CN110560069B - Iron-based Fischer-Tropsch synthesis catalyst and preparation method thereof - Google Patents
Iron-based Fischer-Tropsch synthesis catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 35
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000011591 potassium Substances 0.000 claims abstract description 29
- 238000000975 co-precipitation Methods 0.000 claims abstract description 25
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 238000001694 spray drying Methods 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- 238000004537 pulping Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 description 57
- 239000000243 solution Substances 0.000 description 50
- 239000012065 filter cake Substances 0.000 description 29
- 238000003756 stirring Methods 0.000 description 28
- 238000000967 suction filtration Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 239000012752 auxiliary agent Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000004846 x-ray emission Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 240000004270 Colocasia esculenta var. antiquorum Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- 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
- C10G2/332—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 of the iron-group
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to the field of catalyst synthesis, and discloses an iron-based Fischer-Tropsch synthesis catalyst and a preparation method thereof. The method comprises the steps of carrying out coprecipitation reaction on water-soluble iron salt and water-soluble copper salt and a coprecipitator solution containing a silicon source, a potassium source, a water-soluble alkali source and a water-soluble aluminum source, separating out a precipitate, pulping the precipitate, carrying out spray drying, and roasting to obtain the catalyst. The catalyst contains elements with the weight ratio of Fe, cu, K and SiO 2 Al =100 (0.01-5): (1-7): 5-27): 0.01-4.5), wherein, the Fischer-Tropsch synthesis catalyst contains KAlSiO 4 . The catalyst has the advantages that the K component is not easy to lose in the Fischer-Tropsch synthesis reaction process, so that the activity stability and the effective product yield of the catalyst are greatly improved, and the carbon number is more than 5 (C) 5+ ) The space-time yield of the product reaches more than 1.1g/g-cat.
Description
Technical Field
The invention relates to the field of catalyst synthesis, in particular to an iron-based Fischer-Tropsch synthesis catalyst and a preparation method thereof.
Background
Fischer-Tropsch (F-T) synthesis is the core technology of coal indirect liquefaction, and synthesis gas (CO + H) is usually prepared by the action of F-T synthesis catalysts such as precipitated iron base or supported cobalt 2 ) The catalytic reaction is carried out to synthesize liquid hydrocarbon/wax hydrocarbon products. Precipitated iron-based catalysts, which are inexpensive and readily available in raw materials, are suitable for reaction operating temperatures and H of synthesis gas 2 The advantages of wider ratio of CO and lower methane selectivity are still the key points of research and development in the industry. However, precipitated iron-based catalysts are less stable in the Fischer-Tropsch synthesis than cobalt-based catalysts, which is one of the reasons that industrial application thereof on a larger scale is hindered.
With the development of domestic indirect liquefaction and Fischer-Tropsch synthesis technology, precipitated iron and precipitated iron-manganese catalysts are continuously researched and developed for a long time by Shanxi coal chemical institute of Chinese academy of sciences. From the public report, most of the precipitant is ammonia water precipitant. In addition, the addition method of the potassium auxiliary agent is mainly to add a potassium source compound into a precipitate filter cake after washing and filtering. No matter ICC-I (Fe/Cu/K) series catalysts or ICC-II (Fe/Mn/K) series catalysts, the potassium auxiliary agent is not used, and the indispensable property of the potassium auxiliary agent on the precipitated iron-based Fischer-Tropsch synthesis catalysts is also laterally proved.
CN100584454C discloses an iron based fischer-tropsch synthesis catalyst composition in which the main iron phase is ferrihydrite and the catalyst composition includes alumina as a structural promoter. It also discloses that the use of alumina as a structural promoter in an iron-based catalyst composition whose main iron phase is ferrihydrite increases the activity and selectivity of the catalyst by a factor of 1.5 to 3.
CN101869840A discloses a Fischer-Tropsch synthesis catalyst and a preparation method thereof, wherein an active component of the catalyst is Fe, the catalyst further comprises a transition metal auxiliary agent M, a structure auxiliary agent S and a K auxiliary agent, the transition metal auxiliary agent M is selected from one or a combination of more of Mn, cr and Zn, and the structure auxiliary agent S is SiO 2 Or/and Al 2 O 3 (ii) a The weight ratio of the components is Fe, transition metal additive M, structural additive S: K = 100. However, in the preparation method of the catalyst, the structural auxiliary agent Al 2 O 3 The raw materials of (a) are alumina sol, i.e. water and alumina. It also discloses that a certain amount of transition metal auxiliary agent and structure auxiliary agent (SiO) are added in the preparation process 2 Or/and Al 2 O 3 ) Can realizeThe active phase of the catalyst is well dispersed and stabilized and maintains high stability of the active phase and catalyst structure during the reaction.
However, in the actual application of the catalyst prepared by the above method, there is still a problem that the activity of the catalyst is lowered as the time for the catalytic reaction is prolonged.
The invention finds that the deactivation of the catalyst has a great relationship with the stability of the K component as the time of the catalytic reaction is prolonged. The activity and effective yield (i.e. number of carbon atoms greater than 5 (C)) of the catalyst with greater potassium loss from the bulk of the catalyst during the Fischer-Tropsch synthesis reaction 5+ ) The yield of the product of (a) is much more reduced than in catalysts in which the potassium component is relatively stable. Therefore, how to consolidate the K component in the precipitated iron-based catalyst and effectively prevent the K component from losing from the catalyst body can be a key technical link for improving the activity and the effective yield of the precipitated iron-based Fischer-Tropsch synthesis catalyst.
Disclosure of Invention
The invention aims to solve the problems of catalyst activity stability and effective product yield reduction caused by the loss of a potassium component from a catalyst body in the prior art, and provides an iron-based Fischer-Tropsch synthesis catalyst and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an iron-based fischer-tropsch synthesis catalyst, the method comprising the steps of:
(1) Carrying out coprecipitation reaction on water-soluble iron salt, water-soluble copper salt and a coprecipitator solution, and separating out a precipitate from a reaction product, wherein the coprecipitator solution contains a silicon source, a potassium source, a water-soluble alkali source and a water-soluble aluminum source;
(2) Pulping the precipitate obtained in the step (1) in the presence of deionized water to obtain precipitate slurry; and
(3) And (3) carrying out spray drying on the precipitate slurry obtained in the step (2), and then roasting.
In a second aspect, the invention provides an iron-based Fischer-Tropsch synthesis catalyst prepared by the method of the first aspect, wherein the Fischer-Tropsch synthesis catalyst containsThe elements have the following weight ratio of Fe, cu, K and SiO 2: Al =100 (0.01-5): (1-7): (5-27): (0.01-4.5), wherein aluminum, part of silicon and part of potassium are KAlSiO 4 Exist in the form of (1).
The precipitated iron-based catalyst prepared by the method has the advantages that the stability of the metal component K is greatly improved, so that the loss of the metal component K from an iron catalyst body in the Fischer-Tropsch synthesis reaction process is effectively prevented, and the stability of the component Fe is improved. Compared with the conventional catalyst, the activity stability of the catalyst is greatly improved, the long-period catalytic life of the precipitated iron-based catalyst is effectively prolonged, and the number of carbon atoms is more than 5 (C) 5+ ) The yield of the target product (C) is 5 or more carbon atoms 5+ ) The space-time yield of the product reaches more than 1.1g/g-cat. In addition, compared with the traditional preparation method of the precipitated iron-based catalyst, the method provided by the invention has the advantages that the preparation process is greatly shortened, the discharge capacity is greatly reduced, and the equipment investment and the production operation cost can be greatly reduced.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the catalyst of example 1 of the present invention.
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.
In a first aspect, the invention provides a process for the preparation of an iron-based fischer-tropsch synthesis catalyst, the process comprising the steps of:
(1) Carrying out coprecipitation reaction on water-soluble iron salt, water-soluble copper salt and a coprecipitator solution, and separating out a precipitate from a reaction product, wherein the coprecipitator solution contains a silicon source, a potassium source, a water-soluble alkali source and a water-soluble aluminum source;
(2) Pulping the precipitate obtained in the step (1) in the presence of deionized water to obtain precipitate slurry; and
(3) And (3) carrying out spray drying on the precipitate slurry obtained in the step (2), and then roasting.
In the invention, in the step (1), the water-soluble iron salt is selected from one or more of iron nitrate and iron chloride; the water-soluble copper salt is selected from one or more of copper nitrate, copper chloride, cuprous chloride and copper acetate.
In the present invention, in the step (1), the coprecipitator solution contains a water-soluble aluminum source selected from one or more of sodium aluminate, sodium metaaluminate, potassium aluminate and potassium metaaluminate. The coprecipitate solution contains a silicon source, which may be a soluble silicon compound and/or a silica sol, for example, one or more selected from the group consisting of potassium silicate, sodium silicate, orthosilicic acid, and silica sol. The coprecipitate solution contains a water-soluble alkali source, wherein the water-soluble alkali source is selected from one or more of potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, ammonium carbonate, ammonium bicarbonate and urea, and is preferably the combination of potassium carbonate and potassium bicarbonate. The coprecipitate solution also contains a potassium source, wherein the potassium source is a potassium-containing compound and can be water-soluble potassium salt, such as one or more of potassium silicate, potassium carbonate, potassium bicarbonate, potassium aluminate and potassium metaaluminate. In one embodiment, the potassium source is the same as the water-soluble aluminum source, the silicon source, or the water-soluble alkali source.
In a preferred embodiment, the potassium source, the water-soluble aluminum source and the silicon source are mixed uniformly during the formation of the coprecipitate solution in step (1), which has the advantage that during the coprecipitation process, the two elements K and Al can be adsorbed on the metal micelles and silica micelles in-line and then further interact under the coprecipitation reaction conditions. During subsequent high-temperature treatment (drying and roasting), the interaction is further strengthened and even chemical interaction occurs, so that the effect of firmly binding the potassium element on the surface of the final catalyst crystal grain is achieved.
Preferably, in step (1), the silicon source and the potassium source are added together during the formation of the coprecipitate solution, or the silicon source and the potassium source are the same substance. A water soluble aluminum source is mixed as a water soluble salt with the silicon source and the potassium source.
In the present invention, preferably, the pH of the coprecipitant solution is adjusted to greater than 8, preferably greater than 9.0, at ambient temperature.
In the invention, the amount of each component in the coprecipitator can be adjusted according to other requirements on the premise of completely precipitating Fe element and Cu element.
In the present invention, in step (1), the conditions of the coprecipitation reaction include: the temperature is 40-80 ℃, preferably 45-75 ℃, and more preferably 45-60 ℃; the pH value of the regulation system is 4-8, preferably 4-7; the time is 20-35min.
In the present invention, the adjustment of the temperature during the coprecipitation reaction can be selected according to the prior art, such as jacket heating, electric heating, etc., and the adjustment of the pH during the coprecipitation reaction can be selected according to the prior art, such as adjusting the pH of the reaction system by adjusting the flow rates of the precipitant solution and the water-soluble iron salt and the water-soluble copper salt. After the coprecipitation reaction is completed, the system is aged for a certain period of time, and the precipitate (i.e., filter cake) is separated by suction filtration or the like, and the obtained filter cake is preferably washed once with deionized water, and more preferably the obtained filter cake is not washed.
In the invention, the step (1) is used for realizing the precipitation of the iron element and the copper element, gelling the silicon monomer in the silicon source and simultaneously realizing the loading of the elements K and Al.
In the present invention, in step (2), the cake obtained in step (1) is beaten by mixing and stirring an appropriate amount of deionized water, for example, by beating under high shear conditions.
In the invention, the conditions of the spray drying in the step (3) comprise that the inlet air temperature is 200-350 ℃, and the outlet air temperature is 95-135 ℃; the roasting condition comprises roasting for 8-16 hours at 100-200 ℃, then heating to 400-550 ℃ at the heating rate of 280-350 ℃/hour, and roasting for 3-7 hours at the temperature.
In a second aspect, the invention provides an iron-based fischer-tropsch catalyst prepared by the method of the first aspect, wherein the fischer-tropsch catalyst comprises the following elements in the weight ratio of Fe: cu: K: siO 2 :Al＝100:(0.01-5):(1-7):(5-27):(0.01-4.5)。
In the present invention, the aluminum, part of the silicon and part of the potassium are KAlSiO 4 In the form of alpha-Fe 2 O 3 Exist in the form of (1). This can be determined by X-ray diffraction (XRD) testing.
Preferably, in the catalyst, cu may be present in the form of copper oxide.
In the invention, the catalyst can also contain Na elements, wherein Fe, cu, K, na and SiO 2 The weight ratio of Al is 100 (0.01-5): (1-7): 0.01-1): 5-27): 0.01-4.5, preferably 100 (0.01-4.9): 1-7): 0.01-0.4): 5-27): 0.01-4.5.
The BET specific surface area of the catalyst is 80-180m 2 Per g, preferably from 120 to 165m 2 Per g, pore volume of 0.35-0.65cm 3 A/g, preferably from 0.4 to 0.60m 2 /g。
The catalyst of the invention has the following advantages:
(1) In the catalyst, the stability of the metal component (particularly K) is greatly improved, so that the metal component (particularly K) is prevented from losing from an iron-based catalyst body in the Fischer-Tropsch synthesis reaction process;
(2) The catalyst of the method can maintain long-period stable operation, namely the conversion rate and the effective product yield are stable. And target product (C) 5+ ) The yield is high, and the space-time yield reaches more than 1.1g/g-cat.
(3) Compared with the traditional method, the method for preparing the catalyst has the advantages of simple process, greatly shortened production flow, especially obviously reduced washing times, reduced water consumption, reduced discharge capacity, and greatly reduced equipment investment and operation cost.
The present invention will be described in detail below by way of examples.
Example 1
Weighing 20.0Kg Fe (NO) 3 ) 3 ·9H 2 O，0.42Kg Cu(NO 3 ) 2 ·3H 2 And O, adding 100L of deionized water, stirring and dissolving to obtain a metal salt mixed solution 1. Weighing 9.4Kg KHCO 3 Adding 63.0L deionized water, stirring for dissolving, and adding 1.7Kg of K 2 SiO 3 And stirring for dissolving. 2.1Kg NaAlO was then added to the silicon containing solution 2 And (3) continuously stirring the aqueous solution (the mass concentration is 10 percent), heating the aqueous solution to the reaction temperature required by coprecipitation to obtain a coprecipitator solution 2, wherein the pH value is 8.5. Respectively feeding the two materials 1 and 2 into a precipitation reaction tank through respective delivery pumps to generate coprecipitation. And simultaneously, monitoring the temperature and the pH value of the system in the precipitation reaction tank on line. Controlling the temperature of a precipitation system to be 57 ℃ in a jacket heating mode; the pH value of a system is controlled to be 6.5 by adjusting the conveying pumps of the 1 and 2 solutions; the total precipitation reaction time was completed within 25min. And after the precipitation is finished, aging the precipitation solution for 0.5 hour at the original temperature, then transferring the precipitation solution to a suction filtration device for suction filtration, and removing the filtrate to obtain a filter cake.
Using a filter cake: the mass ratio of water is 2:1, and stirring for 25min under high shear to obtain a catalyst slurry with a total solid content of about 20 wt%. Inputting the catalyst slurry into a spray drying device, and carrying out spray drying under the conditions that the inlet air temperature is 290 ℃ and the outlet air temperature is about 106 ℃, wherein the spraying is finished after about 6 min. The obtained catalyst particles are roasted in a muffle furnace in air at 150 ℃ for 10 hours, then the temperature is raised to 480 ℃ at the rate of 320 ℃/hour, and the catalyst A1 is obtained after roasting at the temperature for 6 hours.
Example 2
Weighing 20.0Kg Fe (NO) 3 ) 3 ·9H 2 O，0.42Kg Cu(NO 3 ) 2 ·3H 2 And O, adding 100L of deionized water, stirring and dissolving to obtain a metal salt mixed solution 1. 10.1Kg of K 2 CO 3 、1.5Kg Na 2 CO 3 2.4Kg of silica sol containing potassium (in SiO) 2 Calculated as 24% solids) was dissolved in 63.0L deionized water and then mixed with 3.5Kg NaAlO 2 Mixing the aqueous solutions (the mass concentration is 10 percent), continuously stirring, and heating to the reaction temperature required by coprecipitation to obtain a coprecipitator solution 2, wherein the pH value is 9. Respectively feeding the two materials 1 and 2 into a precipitation reaction tank through respective delivery pumps to generate coprecipitation. And simultaneously, monitoring the temperature and the pH value of the system in the precipitation reaction tank on line. Controlling the temperature of a precipitation system to be 40 ℃ in a jacket heating mode; the pH value of a system is controlled to be 7.0 by adjusting the conveying pumps of the 1 and 2 solutions; the total precipitation reaction time was completed within 25min. And after the precipitation is finished, aging the precipitation solution for 0.5 hour at the original temperature, then transferring the precipitation solution to a suction filtration device for suction filtration, washing the filtrate once by using deionized water after the filtrate is discarded, and performing suction filtration again to obtain a filter cake.
Using a filter cake: the mass ratio of water is 3:1, and stirring for 25min under high shear to obtain a catalyst slurry with a total solid content of about 22 wt%. Inputting the catalyst slurry into a spray drying device, and carrying out spray drying under the conditions that the inlet air temperature is 310 ℃ and the outlet air temperature is 108 ℃, wherein the spray drying is finished after about 6 min. The obtained catalyst particles are roasted in a muffle furnace in air at 130 ℃ for 14 hours, then the temperature is raised to 520 ℃ at the temperature raising rate of 320 ℃/hour, and the catalyst A2 is obtained after roasting at the temperature for 6 hours.
Example 3
Weighing 20.0Kg Fe (NO) 3 ) 3 ·9H 2 O，0.42Kg Cu(NO 3 ) 2 ·3H 2 And O, adding 100L of deionized water, stirring and dissolving to obtain a metal salt mixed solution 1. Weighing 9.4Kg KHCO 3 Adding 63.0L deionized water, stirring for dissolving, and adding 2.3Kg of K 2 SiO 3 0.5Kg of orthosilicic acid was dissolved by stirring. 2.1Kg NaAlO was then added to the silicon containing solution 2 And (3) continuously stirring the aqueous solution (with the mass concentration of 10 percent), heating to the reaction temperature required by coprecipitation to obtain a coprecipitator solution 2, wherein the pH value is 8.5. Respectively feeding the two materials 1 and 2 into a precipitation reaction tank through respective delivery pumps to generate coprecipitation. And simultaneously, monitoring the temperature and the pH value of the system in the precipitation reaction tank on line. Controlling the temperature of a precipitation system to be 55 ℃ in a jacket heating mode; universal jointThe pH value of a system for controlling the delivery pump by adjusting the solutions 1 and 2 is 5.7; the total precipitation reaction time was completed within 25min. And after the precipitation is finished, aging the precipitation solution for 1.0 hour at the original temperature, then transferring the precipitation solution to a suction filtration device for suction filtration, and removing the filtrate to obtain a filter cake.
Using a filter cake: the mass ratio of water is 4:1 with the filter cake, stirring for 25min under high shear conditions to obtain a catalyst slurry having a total solids content of about 19 wt%. Inputting the catalyst slurry into a spray drying device, and carrying out spray drying under the conditions that the inlet air temperature is 295 ℃ and the outlet air temperature is about 104 ℃, wherein the spraying is finished after about 6 min. The obtained catalyst particles are calcined in a muffle furnace in air at 125 ℃ for 16 hours, then the temperature is raised to 540 ℃ at the temperature raising rate of 320 ℃/hour, and the catalyst A3 is finally obtained after calcining at the temperature for 5 hours.
Example 4
Weighing 7.5Kg FeCl 3 ，0.048Kg CuCl 2 ·2H 2 And O, adding 80L of deionized water, stirring and dissolving to obtain a mixed solution 1. 4.6Kg of K 2 CO 3 、0.5Kg NaHCO 3 2.6Kg of silica sol (in SiO) 2 Solids content 28%) was dissolved in 30.0L deionized water and mixed with 0.65Kg KAlO 2 And (3) continuously stirring the aqueous solution (the mass concentration is 15 percent), heating the aqueous solution to the reaction temperature required by coprecipitation to obtain a coprecipitator solution 2, wherein the pH value is 9.5. Respectively feeding the two materials 1 and 2 into a precipitation reaction tank through respective delivery pumps to generate coprecipitation. And simultaneously, monitoring the temperature and the pH value of the system in the precipitation reaction tank on line. Controlling the temperature of a precipitation system to be 70 ℃ in a jacket heating mode; the pH value of a system is controlled to be 6.0 by adjusting the conveying pumps of the 1 and 2 solutions; the total precipitation reaction time was completed within 25min. And after the precipitation is finished, aging the precipitation solution for 0.5 hour at the original temperature, and then transferring the precipitation solution to a suction filtration device for suction filtration to obtain a filter cake.
Using a filter cake: the mass ratio of water is 2.5:1 and stirring for 30min under a high shear condition to obtain catalyst slurry with the total solid content of about 24 wt%. Inputting the catalyst slurry into a spray drying device, and carrying out spray drying under the conditions that the inlet air temperature is 300 ℃ and the outlet air temperature is about 110 ℃, wherein the spraying is finished after about 6 min. The obtained catalyst particles are roasted in a muffle furnace in air at 140 ℃ for 12 hours, then the temperature is raised to 550 ℃ at the temperature raising rate of 300 ℃/hour, and the catalyst A4 is obtained after roasting at the temperature for 3 hours.
Example 5
Weighing 7.5Kg FeCl 3 ，0.335Kg CuCl 2 ·2H 2 And O, adding 70L of deionized water, stirring and dissolving to obtain a mixed solution 1. 3.1Kg of K 2 CO 3 、0.5Kg KHCO 3 0.6Kg of silica sol containing potassium (in terms of SiO) 2 Calculated as 24% solids) was dissolved in 33.0L deionized water and then mixed with 0.85Kg NaAlO 2 And (3) continuously stirring the aqueous solution (the mass concentration is 15 percent), heating the aqueous solution to the reaction temperature required by coprecipitation to obtain a coprecipitator solution 2, wherein the pH value is 8.5. Respectively feeding the two materials 1 and 2 into a precipitation reaction tank through respective delivery pumps to generate coprecipitation. And simultaneously, monitoring the temperature and the pH value of the system in the precipitation reaction tank on line. Controlling the temperature of a precipitation system to be 40 ℃ in a jacket heating mode; the pH value of a system is controlled to be 7.0 by adjusting the conveying pumps of the 1 and 2 solutions; the total precipitation reaction time was completed within 25min. And after the precipitation is finished, aging the precipitation solution for 0.5 hour at the original temperature, then transferring the precipitation solution to a suction filtration device for suction filtration, washing the filtrate once by using deionized water after the filtrate is discarded, and performing suction filtration again to obtain a filter cake.
Using a filter cake: the mass ratio of water is 3.5:1 and stirring for 30min under a high shear condition to obtain catalyst slurry with the total solid content of about 21 wt%. Inputting the catalyst slurry into a spray drying device, and carrying out spray drying under the conditions that the inlet air temperature is 255 ℃ and the outlet air temperature is about 102 ℃, wherein the spraying is finished after about 6 min. The obtained catalyst particles are roasted in a muffle furnace in air at 130 ℃ for 12 hours, then the temperature is raised to 500 ℃ at the temperature raising rate of 320 ℃/hour, and the catalyst A5 is obtained after roasting at the temperature for 3 hours.
Example 6
An iron-based Fischer-Tropsch synthesis catalyst was prepared as described in example 1, except thatPreparation of a coprecipitate solution, 10.1Kg of K 2 CO 3 、1.5Kg Na 2 CO 3 2.2Kg of potassium water glass (in SiO) 2 Calculated solid content is 25 percent) is dissolved in 63.0L of deionized water, and then the solution is continuously stirred with 4.5Kg of potassium metaaluminate aqueous solution (the mass concentration is 10 percent) and heated to the reaction temperature required by coprecipitation, so as to obtain a coprecipitator solution 2, and the pH value is 10.5. Catalyst A6 was finally obtained.
Comparative example 1
Weighing 20.0Kg Fe (NO) 3 ) 3 ·9H 2 O，0.43Kg Cu(NO 3 ) 2 ·3H 2 And O, adding 100L of deionized water, stirring and dissolving to obtain a metal salt mixed solution 1. Weighing 8.6Kg of Na 2 CO 3 ，1.4Kg KHCO 3 Adding 63.0L deionized water, stirring to dissolve, adding 0.7Kg of K 2 SiO 3 63.0L of deionized water was added, stirred and dissolved to obtain precipitant solution 2. Respectively feeding the two materials 1 and 2 into a precipitation reaction tank through respective delivery pumps to generate coprecipitation. And simultaneously, monitoring the temperature and the pH value of the system in the precipitation reaction tank on line. Controlling the temperature of a precipitation system in a jacket heating mode to 57 ℃; the pH value of a system is controlled to be 6.5 by adjusting the conveying pumps of the 1 and 2 solutions; the total precipitation reaction time was completed within 25min. And after the precipitation is finished, aging the precipitation solution for 0.5 hour at the original temperature, then transferring the precipitation solution to a suction filtration device for suction filtration, and removing the filtrate to obtain a filter cake. And repeatedly washing with deionized water to obtain a precipitate filter cake.
Using a filter cake: the mass ratio of water is 2:1 deionized water and the filter cake are mixed, stirred and pulped, and then 1.90Kg of silica sol (K) containing potassium is added into the slurry while stirring 2 CO 3 Mixing with silica sols of which SiO is 2 24%) and the pH of the system was adjusted to 7.5. Stirring with high shear for 25min. Catalyst slurry with a total solids content of around 20wt% was obtained. The slurry thus obtained was spray-dried under the conditions of example 1 and then calcined. Finally, catalyst D1 was obtained.
Comparative example 2
Weighing 20.0Kg Fe (NO) 3 ) 3 ·9H 2 O，0.45Kg Cu(NO 3 ) 2 ·3H 2 O，1.1Kg Al(NO 3 ) 3 ·9H 2 And O, adding 100L of deionized water, stirring and dissolving to obtain a metal salt mixed solution 1. Weighing 10.6Kg of Na 2 CO 3 63.0L of deionized water was added, stirred and dissolved to obtain precipitant solution 2. Respectively feeding the two materials 1 and 2 into a precipitation reaction tank through respective delivery pumps to generate coprecipitation. And simultaneously, monitoring the temperature and the pH value of the system in the precipitation reaction tank on line. Controlling the temperature of a precipitation system to be 57 ℃ in a jacket heating mode; the pH value of a system is controlled to be 6.5 by adjusting the conveying pumps of the 1 and 2 solutions; the total precipitation reaction time was completed within 25min. And after the precipitation is finished, aging the precipitation solution for 0.5 hour at the original temperature, then transferring the precipitation solution to a suction filtration device for suction filtration, and removing the filtrate to obtain a filter cake. And repeatedly washing the filter cake with deionized water to obtain a precipitate filter cake.
Using a filter cake: the mass ratio of water is 2:1, mixing the deionized water with the filter cake to carry out slurrying. Then 1.90Kg of silica sol (K) containing potassium was added to the slurry while stirring 2 CO 3 Mixed with silica sol of which SiO is 2 24%) and stirring with high shear for 25min. And the pH value of the system is adjusted to 7.2. A catalyst slurry with a total solids content of around 18wt% was obtained. The resulting slurry was spray-dried under the conditions of example 1 and calcined. Finally, catalyst D2 was obtained. .
Comparative example 3
Weighing 20.0Kg Fe (NO) 3 ) 3 ·9H 2 O，0.43Kg Cu(NO 3 ) 2 ·3H 2 O,0.85Kg of alumina sol (wherein, al 2 O 3 Content of (d) 15 wt%), 100L of deionized water was added, stirred and dissolved to obtain a metal salt mixed solution 1. Adding 10.6Kg of Na 2 CO 3 63.0L of deionized water was added and stirred to obtain precipitant solution 2. Respectively feeding the two materials 1 and 2 into a precipitation reaction tank through respective delivery pumps to generate coprecipitation. And simultaneously, monitoring the temperature and the pH value of the system in the precipitation reaction tank on line. Controlling the temperature of a precipitation system to be 57 ℃ in a jacket heating mode; the pH value of a system is controlled to be 6.5 by adjusting the conveying pumps of the 1 and 2 solutions; the total precipitation reaction time is 2Ending within 5min. And after the precipitation is finished, aging the precipitation solution for 0.5 hour at the original temperature, then transferring the precipitation solution to a suction filtration device for suction filtration, and removing the filtrate to obtain a filter cake. And repeatedly washing the filter cake by using deionized water to obtain a precipitate filter cake.
Using a filter cake: the mass ratio of water is 2:1 deionized water and the filter cake are mixed, stirred and pulped, and then 1.90Kg of silica sol (K) containing potassium is added into the slurry while stirring 2 CO 3 Mixing with silica sols of which SiO is 2 24%) to obtain a catalyst slurry having a total solid content of about 20 wt%. The resulting slurry was spray-dried under the conditions of example 1 and calcined. Finally, catalyst D3 was obtained.
Test example
The apparatus used for the test was as follows:
x-ray diffraction testing (XRD) A D8Advance (Cu Ka) apparatus from Bruker was used.
X-ray fluorescence Spectroscopy (XRF) testing an XRF-1800 instrument, manufactured by Shimadzu corporation, was used.
X-ray photoelectron spectroscopy (XPS) testing an Escalab 250Xi instrument was used. Before the test of the reacted catalyst, the reacted catalyst needs to be correspondingly demagnetized, but the component content of the element K in the catalyst is not influenced.
1. Testing of catalyst composition
The catalysts A1 to A6 and D1 to D3 were analyzed by an X-ray fluorescence component analyzer (XRF), and the analysis results are shown in Table 1.
TABLE 1
The catalyst A1 is subjected to an X-ray diffraction (XRD) test, the test result is shown in figure 1, and the characteristic peak of the X-ray diffraction of the catalyst sample is compared with that of a standard PDF card 89-0596 (Fe) 2 O 3 hematite) indicates that the Fe is as a-Fe 2 O 3 Exists in the form of (1); in addition, the X-ray diffraction characteristic peak of the catalyst sample isStandard PDF card 11-0313 (KAlSiO) 4 ) The coincidence indicates that the Al is KAlSiO 4 Exist in the form of (1).
2. Measurement of specific surface area and pore volume of catalyst
The catalysts A1 to A6 and D1 to D3 were analyzed by a low-temperature nitrogen adsorption method, and the analysis results are shown in table 2.
TABLE 2
| Catalyst and process for preparing same | BET specific surface area (m) 2 /g) | Pore volume (cm) 3 /g) |
| A1 | 148.6 | 0.50 |
| A2 | 145.2 | 0.51 |
| A3 | 156.1 | 0.48 |
| A4 | 160.8 | 0.60 |
| A5 | 120.1 | 0.40 |
| A6 | 139.4 | 0.47 |
| D1 | 184.2 | 0.38 |
| D2 | 153.1 | 0.35 |
| D3 | 123.1 | 0.25 |
3. Evaluation of Fischer-Tropsch Synthesis Activity
The catalysts A1 to A6 and D1 to D3 were subjected to Fischer-Tropsch synthesis activity evaluation using a laboratory micro-reverse fixed bed reactor. The catalyst loading was 1.5 grams and diluted with 9.0 grams of quartz sand of equivalent size to ensure a constant temperature zone of reaction temperature. The catalyst is pre-reduced in a reactor for 24 hours in an online way by synthesis gas under the normal pressure condition of 250 ℃, and then H is gradually reduced 2 And the/CO ratio and the reaction pressure are switched to the evaluation conditions to start the Fischer-Tropsch synthesis reaction. The evaluation conditions were as follows: 250 ℃ and 2.5MPa. The space velocity of the synthetic gas in the reactor is 8.0-14 NL/g-cat/h, and the hydrogen-carbon ratio is 1.6-3.0. The data obtained are shown in table 3. The reaction performance evaluation conditions of the catalysts in table 3 were: h 2 /CO＝1.6-3.0、T＝250℃、P＝2.5MPa、SV＝8000-14000mL/(h·g)，t＝460-480h。
TABLE 3
As can be seen from the results in Table 3, the catalysts A1 to A6 of the present invention catalyze the Fischer-Tropsch synthesis reactionWhen the number of carbon atoms is 5 or more (C) 5+ ) The space-time yield of the product is higher and reaches more than 1.1g/g-cat.
4. Test for loss of K component in catalyst during reaction
XRF and XPS were used to measure the content of component K before and after 471h of the reaction for the samples of catalyst A1 and catalysts D1-D3, respectively, and the results are shown in Table 4 below.
TABLE 4 analysis of the bulk (XRF) and surface (XPS) component K/Fe ratios of the catalyst before and after the Fischer-Tropsch synthesis reaction (using scanning of Fe2P and K2P, respectively, in the XPS analysis)
As can be seen from the results in Table 4, the catalysts A1 of the present invention show less loss of the K component over time as compared to the Fischer-Tropsch catalysts D1 to D3 of the comparative examples.
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 (11)
1. A preparation method of an iron-based Fischer-Tropsch synthesis catalyst comprises the following steps:
(1) Carrying out coprecipitation reaction on water-soluble iron salt, water-soluble copper salt and a coprecipitator solution, and separating out a precipitate from a reaction product, wherein the coprecipitator solution contains a silicon source, a potassium source, a water-soluble alkali source and a water-soluble aluminum source;
(2) Pulping the precipitate obtained in the step (1) in the presence of deionized water to obtain precipitate slurry; and
(3) And (3) carrying out spray drying on the precipitate slurry obtained in the step (2), and then roasting.
2. The process of claim 1 wherein the water soluble aluminum source is selected from one or more of sodium aluminate, sodium metaaluminate, potassium aluminate and potassium metaaluminate.
3. The process according to claim 1 or 2, wherein in step (1), the silicon source is selected from one or more of potassium silicate, sodium silicate, orthosilicic acid and silica sol.
4. The process of claim 1 or 2, wherein in step (1), the potassium source is a water-soluble potassium salt.
5. The process of claim 4, wherein in step (1), the potassium source is selected from one or more of potassium silicate, potassium carbonate, potassium bicarbonate, potassium aluminate, and potassium metaaluminate.
6. The process according to claim 1 or 2, wherein in step (1), the water-soluble alkali source is selected from one or more of potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, ammonium carbonate, ammonium bicarbonate and urea.
7. The method according to claim 1 or 2, wherein, in step (1), the conditions of the coprecipitation reaction include: the temperature is 40-80 ℃, and the pH value of the system is regulated to 4-8.
8. The method of claim 1 or 2, wherein in step (3), the conditions of the spray drying comprise: the inlet air temperature is 200-350 ℃, and the outlet air temperature is 95-115 ℃; and/or the presence of a gas in the gas,
the roasting condition comprises roasting for 8-16 hours at 100-200 ℃, then heating to 400-550 ℃ at the heating rate of 280-350 ℃/hour, and roasting for 3-7 hours.
9. The process of any one of claims 1 to 8The iron-based Fischer-Tropsch synthesis catalyst prepared by the method is characterized by comprising the following elements in percentage by weight, fe, cu, K and SiO 2 Al =100 (0.01-5): (1-7): 5-27): 0.01-4.5), the Fischer-Tropsch synthesis catalyst contains KAlSiO 4 。
10. The catalyst of claim 9, wherein Fe is α -Fe 2 O 3 Exist in the form of (1).
11. The catalyst of claim 9 or 10, wherein the catalyst further comprises Na element.
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