CN102671665A - Co-based Fischer-Tropsch synthesis catalyst with high Co content, as well as preparation method and application thereof - Google Patents
Co-based Fischer-Tropsch synthesis catalyst with high Co content, as well as preparation method and application thereof Download PDFInfo
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- CN102671665A CN102671665A CN2012101600225A CN201210160022A CN102671665A CN 102671665 A CN102671665 A CN 102671665A CN 2012101600225 A CN2012101600225 A CN 2012101600225A CN 201210160022 A CN201210160022 A CN 201210160022A CN 102671665 A CN102671665 A CN 102671665A
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Abstract
The invention relates to a Co-based Fischer-Tropsch synthesis catalyst with high Co content, which is characterized by comprising active components and a carrier; the Co-based Fischer-Tropsch synthesis catalyst comprises the components by weight percent: 25-80% of cobalt oxide, 1-15% of non-noble metal oxide in transition metal and the balance of aluminium oxide carrier. The Co-based Fischer-Tropsch synthesis catalyst is high in metal Co content and catalytic activity, and is not added with noble metal component, so that the cost of the catalyst is lowered.
Description
Technical field
The invention belongs to the synthetic field of Fischer-Tropsch, a kind of Co based Fischer-Tropsch synthesis catalyst and preparation and application of high cobalt content specifically are provided.
Background technology
The synthetic process that coal, natural gas or living beings is changed into hydro carbons through synthesis gas under catalyst action that is meant of Fischer-Tropsch.Can obtain numerous clean fuels and chemicals such as gasoline, produce oil, wax, naphtha, low-carbon alkene through this process, so its process is paid close attention to widely and is studied.Advantages such as the catalyst that Fischer-Tropsch synthesis adopts is divided into iron-based and two types of cobalt-baseds, and cobalt-base catalyst has high activity in course of reaction, low water gas shift reaction and become Fischer-Tropsch synthesize in the most rising catalyst.Therefore, efficient, the cheap Co based Fischer-Tropsch synthesis catalyst of design performance will have great technological competitiveness and great commercial promise.
Generally speaking, cobalt-base catalyst often adopts the cobalt salt direct impregnation on the indifferent oxide carrier, and adding second component again is that auxiliary agent is to improve or fortifying catalytic agent performance.Therefore, the load capacity of raising metallic cobalt can increase catalyst activity.Yet because the cobalt tenor of carrier specific surface restriction cobalt-base catalyst is all lower, this directly causes catalyst activity not promote.(Appl.Catal. 1999,186 (1-2): 129-144) summary has contrasted a series of cobalt-base catalyst patents of some companies in recent years such as Gulf, Shell, Exoon, Statoil etc. to Rachid Oukaci etc.These CATALYST Co content are 12 ~ 20%, contain second metal (Ru or Re), are auxiliary agent with La, Zr or alkali-metal oxide, and carrier is Al
2O
3, SiO
2Perhaps TiO
2Deng.Patent CN 101134164A has reported a kind of dipping method of Co based Fischer-Tropsch synthesis catalyst preparation.Catalyst carrier is with the solution impregnating carrier that contains the cobalt metal component, and described dipping satisfies: V
L/ V
C=0.01 ~ 0.09, wherein, V
LBe maceration extract volume, V
CPore volume for carrier.Above-mentioned catalyst and preparation method can not effectively increase the metallic cobalt load capacity.The reduction of active component causes catalyst activity relatively poor.
Summary of the invention
The purpose of this invention is to provide a kind of high cobalt content, highly active alumina load Co catalysts and preparation method and the application in Fischer-Tropsch is synthetic.
Catalyst of the present invention is made up of active component and carrier, and its percentage by weight consists of: cobalt oxide: 25-80%, and non-noble metal oxide in the transition metal: 1-15%, all the other are alumina support.
Base metal is La, Zr, Ti, Ce, Zn or Mn etc. in the aforesaid transition metal.
Preparation of catalysts method of the present invention is following:
(1) with processing the alkali lye that concentration is 1～5mol/L in the bases precipitating reagent adding deionized water;
(2) boehmite is mixed making beating with deionized water and obtain the boehmite slurries, its solid content remains on 40～70%;
(3) 70-90% with solubility cobalt salt weight is dissolved in the boehmite slurries of step (2), obtains to contain cobalt boehmite slurries;
(4) alkali lye of step (1) is added drop-wise to containing in the cobalt boehmite slurries of step (3) that band stirs; Rate of addition is 0.5-2L/h; Keep 40～90 ℃ of slurry temperatures, control endpoint pH 7～10, deposition finished the back static aging 1～6 hour; Obtain precipitating slurry, wash to free from admixture;
(5) after the feed separation after will washing, be 40-100 ℃ of dry 2-12h down with sediment at baking temperature, carry out roasting after the drying, sintering temperature is 200-500 ℃, and roasting time is 3-20 h; Obtain the cobalt-containing catalyst carrier;
(6) measure deionized water by incipient impregnation, will remain solubility cobalt salt (10-30%) and soluble transition metal in base metal salt be dissolved in the deionized water, room temperature condition is down and step (5) gained cobalt-containing catalyst carrier incipient impregnation; Dip time is 30-600 minute; Be 40-100 ℃ of dry 2-12h down at baking temperature afterwards, carry out roasting after the drying, sintering temperature is 200-400 ℃; Roasting time is 3-10 h, obtains final catalyst.
The bases precipitating reagent is ammoniacal liquor, NaOH, sodium carbonate or ammonium carbonate etc. as stated, preferred sodium carbonate
Boehmite average grain scope is the 20-60 micron as stated, and specific area is 150-350m
2/ g, the aperture is 8-15nm, pore volume is 0.35-0.55cm3/g; Impurity content: SiO
2: 1.0-2.0%; Fe
2O
3<0.05%, Na
2O:<0.1%.
The solubility cobalt salt is organic cobalt salt such as cobalt acetate as stated, inorganic cobalt salt such as cobalt nitrate, preferred cobalt nitrate;
Base metal salt is La (NO in the soluble transition metal as stated
3)
3, Zr (NO
3)
4, Ti Cl
4, Zn (NO
3)
2, Mn (NO
3)
2Or Ce (NO
3)
3Deng;
Applying step of the present invention is following:
Make catalyst and in fixed bed reactors, in 300 ℃-600 ℃ hydrogen, reduce, the reducing gas volume space velocity is 500-5000h
-1, reduction pressure is 0.1--1.0Mpa, the recovery time is 5--24h.
Be reflected in the fixed bed reactors and carry out, reaction condition is H
2/ CO (mol) is between 1--3, and reaction temperature is 190--240 ℃, and pressure is 1.0--3.0Mpa, and air speed is 500--5000h
-1
The present invention compared with prior art has following advantage:
1. the catalyst metals cobalt content is high, and catalytic activity is high.
2. catalyst does not add noble metal component, reduces the catalyst cost.
The specific embodiment:
Following embodiment will do further explanation to the present invention, and protection scope of the present invention does not receive the restriction of these embodiment.
Embodiment 1:
Preparation of Catalyst: 10 (wt) % by final catalyst is measured boehmite, mixes making beating with deionized water, and its solid content is 40%, and 80 (wt) % that accounts for final catalyst by cobalt oxide takes by weighing cobalt nitrate, and 90 (wt) % wherein is dissolved in these slurries.The 2mol/L aqueous slkali of preparation capacity under agitation is added drop-wise to above-mentioned slurries, and rate of addition is 0.5L/h, keeps 55 ℃ of slurry temperatures, and control endpoint pH 8.0, deposition finish back static burn in 5h, wash, are filtered to free from admixture.With filter cake dry 8h under 80 ℃,, make catalyst carrier then at 350 ℃ of following roasting 7 h; 10 (wt) % that accounts for final catalyst by zirconia takes by weighing zirconium nitrate; According to the equi-volume impregnating obtain solution and impregnated in above-mentioned carrier, dip time is 5h with residue 30 (wt) % cobalt nitrate, then at 100 ℃ of dry 6h down; At 350 ℃ of roasting 5 h, make catalyst at last.Final catalyst quality percentage is Co
3O
4: ZrO
2: Al
2O
3=80:10:10.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is: 500 ℃, and 1.2 MPa, 2500 h
-1(V/V), constant temperature 8 h.Be reflected in the fixed bed reactors and carry out, reaction condition is: 235 ℃, and 2.0MPa, 3000h
-1(V/V), H
2/ CO=1.8.Reaction result is seen table 1.
Embodiment 2:
Preparation of Catalyst: 74 (wt) % by final catalyst is measured boehmite, mixes making beating with deionized water, and its solid content is 50%, and 25 (wt) % that accounts for final catalyst by cobalt oxide takes by weighing cobalt nitrate, and 80 (wt) % wherein is dissolved in these slurries.The 0.5mol/L aqueous slkali of preparation capacity under agitation is added drop-wise to above-mentioned slurries, and rate of addition is 1.5L/h, keeps 40 ℃ of slurry temperatures, and control endpoint pH 10.0, deposition finish back static burn in 1h, wash, are filtered to free from admixture.With filter cake dry 8h under 50 ℃,, make catalyst carrier then at 350 ℃ of following roasting 7 h; Press La
2O
31 (wt) % that accounts for final catalyst takes by weighing lanthanum nitrate; According to the equi-volume impregnating obtain solution and impregnated in above-mentioned carrier, dip time is 3h with residue 20 (wt) % cobalt nitrate, then at 110 ℃ of dry 6h down; At 200 ℃ of roasting 10 h, make catalyst at last.Final catalyst weight is Co
3O
4: La
2O
3: Al
2O
3=25:1:74.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is: 400 ℃, and 1.0 MPa, 1500 h
-1(V/V), constant temperature 12 h.Be reflected in the fixed bed reactors and carry out, reaction condition is: 235 ℃, and 2.0MPa, 5000h
-1(V/V), H
2/ CO=2.Reaction result is seen table 1.
Embodiment 3:
Preparation of Catalyst: 37 (wt) % by final catalyst is measured boehmite, mixes making beating with deionized water, and its solid content is 60%, and 60 (wt) % that accounts for final catalyst by cobalt oxide takes by weighing cobalt nitrate, and 90 (wt) % wherein is dissolved in these slurries.The 1.5mol/L aqueous slkali of preparation capacity under agitation is added drop-wise to above-mentioned slurries, and rate of addition is 2L/h, keeps 90 ℃ of slurry temperatures, and control endpoint pH 7.0, deposition finish back static burn in 6h, wash, are filtered to free from admixture.With filter cake dry 12h under 40 ℃,, make catalyst carrier then at 200 ℃ of following roasting 20 h; 3 (wt) % that accounts for final catalyst by cerium oxide takes by weighing cerous nitrate; According to the equi-volume impregnating obtain solution and impregnated in above-mentioned carrier, dip time is 10h with residue 10 (wt) % cobalt nitrate, then at 40 ℃ of dry 12h down; At 200 ℃ of roasting 10 h, make catalyst at last.Final catalyst weight is Co
3O
4: CeO
2: Al
2O
3=60:3:37.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is: 600 ℃, and 0.1 MPa, 500 h
-1(V/V), constant temperature 10 h.Be reflected in the fixed bed reactors and carry out, reaction condition is: 225 ℃, and 2.0MPa, 1000h
-1(V/V), H
2/ CO=2.5.Reaction result is seen table 1.
Embodiment 4:
Preparation of Catalyst: 50 (wt) % by final catalyst is measured boehmite, mixes making beating with deionized water, and its solid content is 60%, and 35 (wt) % that accounts for final catalyst by cobalt oxide takes by weighing cobalt acetate, and 85 (wt) % wherein is dissolved in these slurries.The 1mol/L aqueous slkali of preparation capacity under agitation is added drop-wise to above-mentioned slurries, and rate of addition is 0.8L/h, keeps 65 ℃ of slurry temperatures, and control endpoint pH 8.5, deposition finish back static burn in 2h, wash, are filtered to free from admixture.With filter cake dry 4h under 90 ℃,, make catalyst carrier then at 380 ℃ of following roasting 11 h; 15 (wt) % that accounts for final catalyst by zinc oxide takes by weighing zinc nitrate; According to the equi-volume impregnating obtain solution and impregnated in above-mentioned carrier, dip time is 3h with residue 15 (wt) % cobalt acetate, then at 100 ℃ of dry 2h down; At 500 ℃ of roasting 3 h, make catalyst at last.Final catalyst weight is Co
3O
4: ZnO:Al
2O
3=35:15:50.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is: 600 ℃, and 0.2MPa, 500 h
-1(V/V), constant temperature 24 h.Be reflected in the fixed bed reactors and carry out, reaction condition is: 190 ℃, and 3.0MPa, 1000h
-1(V/V), H
2/ CO=3.Reaction result is seen table 1.
Embodiment 5:
Preparation of Catalyst: 15 (wt) % by final catalyst is measured boehmite, mixes making beating with deionized water, and its solid content is 65%, and 70 (wt) % that accounts for final catalyst by cobalt oxide takes by weighing cobalt nitrate, and 75 (wt) % wherein is dissolved in these slurries.The 1mol/L aqueous slkali of preparation capacity under agitation is added drop-wise to above-mentioned slurries, and rate of addition is 1L/h, keeps 85 ℃ of slurry temperatures, and control endpoint pH 8.5, deposition finish back static burn in 4.5h, wash, are filtered to free from admixture.With filter cake dry 7h under 80 ℃,, make catalyst carrier then at 350 ℃ of following roasting 11h; 15 (wt) % that accounts for final catalyst by manganese oxide takes by weighing manganese nitrate; According to the equi-volume impregnating obtain solution and impregnated in above-mentioned carrier, dip time is 10h with residue 25 (wt) % cobalt nitrate, then at 70 ℃ of dry 3h down; At 450 ℃ of roasting 6h, make catalyst at last.Final catalyst weight is Co
3O
4: MnO
2: Al
2O
3=70:15:15.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is: 300 ℃, and 0.1MPa, 5000 h
-1(V/V), constant temperature 18 h.Be reflected in the fixed bed reactors and carry out, reaction condition is: 240 ℃, and 2.0MPa, 1500h
-1(V/V), H
2/ CO=1.6.Reaction result is seen table 1.
Embodiment 6:
Preparation of Catalyst: 40 (wt) % by final catalyst is measured boehmite, mixes making beating with deionized water, and its solid content is 50%, and 55 (wt) % that accounts for final catalyst by cobalt oxide takes by weighing cobalt nitrate, and 80 (wt) % wherein is dissolved in these slurries.The 2mol/L aqueous slkali of preparation capacity under agitation is added drop-wise to above-mentioned slurries, and rate of addition is 1L/h, keeps 70 ℃ of slurry temperatures, and control endpoint pH 8.0, deposition finish back static burn in 3h, wash, are filtered to free from admixture.With filter cake dry 8h under 80 ℃,, make catalyst carrier then at 350 ℃ of following roasting 6h; 8 (wt) % that accounts for final catalyst by zirconia takes by weighing zirconium oxychloride; According to the equi-volume impregnating obtain solution and impregnated in above-mentioned carrier, dip time is 5h with residue 20 (wt) % cobalt nitrate, then at 80 ℃ of dry 6h down; At 350 ℃ of roasting 5 h, make catalyst at last.Final catalyst weight is Co
3O
4: ZrO
2: Al
2O
3=55:5:40.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is: 350 ℃, and 1.2 MPa, 2500 h
-1(V/V), constant temperature 12 h.Be reflected in the fixed bed reactors and carry out, reaction condition is: 210 ℃, and 2.0MPa, 1200h
-1(V/V), H
2/ CO=1.7.Reaction result is seen table 1.
Embodiment 7:
Preparation of Catalyst: 48 (wt) % by final catalyst is measured boehmite, mixes making beating with deionized water, and its solid content is 60%, and 45 (wt) % that accounts for final catalyst by cobalt oxide takes by weighing cobalt nitrate, and 85 (wt) % wherein is dissolved in these slurries.The 2mol/L aqueous slkali of preparation capacity under agitation is added drop-wise to above-mentioned slurries, and rate of addition is 1L/h, keeps 55 ℃ of slurry temperatures, and control endpoint pH 8.0, deposition finish back static burn in 5h, wash, are filtered to free from admixture.With filter cake dry 8h under 80 ℃,, make catalyst carrier then at 450 ℃ of following roasting 9 h; 7 (wt) % that accounts for final catalyst by titanium oxide takes by weighing titanium tetrachloride; According to the equi-volume impregnating obtain solution and impregnated in above-mentioned carrier, dip time is 9h with residue 15 (wt) % cobalt nitrate, then at 85 ℃ of dry 6h down; At 300 ℃ of roasting 10 h, make catalyst at last.Final catalyst weight is Co
3O
4: TiO
2: Al
2O
3=45:7:48.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is: 500 ℃, and 1.2 MPa, 2500 h
-1(V/V), constant temperature 16 h.Be reflected in the fixed bed reactors and carry out, reaction condition is: 220 ℃, and 3.0MPa, 800h
-1(V/V), H
2/ CO=2.2.Reaction result is seen table 1.
Embodiment 8:
Preparation of Catalyst: 48 (wt) % by final catalyst is measured boehmite, mixes making beating with deionized water, and its solid content is 65%, and 50 (wt) % that accounts for final catalyst by cobalt oxide takes by weighing cobalt acetate, and 90 (wt) % wherein is dissolved in these slurries.The 0.8mol/L aqueous slkali of preparation capacity under agitation is added drop-wise to above-mentioned slurries, and rate of addition is 1.2L/h, keeps 75 ℃ of slurry temperatures, and control endpoint pH 7.5, deposition finish back static burn in 3.5h, wash, are filtered to free from admixture.With filter cake dry 8h under 80 ℃,, make catalyst carrier then at 330 ℃ of following roasting 8h; 2 (wt) % that accounts for final catalyst by lanthana takes by weighing lanthanum chloride; According to the equi-volume impregnating obtain solution and impregnated in above-mentioned carrier, dip time is 5h with residue 10 (wt) % cobalt acetate, then at 100 ℃ of dry 6h down; At 350 ℃ of roasting 5 h, make catalyst at last.Final catalyst weight is Co
3O
4: La
2O
3: Al
2O
3=50:2:48.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is: 500 ℃, and 1.2 MPa, 2500 h
-1(V/V), constant temperature 14 h.Be reflected in the fixed bed reactors and carry out, reaction condition is: 200 ℃, and 1.0MPa, 2500h
-1(V/V), H
2/ CO=2.1.Reaction result is seen table 1.
Table 1 catalyst test condition and reaction result
| Catalyst | Reaction condition | CO conversion ratio % | C 1Selectivity % | C 5+ selectivity |
| Example 1 | 235 oC，3000h -1， | 62.7 | 7.8 | 85.7 |
| Example 2 | 235 oC，5000h -1， | 55.9 | 8.1 | 88.1 |
| Example 3 | 225 oC，1000h -1， | 72.4 | 7.2 | 90.5 |
| Example 4 | 190 oC，1000h -1， | 54.1 | 5.1 | 91.2. |
| Example 5 | 240 oC，1500h -1， | 91.8 | 9.8 | 83.2 |
| Example 6 | 210 oC，1200h -1， | 75.5 | 7.9 | 90.1 |
| Example 7 | 220 oC，800h -1， | 63.5 | 6.4 | 89.7 |
| Example 8 | 200 oC，2500h -1， | 78.1 | 7.5 | 87.5 |
Claims (10)
1. the Co based Fischer-Tropsch synthesis catalyst of a high cobalt content is characterized in that catalyst is made up of active component and carrier, and its percentage by weight consists of: cobalt oxide: 25-80%, and non-noble metal oxide in the transition metal: 1-15%, all the other are alumina support.
2. the Co based Fischer-Tropsch synthesis catalyst of a kind of high cobalt content as claimed in claim 1 is characterized in that base metal is La, Zr, Ti, Ce, Zn or Mn in the described transition metal.
3. according to claim 1 or claim 2 a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst of high cobalt content is characterized in that comprising the steps:
(1) with processing the alkali lye that concentration is 1～5mol/L in the bases precipitating reagent adding deionized water;
(2) boehmite is mixed making beating with deionized water and obtain the boehmite slurries, its solid content remains on 40～70%;
(3) 70-90% with solubility cobalt salt weight is dissolved in the boehmite slurries of step (2), obtains to contain cobalt boehmite slurries;
(4) alkali lye of step (1) is added drop-wise to containing in the cobalt boehmite slurries of step (3) that band stirs; Rate of addition is 0.5-2L/h; Keep 40～90 ℃ of slurry temperatures, control endpoint pH 7～10, deposition finished the back static aging 1～6 hour; Obtain precipitating slurry, wash to free from admixture;
(5) after the feed separation after will washing, be 40-100 ℃ of dry 2-12h down with sediment at baking temperature, carry out roasting after the drying, sintering temperature is 200-500 ℃, and roasting time is 3-20 h; Obtain the cobalt-containing catalyst carrier;
Measure deionized water by incipient impregnation, will remain solubility cobalt salt (10-30%) and soluble transition metal in base metal salt be dissolved in the deionized water, room temperature condition is down and step (5) gained cobalt-containing catalyst carrier incipient impregnation; Dip time is 30-600 minute; Be 40-100 ℃ of dry 2-12h down at baking temperature afterwards, carry out roasting after the drying, sintering temperature is 200-400 ℃; Roasting time is 3-10 h, obtains final catalyst.
4. the preparation method of the Co based Fischer-Tropsch synthesis catalyst of a kind of high cobalt content as claimed in claim 3 is characterized in that described bases precipitating reagent is ammoniacal liquor, NaOH, sodium carbonate or ammonium carbonate.
5. the preparation method of the Co based Fischer-Tropsch synthesis catalyst of a kind of high cobalt content as claimed in claim 4 is characterized in that described bases precipitating reagent is a sodium carbonate.
6. the preparation method of the Co based Fischer-Tropsch synthesis catalyst of a kind of high cobalt content as claimed in claim 3 is characterized in that described boehmite average grain scope is the 20-60 micron, and specific area is 150-350m
2/ g, the aperture is 8-15nm, pore volume is 0.35-0.55cm3/g; Impurity content: SiO
2: 1.0-2.0%; Fe
2O
3<0.05%, Na
2O:<0.1%.
7. the preparation method of the Co based Fischer-Tropsch synthesis catalyst of a kind of high cobalt content as claimed in claim 3 is characterized in that described solubility cobalt salt is cobalt acetate or cobalt nitrate.
8. the preparation method of the Co based Fischer-Tropsch synthesis catalyst of a kind of high cobalt content as claimed in claim 7 is characterized in that described solubility cobalt salt is a cobalt nitrate.
9. the preparation method of the Co based Fischer-Tropsch synthesis catalyst of a kind of high cobalt content as claimed in claim 3 is characterized in that base metal salt is La (NO in the described soluble transition metal
3)
3, Zr (NO
3)
4, Ti Cl
4, Zn (NO
3)
2, Mn (NO
3)
2Or Ce (NO
3)
3
10. the application of the Co based Fischer-Tropsch synthesis catalyst of a kind of high cobalt content as claimed in claim 3 is characterized in that comprising the steps:
(1) make catalyst in fixed bed reactors in 300 ℃--reduce in 600 ℃ the hydrogen, the reducing gas volume space velocity is 500-5000h
-1, reduction pressure is 0.1--1.0Mpa, the recovery time is 5--24h;
(2) be reflected in the fixed bed reactors and carry out, reaction condition is H
2/ CO (mol) is between 1--3, and reaction temperature is 190--240 ℃, and pressure is 1.0--3.0Mpa, and air speed is 500--5000h
-1
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| CN103143364A (en) * | 2013-03-12 | 2013-06-12 | 上海中科高等研究院 | High-dispersion nano-composite catalyst, and preparation method and applications thereof |
| CN103272603A (en) * | 2013-05-21 | 2013-09-04 | 神华集团有限责任公司 | Fischer-Tropsch catalyst containing zinc-cobalt base and preparation method thereof |
| CN103769109A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic gas conversion catalyst, and preparation method and applications thereof |
| CN103769098A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic gas conversion catalyst, and preparation method and applications thereof |
| CN103785392A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
| CN104162441A (en) * | 2014-08-19 | 2014-11-26 | 中国科学院山西煤炭化学研究所 | High-dispersion Fischer-Tropsch synthesis cobalt-based catalyst as well as preparation method and application thereof |
| JP2016182542A (en) * | 2015-03-25 | 2016-10-20 | 株式会社日本触媒 | Method for producing metal catalyst and metal catalyst obtained by the method |
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