9. the application of a kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst as described in claim 1-4 any one, is characterized in that application process is as follows:
(1) catalyst reduces in fixed bed reactors in the hydrogen of 300～600 DEG C, and reducing gas volume space velocity is 500～2000h
-1, reduction pressure is 0.1～1.0Mpa, the recovery time is 5～20h;
(2) reaction is carried out in fixed bed reactors, and reaction condition is: H
2the mol ratio of/CO is between 1～3, and reaction temperature is 190 DEG C～240 DEG C, and pressure is 1.0～3.0Mpa, and volume space velocity is 500～2000h
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410199499.3A CN103977801B (en) | 2014-05-13 | 2014-05-13 | A kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst and method for making and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410199499.3A CN103977801B (en) | 2014-05-13 | 2014-05-13 | A kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst and method for making and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103977801A true CN103977801A (en) | 2014-08-13 |
| CN103977801B CN103977801B (en) | 2016-02-24 |
Family
ID=51270112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410199499.3A Active CN103977801B (en) | 2014-05-13 | 2014-05-13 | A kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst and method for making and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103977801B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115845854A (en) * | 2022-11-28 | 2023-03-28 | 高潞空气化工产品(上海)能源科技有限公司 | High-thermal-conductivity high-temperature-resistant catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778876A (en) * | 2004-11-23 | 2006-05-31 | 北京化工大学 | Metal carrier catalyst for methane catalyzed burning and production thereof |
| CN1781595A (en) * | 2004-12-03 | 2006-06-07 | 中国石油化工股份有限公司 | Foam metal hydrogenating catalyst and its preparing method and use |
| CN101314140A (en) * | 2007-05-31 | 2008-12-03 | 碧氢科技开发股份有限公司 | Porous catalyst structure and its preparation |
| CN101570462A (en) * | 2008-04-30 | 2009-11-04 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method |
| CN103084218A (en) * | 2013-01-28 | 2013-05-08 | 江苏帕艾尼尔科技有限公司 | Method for loading coating on sponge metal and coating prepared by same |
-
2014
- 2014-05-13 CN CN201410199499.3A patent/CN103977801B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778876A (en) * | 2004-11-23 | 2006-05-31 | 北京化工大学 | Metal carrier catalyst for methane catalyzed burning and production thereof |
| CN1781595A (en) * | 2004-12-03 | 2006-06-07 | 中国石油化工股份有限公司 | Foam metal hydrogenating catalyst and its preparing method and use |
| CN101314140A (en) * | 2007-05-31 | 2008-12-03 | 碧氢科技开发股份有限公司 | Porous catalyst structure and its preparation |
| CN101570462A (en) * | 2008-04-30 | 2009-11-04 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method |
| CN103084218A (en) * | 2013-01-28 | 2013-05-08 | 江苏帕艾尼尔科技有限公司 | Method for loading coating on sponge metal and coating prepared by same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115845854A (en) * | 2022-11-28 | 2023-03-28 | 高潞空气化工产品(上海)能源科技有限公司 | High-thermal-conductivity high-temperature-resistant catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103977801B (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104226354B (en) | A kind of catalyzer for acetone hydrogenation preparing isopropanol and method for making and application | |
| CN104001514B (en) | A kind of eggshell type Co based Fischer-Tropsch synthesis catalyst and preparation method and application | |
| Li et al. | Hydrogen production from NaBH4 hydrolysis via Co-ZIF-9 catalyst | |
| CN103785470B (en) | A kind of preparation method for the synthesis of acrylic acid catalyst | |
| CN103933978A (en) | Supported nanocatalyst for catalytic conversion of carbon dioxide as well as preparation method and application thereof | |
| CN111774070A (en) | Catalyst for preparing methyl formate by catalyzing dehydrogenation of methanol, preparation method and application thereof | |
| CN111215080A (en) | For regulating CO2The hydrogenation target product is C2-4Catalyst for olefin and preparation method thereof | |
| CN104190414A (en) | Sodium borohydride reduction adopted method for preparing Pd/alpha-Al2O3 catalyst | |
| CN114917912B (en) | Catalyst for preparing methanol and co-producing ethylene glycol through ethylene carbonate hydrogenation, preparation method and use method | |
| CN103977801B (en) | A kind of high-termal conductivity Co based Fischer-Tropsch synthesis catalyst and method for making and application | |
| CN105688901A (en) | Preparation method of hydrogenation catalyst for preparing H2O2 | |
| CN103664514B (en) | Method of preparing fatty alcohol by virtue of hydrogenation of aliphatic ester | |
| CN104001556B (en) | A kind of high-termal conductivity egg-shell catalyst carrier and preparation method and application | |
| CN104069870B (en) | A kind of catalyst of synthesising gas systeming carbinol and preparation method and application | |
| CN102600836B (en) | Preparation method and application of catalyst for synthesizing dialkyl succinate | |
| CN105833883A (en) | Previous metal modified catalyst for fischer-tropsch synthesis and preparation method thereof | |
| CN102784640A (en) | Catalyst for synthesizing oxalate by CO coupling reaction and preparation method thereof | |
| CN104475170B (en) | Aluminum silicon alloy catalyst carrier as well as preparation method and application thereof | |
| CN103977840B (en) | A kind of high-termal conductivity catalyst carrier and preparation method and application | |
| CN109718777A (en) | A kind of alcohol reforming catalyst for preparing hydrogen and its preparation method and application and alcohol reforming hydrogen production process | |
| CN113649049A (en) | Maleic anhydride selective hydrogenation catalyst, and preparation method and application method thereof | |
| CN102626638A (en) | Catalyst for preparation of 1,2-pentanediol | |
| CN112547071A (en) | Catalyst for preparing tetrahydrofuran by furan hydrogenation and preparation method and application thereof | |
| CN104368359A (en) | Catalyst for preparing 3-pentanol through 3-pentanone hydrogenation and preparation method of catalyst for preparing 3-pentanol through 3-pentanone hydrogenation | |
| CN111039755A (en) | Application of nickel boride catalyst in selective hydrogenation of alkynol |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180606 Address after: 030001 78 building, 27 Taoyuan South Road, Yingze District, Taiyuan, Shanxi. Patentee after: Zhongke Lu'an Energy Technology Co., Ltd. Address before: No. 27, Taoyuan South Road, Yingze District, Taiyuan, Shanxi Patentee before: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences |