CN110252358B - Fischer-Tropsch synthesis cobalt catalyst, preparation method thereof and Fischer-Tropsch synthesis method - Google Patents
Fischer-Tropsch synthesis cobalt catalyst, preparation method thereof and Fischer-Tropsch synthesis method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- 239000010941 cobalt Substances 0.000 title claims abstract description 77
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 77
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 56
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001308 synthesis method Methods 0.000 title abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 42
- 239000011572 manganese Substances 0.000 claims abstract description 41
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012688 phosphorus precursor Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 6
- 230000002779 inactivation Effects 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 24
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- 230000009849 deactivation Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
Abstract
The invention relates to the field of catalysts for Fischer-Tropsch synthesis, and discloses a Fischer-Tropsch synthesis cobalt catalyst, a preparation method thereof and a Fischer-Tropsch synthesis method. A preparation method of a Fischer-Tropsch synthesis cobalt catalyst comprises the following steps: (A) soaking the carrier in a mixed solution of a cobalt precursor and a manganese precursor, and drying and roasting to obtain a first modified catalyst; (B) and (3) dipping the first modified catalyst in a phosphorus precursor solution, and drying to obtain the Fischer-Tropsch synthesis cobalt catalyst. According to the invention, the cobalt catalyst for Fischer-Tropsch synthesis is modified by simultaneously using the catalytic auxiliary agents Mn and P, Co and Mn are loaded on the carrier firstly, then P is loaded, and a Co-impregnation method is adopted for loading, so that the stability of the cobalt catalyst for Fischer-Tropsch synthesis is greatly improved, the inactivation rate of the catalyst is greatly reduced, and the catalyst has great industrial application potential.
Description
Technical Field
The invention relates to the field of catalysts for Fischer-Tropsch synthesis, in particular to a Fischer-Tropsch synthesis cobalt catalyst and a preparation method thereof, and a Fischer-Tropsch synthesis method by adopting the Fischer-Tropsch synthesis cobalt catalyst.
Background
The Fischer-Tropsch synthesis reaction refers to synthesis gas (H)2+ CO) is converted to hydrocarbons and other chemicals over a catalyst at a temperature and pressure. In recent years, due to the growing shortage of petroleum resources, Fischer-Tropsch synthesis has attracted much attention from researchers in various countries around the world. Generally, the reaction of Fischer-Tropsch synthesis to produce hydrocarbons can be represented by the following equation:
mCO+(2m+1)H2→CmH2m+2+mH2O (1)
mCO+2mH2→CmH2m+mH2O (2)
2mCO+(m+1)H2→CmH2m+2+mCO2 (3)
in the Fischer-Tropsch synthesis reaction and the Fischer-Tropsch synthesis process, the catalyst is one of the most important core technologies. Iron (Fe), cobalt (Co), nickel (Ni) and ruthenium (Ru) are main metal elements which can be used as active components of the Fischer-Tropsch synthesis catalyst, and long-term theoretical research and practical experience show that: fe and Co are two metal elements which have the most industrial application value and are used as active components of the catalyst; currently, fischer-tropsch synthesis catalysts commonly used in the world are mainly two major systems, namely, iron (Fe) catalysts and cobalt (Co) catalysts.
Compared with an iron-based Fischer-Tropsch catalyst, the cobalt-based Fischer-Tropsch catalyst has the characteristics of high catalytic activity, high linear chain saturated heavy hydrocarbon selectivity, low water-gas shift reaction and the like. The Fischer-Tropsch cobalt catalyst has higher price, so the requirement on the service life of the Fischer-Tropsch cobalt catalyst is higher, and the stability of the catalyst is always a key point and a difficult point.
Fischer Tropsch Synthesis using a catalyzed cobalt-based catalyst, Catalysis Today, S.Iqbal et al,2016,272: 74-79 and US9416067B2 disclose a Fischer-Tropsch Synthesis cobalt catalyst modified by La and/or P, wherein cobalt salt and manganese salt are subjected to coprecipitation, washing and drying, then are impregnated and added with La and/or P for modification, and finally are roasted to obtain the catalyst. Compared with the cobalt-manganese coprecipitation catalyst which is not modified, the activity of the catalyst is reduced after P modification, and the selectivity of the byproduct methane and carbon dioxide is reduced. The above documents relate only to the activity of the catalyst, the selectivity to carbon dioxide and methane, and do not teach how to improve the stability of the catalyst. In fact, after the catalyst prepared by the cobalt-manganese coprecipitation method is modified by using P, the active phase cobalt has small crystal grains, and is easy to oxidize or sinter to grow in the reaction process, so that the activity of the catalyst is gradually reduced in the reaction process, and the stability of the catalyst is poor. Aiming at the problem of stability of the cobalt catalyst for Fischer-Tropsch synthesis:
《Fischer-Tropsch synthesis in slurry-phase reactors over Mn-and Zr-modified Co/SiO2catalysts Mn-Zr-Co/SiO are disclosed by catalytes, Fuel Process Technol, Y.L.Liu, et al,2009,90:901-2The catalyst was modified by Mn and Zr.
CN105582905A discloses a modified gamma-alumina carrier, a preparation method and application thereof. The modified gamma-alumina carrier contains 0.5-5 wt% of rare earth metal elements and 0.5-4 wt% of auxiliary elements, wherein the rare earth metal elements are selected from one or more of La, Ce, Y, Sm or Gd, and the auxiliary elements are selected from one or more of Si, Zr or Ti. The addition of rare earth elements can improve the pore size distribution of the alumina carrier, the addition of auxiliary elements of silicon, titanium or zirconium can react with active sites of the alumina carrier to generate stable compounds, the Fischer-Tropsch synthesis cobalt catalyst prepared by adopting the modified alumina avoids the problems of dissolution and the like of the carrier in the slurry state dipping process, the reaction period shows high activity, and the stability of the catalyst is also improved.
In summary, in the prior art, although some documents mention improvement of the stability of the cobalt catalyst for fischer-tropsch synthesis by modifying the catalyst with metals, non-metals, rare earth elements, etc., for example, the cobalt catalyst is modified with Mn — Zr, La, Ce, Y, Sm, Gd, Si or Ti, etc. In the industrial application of Fischer-Tropsch synthesis, although the stability of the catalyst is improved to a certain extent, the stability of the prepared catalyst is still not high, and the problem of further improving the stability of the Fischer-Tropsch synthesis cobalt catalyst is still a problem.
Disclosure of Invention
The invention aims to overcome the problem of poor stability of a Fischer-Tropsch synthesis cobalt catalyst in the prior art, and provides the Fischer-Tropsch synthesis cobalt catalyst, a preparation method thereof and a Fischer-Tropsch synthesis method.
In order to achieve the above object, the first aspect of the present invention provides a method for preparing a cobalt catalyst for fischer-tropsch synthesis, comprising the steps of:
(A) soaking a carrier in a mixed solution of a cobalt precursor and a manganese precursor, and carrying out first drying and roasting to obtain a first modified catalyst;
(B) and (3) dipping the first modified catalyst in a phosphorus precursor solution, and carrying out second drying to obtain the Fischer-Tropsch synthesis cobalt catalyst.
Preferably, the cobalt precursor is at least one of cobalt nitrate, cobalt acetate and cobalt chloride.
Preferably, the manganese precursor is manganese nitrate or manganese acetate.
Preferably, the support is alumina, silica or titania; preferably, the specific surface area of the carrier is 50 to 200m2(iii) a pore volume of 0.3 to 1.5 mL/g.
Preferably, the phosphorus precursor is at least one of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate.
Preferably, the conditions of the first drying include: the drying temperature is 70-120 ℃, and the drying time is 1-10 h; the roasting conditions comprise: the roasting temperature is 250-400 ℃, and the roasting time is 1-10 h; the conditions of the second drying include: the drying temperature is 70-120 ℃, and the drying time is 1-10 h.
The invention provides a Fischer-Tropsch synthesis cobalt catalyst prepared by the method, wherein the catalyst comprises a carrier, and a catalytic active component Co and a catalytic promoter which are loaded on the carrier, and the catalytic promoter contains Mn and P.
Preferably, the weight ratio of the catalytic active component Co to the carrier is (15-50): 100, preferably (25-35): 100, respectively; the molar ratio of Mn to the active component Co is (3-15): 100, preferably (5-10): 100, respectively; the molar ratio of P to the active component Co is (2-10): 100, preferably (4-8): 100.
preferably, the support is alumina, silica or titania.
Preferably, the specific surface area of the carrier is 50 to 200m2(iii) a pore volume of 0.3 to 1.5 mL/g.
In a third aspect, the invention provides a fischer-tropsch synthesis method, comprising reacting synthesis gas in the presence of a fischer-tropsch cobalt catalyst, wherein the fischer-tropsch cobalt catalyst is as described above.
According to the invention, the catalytic assistants Mn and P are used for modifying the Fischer-Tropsch synthesis cobalt catalyst, and the coupling effect of the Mn and P assistants is utilized, so that the stability of the Fischer-Tropsch synthesis cobalt catalyst is greatly improved, and the inactivation rate of the catalyst is greatly reduced.
In addition, in the preparation method, the Co and Mn are loaded on the carrier firstly, then the P is loaded, and the loading is carried out by a Co-impregnation method, so that the activity and the stability of the Fischer-Tropsch synthesis cobalt catalyst are greatly improved, and the preparation method has great industrial application potential.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a Fischer-Tropsch synthesis cobalt catalyst, which comprises the following steps:
(A) soaking a carrier in a mixed solution of a cobalt precursor and a manganese precursor, and carrying out first drying and roasting to obtain a first modified catalyst;
(B) and (3) dipping the first modified catalyst in a phosphorus precursor solution, and carrying out second drying to obtain the Fischer-Tropsch synthesis cobalt catalyst.
According to the method of the present invention, the cobalt precursor may be a soluble cobalt salt containing no elemental sulfur, and may be, for example, but not limited to, at least one of cobalt nitrate, cobalt acetate, and cobalt chloride. The sulfur element contained in the catalyst causes a sharp decrease in the activity of the catalyst, so that the precursor of cobalt contains no sulfur element.
According to the method of the present invention, the manganese precursor may be a water-soluble manganese salt as is conventional in the art, such as, but not limited to, manganese nitrate or manganese acetate. After the calcination step, it can become manganese oxide.
According to the method of the invention, the mixed solution of the cobalt precursor and the manganese precursor is an aqueous solution of the cobalt precursor and the manganese precursor, and the amount of water is greater than or equal to the pore volume of the carrier, so that the cobalt precursor and the manganese precursor are fully dissolved, for example, equal-volume impregnation can be performed, that is, the amount of water is equal to the pore volume of the carrier; slurry impregnation is also possible, i.e. the amount of water used is greater than the pore volume of the support.
According to the process of the present invention, the support may be a support for a fischer-tropsch synthesis cobalt catalyst as is conventional in the art, and may be, for example but not limited to, alumina, silica or titania and the like.
In a preferred embodiment of the present invention, the specific surface area of the support may be 50 to 200m2(iii) a pore volume of 0.3 to 1.5 mL/g.
According to the method of the present invention, the phosphorus precursor may be, but is not limited to, at least one of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate.
According to the method of the present invention, the phosphorus precursor solution is an aqueous solution of a phosphorus precursor, and the amount of water used is not particularly limited so as to sufficiently dissolve the phosphorus precursor.
According to the method of the present invention, the conditions of the first drying may include, but are not limited to: the drying temperature is 70-120 ℃, and the drying time is 1-10 h; the conditions of the calcination may include, but are not limited to: the roasting temperature is 250-400 ℃, and the roasting time is 1-10 h; the conditions of the second drying may include, but are not limited to: the drying temperature is 70-120 ℃, and the drying time is 1-10 h.
The invention provides a Fischer-Tropsch synthesis cobalt catalyst prepared by the method, wherein the catalyst comprises a carrier, and a catalytic active component Co and a catalytic promoter which are loaded on the carrier, and the catalytic promoter contains Mn and P.
In the present invention, the weight ratio of the catalytically active component Co to the support may be (15 to 50): 100, preferably (25-35): 100, wherein the weight of Co means the weight in terms of Co element.
In the present invention, the molar ratio of Mn to the active component Co may be (3 to 15): 100, preferably (5-10): 100, the molar amounts of Mn and Co refer to the molar amounts of Mn and Co elements.
In the present invention, the molar ratio of P to the active component Co may be (2-10): 100, preferably (4-8): 100, wherein the molar amount of P, Co refers to the molar amount based on P, Co elements.
The stability is very good in the preferred molar ratio range of Mn, P and active component Co.
In the present invention, the carrier may be a carrier of a fischer-tropsch synthesis cobalt catalyst conventional in the art, such as but not limited to alumina, silica or titania, and the like.
In a preferred embodiment of the present invention, the specific surface area of the support may be 50 to 200m2(iii) a pore volume of 0.3 to 1.5 mL/g.
In a third aspect, the invention provides a fischer-tropsch synthesis method, comprising reacting synthesis gas in the presence of a fischer-tropsch cobalt catalyst, wherein the fischer-tropsch cobalt catalyst is as described above.
The present invention will be described in detail below by way of examples.
Example 1
14.82 g of cobalt nitrate hexahydrate and 0.96 g of manganese nitrate tetrahydrate are taken, 3 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g) soaking, and mixing uniformlyStanding for 4h, drying at 100 ℃ for 4h, and then roasting at 300 ℃ for 6h to obtain the first modified Fischer-Tropsch cobalt catalyst. 0.3 g of phosphoric acid is weighed, added with 7 g of water to be dissolved, mixed and impregnated with the first modified catalyst, kept stand for 4 hours, and dried at 80 ℃ for 6 hours to obtain an S1 catalyst.
Example 2
12.4 g of cobalt nitrate hexahydrate and 0.53 g of manganese nitrate tetrahydrate are taken, 3 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the first modified Fischer-Tropsch cobalt catalyst. 0.17 g of phosphoric acid is weighed, added with 6 g of water to be dissolved, mixed and impregnated with the first modified catalyst, kept stand for 4 hours, and dried at 80 ℃ for 6 hours to obtain an S2 catalyst.
Example 3
17.3 g of cobalt nitrate hexahydrate and 1.49 g of manganese nitrate tetrahydrate are taken, 3 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the first modified Fischer-Tropsch cobalt catalyst. 0.47 g of phosphoric acid was weighed, dissolved in 6 g of water, mixed and impregnated with the first modified catalyst obtained above, allowed to stand for 4 hours, and dried at 80 ℃ for 6 hours to obtain an S3 catalyst.
Example 4
7.41 g of cobalt nitrate hexahydrate and 0.19 g of manganese nitrate tetrahydrate are taken, 3 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 70 ℃ for 10h, and roasting at 400 ℃ for 1h to obtain the first modified Fischer-Tropsch cobalt catalyst. 0.05 g of phosphoric acid is weighed, added with 6 g of water to be dissolved, mixed and impregnated with the first modified catalyst, and dried at 70 ℃ for 10 hours after standing for 4 hours to obtain an S4 catalyst.
Example 5
24.7 g of cobalt nitrate hexahydrate and 3.1 g of manganese acetate tetrahydrate are taken, 6 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese acetate tetrahydrate to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 120 ℃ for 1h, and roasting at 250 ℃ for 10h to obtain the first modified Fischer-Tropsch cobalt catalyst. 0.97 g of ammonium dihydrogen phosphate was weighed, dissolved in 6 g of water, mixed and impregnated with the first modified catalyst obtained above, allowed to stand for 4 hours, and dried at 120 ℃ for 1 hour to obtain an S5 catalyst.
Comparative example 1
14.82 g of cobalt nitrate hexahydrate is taken, 3 g of water is added to be dissolved to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the D1 catalyst.
Comparative example 2
14.82 g of cobalt nitrate hexahydrate and 0.96 g of manganese nitrate tetrahydrate are taken, 3 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the D2 catalyst.
Comparative example 3
14.82 g of cobalt nitrate hexahydrate is taken, 3 g of water is added to be dissolved to obtain a solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the Fischer-Tropsch cobalt catalyst. 0.3 g of phosphoric acid is weighed, added with 6 g of water to be dissolved, mixed and impregnated with the catalyst, kept stand for 4 hours and dried at 80 ℃ for 6 hours to obtain the D3 catalyst.
Comparative example 4
14.82 g of cobalt nitrate hexahydrate and 0.13 g of manganese nitrate tetrahydrate are taken, 3 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate to obtain a mixed solution, and 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 0.7 mL/g) is addedProduct 170m2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the first modified Fischer-Tropsch cobalt catalyst. 0.05 g of phosphoric acid is weighed, added with 6 g of water to be dissolved, mixed and impregnated with the first modified catalyst, kept stand for 4 hours, and dried at 80 ℃ for 6 hours to obtain the D4 catalyst.
Comparative example 5
14.82 g of cobalt nitrate hexahydrate and 2.56 g of manganese nitrate tetrahydrate are taken, 3 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the first modified Fischer-Tropsch cobalt catalyst. 0.75 g of phosphoric acid is weighed, added with 6 g of water to be dissolved, mixed and impregnated with the first modified catalyst, kept stand for 4 hours and dried at 80 ℃ for 6 hours to obtain the D5 catalyst.
Comparative example 6
14.82 g of cobalt nitrate hexahydrate and 0.3 g of manganese nitrate tetrahydrate are taken, 3 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the first modified Fischer-Tropsch cobalt catalyst. 0.075 g of phosphoric acid is weighed, added with 6 g of water to be dissolved, mixed and impregnated with the first modified catalyst, and the mixture is dried for 6 hours at 80 ℃ after standing for 4 hours to obtain a D6 catalyst.
Comparative example 7
14.82 g of cobalt nitrate hexahydrate and 2.2 g of manganese nitrate tetrahydrate are taken, 3 g of water is added to dissolve the cobalt nitrate hexahydrate and the manganese nitrate tetrahydrate to obtain a mixed solution, 10 g of alumina carrier (purchased from sasol company, with the pore volume of 0.7mL/g and the specific surface area of 170 m) is added2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the first modified Fischer-Tropsch cobalt catalyst. 0.6 g of phosphoric acid is weighed, added with 6 g of water to be dissolved, mixed and impregnated with the first modified catalyst, kept stand for 4 hours and dried at 80 ℃ for 6 hours to obtain the D7 catalyst.
Comparative example 8
14.82 g of cobalt nitrate hexahydrate, 0.96 g of manganese nitrate tetrahydrate and 0.3 g of phosphoric acid were added to 9 g of water to be dissolved to obtain a mixed solution, and 10 g of an alumina carrier (purchased from sasol company, pore volume 0.7mL/g, specific surface area 170 m) was added2/g), uniformly mixing, standing for 4h, drying at 100 ℃ for 4h, and roasting at 300 ℃ for 6h to obtain the D8 catalyst.
Comparative example 9
Dissolving 14.82 g of cobalt nitrate hexahydrate and 0.96 g of manganese nitrate tetrahydrate in 50mL of water, dropwise adding 25-28% ammonia water at 80 ℃ until the pH of the final solution is 8.3, filtering, washing with deionized water, and drying at 110 ℃ for 24 hours to obtain the precursor. Dissolving 0.3 g of phosphoric acid into 5mL of water, dropwise adding the solution into the precursor, uniformly stirring, drying at 110 ℃ for 24h, and finally roasting at 500 ℃ for 24h to obtain the D9 catalyst.
Test example 1
Evaluation of catalytic performance of the catalyst of S1 was carried out:
1 g of S1 catalyst (prepared in example 1) was charged to a fixed bed, initially in H2Reducing for 14h under atmosphere, space velocity of 6000mL/g/h, normal pressure and temperature of 400 ℃, then switching the reducing gas into reaction gas, and carrying out reaction under the following reaction conditions: feed gas group H2/CO/N266/33/1, space velocity 8000h-1The CO conversion rates of the reaction are respectively measured at the pressure of 2MPa and the temperature of 215 ℃ for 2h and 102h, and the CO conversion rate is obtained2hAnd CO conversion102hAnd the deactivation rate D is calculated,
deactivation rate D ═ CO conversion2h-CO conversion102h)/100h
The test results are shown in Table 1.
Test examples 2 to 5
The procedure of example 1 was followed except that the catalyst was S2-S5.
Testing of comparative examples 1 to 9
The process of example 1 was followed except that the catalyst was D1-D9.
TABLE 1
| Catalyst and process for preparing same | Reaction temperature of | Conversion of CO2h，％ | Conversion of CO102h，％ | Deactivation rate D,%/h |
| S1 | 215 | 42.7 | 42.6 | 0.001 |
| S2 | 215 | 44.5 | 44.4 | 0.001 |
| S3 | 215 | 41.7 | 41.6 | 0.001 |
| S4 | 215 | 47.5 | 47.2 | 0.003 |
| S5 | 215 | 37.8 | 37.5 | 0.002 |
| D1 | 215 | 55.5 | 44.9 | 0.106 |
| D2 | 215 | 50.4 | 43.8 | 0.066 |
| D3 | 215 | 48.8 | 43.4 | 0.054 |
| D4 | 215 | 54.4 | 44.0 | 0.104 |
| D5 | 215 | 34.1 | 30.1 | 0.04 |
| D6 | 215 | 51.2 | 44.8 | 0.064 |
| D7 | 215 | 36.5 | 31.2 | 0.053 |
| D8 | 215 | 45.2 | 40.1 | 0.051 |
| D9 | 215 | 35.4 | 30.6 | 0.048 |
The results in table 1 show that the catalyst of the present invention modifies the cobalt catalyst for fischer-tropsch synthesis by using the catalytic assistants Mn and P simultaneously, which greatly improves the stability of the cobalt catalyst for fischer-tropsch synthesis and greatly reduces the deactivation rate of the catalyst. As can be seen from the results of examples 1 to 5 and comparative examples 1 to 7, when the catalyst was modified with both Mn and P, the deactivation rate was only 0.002%/h or less, and in the preferred range, the deactivation rate reached 0.001%/h, and the deactivation rate was very low; without using Mn and P (comparative example 1), or using Mn alone (comparative example 2), modifying the catalyst with P alone (comparative example 3), or even if using Mn and P, but the proportional relationship is not within the scope of the present invention (comparative examples 4-7), the deactivation rates are 0.106%/h, 0.066%/h, 0.054%/h, 0.104%/h, 0.04%/h, 0.064%/h and 0.053%/h, respectively; the deactivation rates of comparative examples 1-7 were 106 times, 66 times, 54 times, 104 times, 40 times, 64 times, and 53 times, respectively, as compared to the deactivation rates of 0.001%/h in the preferred ranges of manganese and phosphorus of examples 1-3 of the present invention. This shows that the prepared cobalt catalyst for Fischer-Tropsch synthesis can greatly improve the stability of the cobalt catalyst for Fischer-Tropsch synthesis when the cobalt catalyst contains both Mn and P and is within the range defined by the invention.
In the comparative example 8, although Mn and P are used simultaneously, Co, Mn and P are loaded on the carrier simultaneously, but the method of loading Co and Mn firstly and then loading P is not adopted, so that the deactivation rate of the Fischer-Tropsch synthesis cobalt catalyst is as high as 0.051%/h, and the stability is poor.
Comparative example 9 while Mn and P were also used at the same time, the co-impregnation method of the present invention was replaced with the co-precipitation method in the loading manner, and the activity and stability of the fischer-tropsch cobalt catalyst prepared were reduced.
Therefore, the catalyst has the advantages that the catalyst auxiliaries Mn and P are used simultaneously, the contents of Mn and P are limited, so that the Fischer-Tropsch synthesis cobalt catalyst is modified, Co and Mn are loaded on the carrier firstly, then P is loaded, and a Co-impregnation method is adopted for loading, so that the stability of the Fischer-Tropsch synthesis cobalt catalyst is greatly improved, and the inactivation rate of the catalyst is greatly reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A preparation method of a Fischer-Tropsch synthesis cobalt catalyst comprises the following steps:
(A) soaking a carrier in a mixed solution of a cobalt precursor and a manganese precursor, and carrying out first drying and roasting to obtain a first modified catalyst;
(B) dipping the first modified catalyst in a phosphorus precursor solution, and carrying out second drying to obtain a Fischer-Tropsch synthesis cobalt catalyst; the catalyst comprises a carrier, and a catalytic active component Co and a catalytic promoter which are loaded on the carrier, wherein the catalytic promoter contains Mn and P; wherein the weight ratio of the catalytic active component Co to the carrier is (15-50): 100, respectively; the molar ratio of Mn to the active component Co is (3-15): 100, respectively; the molar ratio of P to the active component Co is (2-10): 100.
2. the method of claim 1, wherein the cobalt precursor is at least one of cobalt nitrate, cobalt acetate, and cobalt chloride.
3. The method of claim 1 or 2, wherein the manganese precursor is manganese nitrate or manganese acetate.
4. The process of claim 1, wherein the support is alumina, silica or titania.
5. The process according to claim 1 or 4, wherein the support has a specific surface area of 50 to 200m2(iii) a pore volume of 0.3 to 1.5 mL/g.
6. The method of claim 1, wherein the phosphorus precursor is at least one of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate.
7. The method of claim 1, wherein the first drying conditions comprise: the drying temperature is 70-120 ℃, and the drying time is 1-10 h; the roasting conditions comprise: the roasting temperature is 250-400 ℃, and the roasting time is 1-10 h; the conditions of the second drying include: the drying temperature is 70-120 ℃, and the drying time is 1-10 h.
8. A fischer-tropsch cobalt catalyst prepared by the process of any one of claims 1 to 7.
9. The Fischer-Tropsch synthesis cobalt catalyst of claim 8, wherein the weight ratio of the catalytically active component Co to the support is (25-35): 100, respectively; the molar ratio of Mn to the active component Co is (5-10): 100, respectively; the molar ratio of P to the active component Co is (4-8): 100.
10. the fischer-tropsch synthesis cobalt catalyst of claim 8, wherein the support is alumina, silica or titania.
11. The fischer-tropsch synthesis cobalt catalyst of claim 10, wherein the support has a specific surface area of from 50 to 200m2(iii) a pore volume of 0.3 to 1.5 mL/g.
12. A fischer-tropsch synthesis process comprising reacting synthesis gas in the presence of a fischer-tropsch cobalt catalyst, the fischer-tropsch cobalt catalyst as claimed in any one of claims 8 to 11.
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