CN104588023B - Fischer-Tropsch synthesis catalyst, and preparation method and application thereof - Google Patents
Fischer-Tropsch synthesis catalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN104588023B CN104588023B CN201310529634.1A CN201310529634A CN104588023B CN 104588023 B CN104588023 B CN 104588023B CN 201310529634 A CN201310529634 A CN 201310529634A CN 104588023 B CN104588023 B CN 104588023B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- fischer
- nitrate
- hours
- roasting
- 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.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a Fischer-Tropsch synthesis catalyst, and a preparation method and an application thereof. The catalyst is a composite metal oxide with a perovskite structure, and the general formula of the catalyst is A＜x＞A'＜1-x＞B＜y＞B'＜1-y＞O＜3＞, wherein A is rare earth metal lanthanum, A' is metallic potassium, B is transition metal nickel, B' is transition metal cobalt, x is greater than 0.7 and smaller than 1, and y is greater than 0 and smaller than 0.35. The preparation method of the cobalt-based Fischer-Tropsch synthesis catalyst comprises the following steps: preparing a solution with cobalt nitrate, nickel nitrate, potassium nitrate and lanthanum nitrate as precursors and citric acid or glycol as a complexing agent, uniformly stirring, carrying out water evaporation to make the solution become a viscous gel from a transparent sol, drying, and roasting to obtain the composite oxide Fischer-Tropsch synthesis catalyst with the perovskite structure. The catalyst can be applied to Fischer-Tropsch synthesis reactions. The catalyst can be adopted to make the CO conversion rate reach 90% or more and guarantee very high C＜5＞＜+＞ selectivity.
Description
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and its preparation method and application, belong to urging in F- T synthesis field
Change technology.
Background technology
F- T synthesis refer to synthesis gas（Carbon monoxide and hydrogen）Catalyze and synthesize the anti-of liquid hydrocarbon fuel on a catalyst
Should.F- T synthesis have the advantages that to be independent of oil, product cleans.With world energy sources structure from single oil dependent form to
Coal, oil and natural gas alliance type change and environmental requirement increasingly improves, and F- T synthesis technology will be developed rapidly.
Efficient co-based fischer-tropsch catalyst is one of key technology in F- T synthesis technology, and each major oil companies priority is opened
Send out with amorphous Si O2、TiO2And Al2O3Co based Fischer-Tropsch synthesis catalyst for main carriers.
US6765026B2 discloses the Fischer-Tropsch synthesis method that a kind of application special catalyst is catalyzed.The method adopts
Catalyst precursor be a kind of iron group（Especially cobalt）The soluble compounds of the soluble compounds of metal or salt and platinum or salt.Will
Presoma is contacted with the solution of hydroxyhy-drocarbyl amines or ammonium hydroxide, obtains a kind of special catalyst, makes C5 +Hydrocarbon selective reaches
To 58% ~ 80%.But it is worth low gaseous products CH using the method4Selectivity be up to 10%.So that proposing a kind of new
Fischer-Tropsch synthesis method is to reduce CH further4Selectively.
CN1417292A reports a kind of preparation method with activated carbon for carrier Co based Fischer-Tropsch synthesis catalyst, for
Synthesis gas prepares linear paraffin within 20 for the carbon number for raw material and carbon number is concentrated mainly on the hydro carbons of diesel oil distillate section.In reaction
Temperature is 240 DEG C, reaction pressure 2.5MPa, air speed 500h-1Under the conditions of, the conversion ratio of fixed bed reaction system CO is 64.1%,
CH4Selectivity be 8.5%, C5 +It is selectively 80.7%.
CN101224430A reports a kind of hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, and noble metal and cobalt are negative
It is downloaded on silica supports, then carry out organically-modified.Wherein when noble metal adopts Pt, catalyst system 15%Co0.8%
Pt/SiO2, organically-modified reagent adopts dimethyldiethoxysilane modified, and on pressurization static bed, reaction condition is 230
DEG C, 1.0MPa, 1000h-1（V/V）, H2The conversion ratio of/CO=3/1, CO is 72.7%, and the selectivity of methane is 8.4%.Above-mentioned technology
CH4Selectively need to reduce further, C5 +Selectively need to improve further.
Content of the invention
For the deficiencies in the prior art, the present invention provides a kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof and answers
With.CO conversion ratio can be made to reach more than 90% and ensure very high C simultaneously using this catalyst5 +Selectively.
A kind of fischer-tropsch synthetic catalyst, this catalyst is the metal composite oxide with perovskite structure, and its formula is
AxA’1-xByB’1-yO3, wherein A is rare earth lanthanum, and A ' is metallic potassium, and B is transiting metal nickel, and B ' is transition metals cobalt, 0.7<x
<1,0<y<0.35.
A kind of preparation method of fischer-tropsch synthetic catalyst, including following process：With cobalt nitrate, nickel nitrate, potassium nitrate, nitric acid
Lanthanum is presoma, with citric acid or ethylene glycol as complexing agent, wiring solution-forming mixing and stirring, and then carry out moisture evaporation,
The colloidal sol of solution went from clear is transformed into sticky gel, finally dry, roasting, and the sample after roasting is to have perovskite structure
Composite oxides fischer-tropsch synthetic catalyst.
In the preparation method of fischer-tropsch synthetic catalyst of the present invention, complexing agent and metal ion mol ratio are 1：1～8：1, excellent
Elect 1 as：1～4：1.Prepare and agitating solution is at 20～90 DEG C, carry out at preferably 50～70 DEG C.Stir speed (S.S.) be 200～
500rpm, preferably 300～400rpm.Mixing time is 3～8 hours, preferably 4～6 hours.Baking temperature is 60～200
DEG C, preferably 80～150 DEG C.Drying time is 1～36 hour, preferably 8～24 hours.Sintering temperature is 600～1000 DEG C,
Roasting time is roasting 2 ~ 15 hours, roasting 3～8 hours preferably at 700～900 DEG C.
The method of reducing of fischer-tropsch synthetic catalyst of the present invention, reduces mode using conventional method of reducing or segmentation, preferably
The latter.Described segmentation reduction mode reduces 4 ~ 20h first under the atmosphere of hydrogen, and reduction temperature is 300-400 DEG C, reduces pressure
0.5 ~ 1.5MPa, then reduces 4 ~ 18h under the atmosphere of hydrogen and methane mixed gas, and reduction temperature is 180 ~ 240 DEG C, reduction pressure
Power is 0.5 ~ 3MPa, and the volumetric mixture ratio of hydrogen and methane gas is 10：1~1：1.Can be carried further using segmentation reduction mode
The activity stability of high catalyst and the selectivity reducing methane.
The application of fischer-tropsch synthetic catalyst of the present invention：Reaction temperature is 180 ~ 250 DEG C, F- T synthesis unstripped gas（By hydrogen
With carbon monoxide composition）Volume space velocity be 200 ~ 1000h-1, reaction pressure is 1.0 ~ 4.0MPa, H in unstripped gas2/ CO=1～3
（Mol ratio）.
The present invention prepares a kind of metal composite oxide with perovskite structure as fischer-tropsch synthetic catalyst, and it leads to
Formula is AxA’1-xByB’1-yO3, wherein A is rare earth lanthanum, and A ' is metallic potassium, and B is transiting metal nickel, and B ' is transition metals cobalt,
0.7<x<1,0<y<0.35, this catalyst has special duct and surface nature.Rare earth lanthanum on A position can improve calcium
The structural stability of titanium ore and thermally-stabilised, can not only improve stability and the anti-carbon deposit energy of perovskite after the doping metals potassium of A ' position
Power, moreover it is possible to the valence state of adjustment B position metal, increases the quantity of Lattice Oxygen, improves activity；The doping of nickel on B position, makes cobalt metal ion
Electric charge, radius change, so that active component cobalt reduction degree improves, and then are conducive to improving the activity of catalyst, and
Be conducive to improving C5 +Selectively.
The composite oxides fischer-tropsch synthetic catalyst that the present invention has perovskite structure adopts citric acid complex one-step method system
Standby, operating process is simple, and technical maturity is suitable to industrial production.
The present invention has the application in Fischer-Tropsch synthesis of the composite oxides of perovskite structure.Experiment shows, suitable
Preferably under process conditions, this catalyst can make CO conversion ratio reach more than 90% and ensure C simultaneously5 +Selectivity can reach
More than 90%（Selectively press certain product and all product（Except water）Weight ratio meter calculate）, greatly reduce follow-up product
The investment of thing separation equipment and operating cost, are conducive to economy when improving F- T synthesis technology application.
Specific embodiment
Further illustrate process and the effect of the inventive method with reference to embodiment.
Embodiment 1
Take 20.7gCo (NO3)26H2O and 2.3gNi (NO3)26H2O puts in the beaker of 500mL so as to Co and Ni's rubs
Your ratio is 0.9/0.1, adds the distilled water of 100mL, then beaker is placed in 80 DEG C of water-bath, and mixing speed is 400rpm,
Stir and dissolve to whole.Take 30.87g La (NO3)36H2O and 0.8gKNO3It is placed with the beaker of 100mL distilled water, stirring
To whole dissolvings so as to the mol ratio of La and K is 0.9/0.1.Then lanthanum nitrate and potassium nitrate solution be added drop-wise to cobalt nitrate and
In nickel nitrate solution, stir in dropping.Take 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2：1, put into
Have in the beaker of 100mL to stir and dissolve to whole, now after above-mentioned mixed solution stirs 30 minutes, slowly add citric acid
Solution, stirs in dropping.After 5 hours of stirring, brown solution has been dehydrated the gel becoming thick, gel is taken out and puts
Enter in 110 DEG C of drying box, be dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with 3 DEG C/
The heating rate of min rises to 600 DEG C from room temperature, 3 hours of constant temperature calcining, then rises to 800 DEG C with the heating rate of 10 DEG C/min,
4 hours of constant temperature calcining, obtain catalyst C-1.
Embodiment 2
Take 21.85gCo (NO3)26H2O and 1.15gNi (NO3)26H2O puts in the beaker of 500mL so as to Co and Ni
Mol ratio is 0.95/0.05, adds the distilled water of 100mL, then beaker is placed in 80 DEG C of water-bath, mixing speed is
400rpm, stirs and dissolves to whole.Take 29.15g La (NO3)36H2O and 1.2gKNO3It is placed with the beaker of 100mL distilled water
In, stir to whole dissolvings so as to the mol ratio of La and K is 0.85/0.15.Then lanthanum nitrate and potassium nitrate solution are added drop-wise to
In cobalt nitrate solution, stir in dropping.Take 60g citric acid, citric acid and metal ion total amount mol ratio are 1.8：1, put into
Have in the beaker of 100mL to stir and dissolve to whole, now after above-mentioned mixed solution stirs 30 minutes, slowly add citric acid
Solution, stirs in dropping.After 5 hours of stirring, brown solution has been dehydrated the gel becoming thick, gel is taken out and puts
Enter in 110 DEG C of drying box, be dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with 3 DEG C/
The heating rate of min rises to 700 DEG C from room temperature, 3 hours of constant temperature calcining, then rises to 800 DEG C with the heating rate of 10 DEG C/min,
4 hours of constant temperature calcining, obtain catalyst C-2.
Embodiment 3
Take 16.1gCo (NO3)26H2O and 6.9gNi (NO3)26H2O puts in the beaker of 500mL so as to Co and Ni's rubs
Your ratio is 0.7/0.3, adds the distilled water of 100mL, then beaker is placed in 80 DEG C of water-bath, and mixing speed is 400rpm,
Stir and dissolve to whole.Take 27.44g La (NO3)36H2O and 1.6gKNO3It is placed with the beaker of 100mL distilled water, stirring
To whole dissolvings so as to the mol ratio of La and K is 0.8/0.2.Then lanthanum nitrate and potassium nitrate solution are added drop-wise to cobalt nitrate molten
In liquid, stir in dropping.Take 80g citric acid, citric acid and metal ion total amount mol ratio are 2.4：1, it is placed with 100mL
Beaker in stir and dissolve to whole, now after above-mentioned mixed solution stirs 30 minutes, slowly add citric acid solution, side
The stirring of dropping side.After 5 hours of stirring, brown solution has been dehydrated the gel becoming thick, gel is taken out and puts into 110
DEG C drying box in, be dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the liter of 3 DEG C/min
Warm speed rises to 600 DEG C from room temperature, 2 hours of constant temperature calcining, then rises to 800 DEG C with the heating rate of 10 DEG C/min, and constant temperature roasts
Burn 2 hours, obtain catalyst C-3.
Embodiment 4
Take 20.7gCo (NO3)26H2O and 2.3gNi (NO3)26H2O puts in the beaker of 500mL so as to Co and Ni's rubs
Your ratio is 0.9/0.1, adds the distilled water of 100mL, then beaker is placed in 80 DEG C of water-bath, and mixing speed is 400rpm,
Stir and dissolve to whole.Take 29.15g La (NO3)36H2O and 1.2gKNO3It is placed with the beaker of 100mL distilled water, stirring
To whole dissolvings so as to the mol ratio of La and K is 0.85/0.15.Then lanthanum nitrate and potassium nitrate solution are added drop-wise to cobalt nitrate
In nickel nitrate solution, stir in dropping.Take 60g citric acid, citric acid and metal ion total amount mol ratio are 1.8：1, put
Stir in the beaker entering to have 100mL and dissolve to whole, now after above-mentioned mixed solution stirs 30 minutes, slowly add lemon
Acid solution, stirs in dropping.After 5 hours of stirring, brown solution has been dehydrated the gel becoming thick, and gel is taken out
Put in 110 DEG C of drying box, be dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with 3
DEG C/heating rate of min rises to 700 DEG C from room temperature, 2 hours of constant temperature calcining, then rise to 800 with the heating rate of 10 DEG C/min
DEG C, 3 hours of constant temperature calcining, obtain catalyst C-4.
Comparative example 1
Contain the composite metal catalyst of lanthanum, nickel, cobalt using coprecipitation preparation.（No perovskite structure）, lanthanum in oxide,
Nickel, the content of cobalt are with embodiment 1.
Comparative example 2
Infusion process Supported Co, lanthanum, nickel are adopted for carrier with silica, cobalt, lanthanum, the mol ratio of nickel are with embodiment 1.
Embodiment 5
Activity rating is carried out to the catalyst prepared by embodiment and comparative example, evaluation test continuously stirs autoclave in high pressure
In reactor, using paraffin as solvent, with reductase 12 at 350 DEG C of pure hydrogen 0 hour, pressure was 1.0MPa.Switching and merging gas after cooling
Reacted.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 220 DEG C, 500h-1, 2.0MPa, H2/CO=2
（Mol ratio）.Evaluation result is shown in Table 1.
Table 1 catalyst reaction performance
| Catalyst | CO conversion ratio（%） | C5 +Selectively（wt%） | CH4Selectively（wt%） |
| C-1 | 92.5 | 90.2 | 4.58 |
| B-1 | 37.9 | 62.4 | 23.1 |
| B-2 | 71.7 | 75.7 | 10.7 |
| C-2 | 91.9 | 90.3 | 4.97 |
| C-3 | 92.1 | 90.7 | 4.81 |
| C-4 | 91.7 | 90.1 | 4.53 |
Embodiment 6
Activity rating is carried out to the catalyst of embodiment 1-4, evaluation test in high pressure CSTR, with
As solvent, using segmentation method of reducing, the reducing condition of wherein embodiment 1 is paraffin：Reduce in a hydrogen atmosphere first
10h, 350 DEG C of reduction temperature, reduce pressure 1MPa, then volume ratio be 5：Reduce under 1 hydrogen and the mixed atmosphere of methane
10h, 210 DEG C of reduction temperature, reduce pressure 1MPa；The reducing condition of embodiment 2 is：Reduce 6h first in a hydrogen atmosphere, also
300 DEG C of former temperature, reduces pressure 0.6MPa, is then 4 in volume ratio：8h is reduced, also under 1 hydrogen and the mixed atmosphere of methane
200 DEG C of former temperature, reduces pressure 0.5MPa；The reducing condition of embodiment 3 is：Reduce 15h, reduction temperature first in a hydrogen atmosphere
Degree 350 DEG C, reduce pressure 1MPa, then volume ratio be 10：15h, reduction temperature is reduced under 1 hydrogen and the mixed atmosphere of methane
220 DEG C of degree, reduces pressure 2MPa；The reducing condition of embodiment 4 is：Reduce 5h, reduction temperature 400 first in a hydrogen atmosphere
DEG C, reduce pressure 1MPa, then volume ratio be 2：15h, reduction temperature 190 is reduced under 1 hydrogen and the mixed atmosphere of methane
DEG C, reduce pressure 2.5MPa.After reduction terminates, cooling switching and merging gas is reacted.Reaction effluent is respectively by hot trap, cold-trap
Collect.Reaction condition is 220 DEG C, 500h-1, 2.0MPa, H2/CO=2（Mol ratio）.200h operating evaluation result is shown in Table 2.
Table 2 catalyst reaction performance
| Catalyst | CO conversion ratio（%） | C5 +Selectively（wt%） | CH4Selectively（wt%） |
| C-1 | 92.7 | 92.4 | 2.04 |
| C-2 | 92.3 | 91.3 | 2.13 |
| C-3 | 92.2 | 91.7 | 2.13 |
| C-4 | 91.9 | 91.4 | 2.22 |
Claims (9)
1. a kind of method of reducing of fischer-tropsch synthetic catalyst it is characterised in that：Mode is reduced using segmentation；Described segmentation reduction side
Formula reduces 4 ~ 20h first under the atmosphere of hydrogen, and reduction temperature is 300-400 DEG C, reduces pressure 0.5 ~ 1.5MPa, then in hydrogen
Under the atmosphere of gas and methane mixed gas reduce 4 ~ 18h, reduction temperature be 180 ~ 240 DEG C, reduction pressure be 0.5 ~ 3MPa, hydrogen with
The volumetric mixture ratio of methane gas is 10：1~1：1；Wherein, this fischer-tropsch synthetic catalyst is the composition metal with perovskite structure
Oxide, formula is AxA’1-xByB’1-yO3, wherein A is rare earth lanthanum, and A ' is metallic potassium, and B is transiting metal nickel, and B ' was
Cross metallic cobalt, 0.7<x<1,0<y<0.35.
2. the method for reducing described in claim 1 it is characterised in that：With cobalt nitrate, potassium nitrate, lanthanum nitrate, nickel nitrate as forerunner
Body, citric acid or ethylene glycol are complexing agent, wiring solution-forming mixing and stirring；Then moisture evaporation, solution went from clear are carried out
Colloidal sol be transformed into sticky gel, be finally dried, roasting, the composite oxides F- T synthesis obtaining having perovskite structure urge
Agent.
3. according to the method for reducing described in claim 2 it is characterised in that：Complexing agent and metal ion mol ratio are 1：1～8：
1.
4. according to the method for reducing described in claim 3 it is characterised in that：Complexing agent and metal ion mol ratio are 1：1～4：
1.
5. according to the method for reducing described in claim 2 it is characterised in that：Prepare and agitating solution carried out at 20～90 DEG C,
Mixing time is 3～8 hours, and mixing speed is 200～500rpm.
6. according to the method for reducing described in claim 5 it is characterised in that：Prepare and agitating solution carried out at 50～70 DEG C,
Mixing time is 4～6 hours, and stir speed (S.S.) is 300～400rpm.
7. according to the method for reducing described in claim 2 it is characterised in that：Baking temperature is 60～200 DEG C, and drying time is 1
～36 hours, roasting roasting 2-15 hour at 400～1000 DEG C.
8. according to the method for reducing described in claim 7 it is characterised in that：Baking temperature is 80～150 DEG C, and drying time is 8
～24 hours, roasting roasting 3～8 hours at 700～900 DEG C.
9. a kind of Fischer-Tropsch synthesis method it is characterised in that：Using the catalyst described in claim 1 and method of reducing, Fischer-Tropsch closes
The reaction temperature becoming is 180 ~ 250 DEG C, and the volume space velocity of F- T synthesis unstripped gas is 400 ~ 1000h-1, reaction pressure be 1.0 ~
5.0MPa, H in unstripped gas2Mol ratio=1～3 of/CO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310529634.1A CN104588023B (en) | 2013-11-01 | 2013-11-01 | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310529634.1A CN104588023B (en) | 2013-11-01 | 2013-11-01 | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104588023A CN104588023A (en) | 2015-05-06 |
| CN104588023B true CN104588023B (en) | 2017-02-22 |
Family
ID=53114278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310529634.1A Active CN104588023B (en) | 2013-11-01 | 2013-11-01 | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104588023B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040248A (en) * | 2016-06-12 | 2016-10-26 | 常州大学 | Method for preparing load type ternary metal oxide catalyst |
| CN108728153B (en) * | 2017-04-19 | 2021-05-14 | 中国石油化工股份有限公司 | Production method of low-carbon olefin and low-carbon olefin production system |
| CN108728152B (en) * | 2017-04-19 | 2021-05-14 | 中国石油化工股份有限公司 | Synthetic oil production method and synthetic oil production system |
| CN108728151B (en) * | 2017-04-19 | 2021-05-14 | 中国石油化工股份有限公司 | Alpha-olefin production method and alpha-olefin production system |
| CN108097239B (en) * | 2017-12-15 | 2020-05-19 | 华中科技大学 | A new type of coal char carbon dioxide gasification catalyst and preparation method thereof |
| CN110732346A (en) * | 2018-07-18 | 2020-01-31 | 华东理工大学 | polymetallic methanation catalyst, and preparation method and application thereof |
| CN111068745B (en) * | 2018-10-19 | 2023-02-17 | 中国石油化工股份有限公司 | Process for producing alpha-olefins |
| CN110589763B (en) * | 2019-09-02 | 2023-02-10 | 四川普瑞思达科技服务有限公司 | Method for preparing hydrogen by catalytic cracking of acetylene |
| CN113600200A (en) * | 2021-07-16 | 2021-11-05 | 南昌大学 | Preparation method of anti-carbon deposition methane dry gas reforming Ni-based alkaline earth metal modified catalyst |
| CN114700081B (en) * | 2022-03-18 | 2023-06-20 | 南京大学 | Preparation and application of a perovskite metal cerium salt with properties regulated by transition metal ions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909016A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for stepwise activating dehydrogenation catalyst by using gas mixture of hydrocarbon/hydrogen and hydrogen gas |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195088A (en) * | 2007-12-24 | 2008-06-11 | 上海兖矿能源科技研发有限公司 | Catalyst for synthesizing gas and liquid fuel, preparation method and application thereof |
| CN103373704B (en) * | 2012-04-12 | 2015-08-12 | 中国石油化工股份有限公司 | The application of a kind of composite metal oxide oxygen carrier in recycle chemistry chain hydrogen production and preparation |
-
2013
- 2013-11-01 CN CN201310529634.1A patent/CN104588023B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909016A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for stepwise activating dehydrogenation catalyst by using gas mixture of hydrocarbon/hydrogen and hydrogen gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104588023A (en) | 2015-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104588023B (en) | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN110327933B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN103785391B (en) | A kind of high activity fischer-tropsch synthetic catalyst and its preparation method and application | |
| CN103599788B (en) | A kind of cobalt-base catalyst for CO hydrogenation and its preparation method and application | |
| CN108380218A (en) | A kind of uniform nickel cobalt (alloy) catalyst of support type and preparation method thereof | |
| CN103611540B (en) | A kind of Catalysts and its preparation method for CO hydrogenation and application | |
| CN106799228B (en) | Catalyst for preparing hydrogen by reforming methanol and preparation and application thereof | |
| CN107597119B (en) | Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof | |
| CN104588033B (en) | Slurry bed Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN103589446B (en) | A kind of method of iron-based liquid hydrocarbon | |
| CN107774269A (en) | Co deposited synthesis copper ceria catalyst, preparation method and application | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN102441386A (en) | Novel Fischer-Tropsch synthesis method | |
| CN103599779B (en) | A kind of CuO/ZrO 2water gas converting catalyst and preparation method thereof | |
| CN104588022B (en) | Reduction method of Fischer-Tropsch synthesis catalyst | |
| CN112403491A (en) | Catalyst for preparing liquid fuel by high-selectivity conversion of synthesis gas and preparation method and application thereof | |
| CN103785392B (en) | A kind of fischer-tropsch synthetic catalyst and its preparation method and application | |
| CN102864008B (en) | Composite oxide oxygen carrier and preparation method and application thereof | |
| CN103623828B (en) | A kind of synthesizing liquid hydrocarbon cobalt-base catalyst and its preparation method and application | |
| CN114260016A (en) | A method of using Pd/ZnFexAl2-xO4 catalyst for methanol reforming to produce hydrogen | |
| CN103586033B (en) | A kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application | |
| CN106861705A (en) | A kind of modification type meso-porous nano copper zinc complexes and its preparation method and application | |
| CN103374429B (en) | A kind of composite metal oxide oxygen carrier and its preparation method and application | |
| CN103586038B (en) | A kind of fischer-tropsch synthetic catalyst and its preparation method and application | |
| CN101559375B (en) | Catalyst for preparing hydrogen from coke-oven gas in oxygen-permeable membrane reactor and preparation method 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 |