CN103230810A - 合成气制低碳烯烃的费托合成催化剂、改性分子筛载体及制备方法 - Google Patents
合成气制低碳烯烃的费托合成催化剂、改性分子筛载体及制备方法 Download PDFInfo
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- CN103230810A CN103230810A CN2013101476082A CN201310147608A CN103230810A CN 103230810 A CN103230810 A CN 103230810A CN 2013101476082 A CN2013101476082 A CN 2013101476082A CN 201310147608 A CN201310147608 A CN 201310147608A CN 103230810 A CN103230810 A CN 103230810A
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- Prior art keywords
- molecular sieve
- salt
- preparation
- praseodymium
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims abstract description 111
- 239000000243 solution Substances 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 23
- 150000001213 Praseodymium Chemical class 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- -1 praseodymium salt modified molecular sieve Chemical class 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 28
- 150000000703 Cerium Chemical class 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 229910002796 Si–Al Inorganic materials 0.000 claims description 22
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 13
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 4
- 150000003891 oxalate salts Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 abstract 5
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 abstract 2
- 229910052710 silicon Inorganic materials 0.000 abstract 2
- 239000010703 silicon Substances 0.000 abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 25
- 239000010949 copper Substances 0.000 description 20
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 16
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229940072033 potash Drugs 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 9
- 235000015320 potassium carbonate Nutrition 0.000 description 9
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001417 caesium ion Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0358—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7065—CHA-type, e.g. Chabazite, LZ-218
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明提供一种合成气制低碳烯烃的费托合成催化剂、改性分子筛载体及制备方法,费托合成催化剂组分为分子筛载体和活性组分,分子筛为经铈盐和/或镨盐改性的硅铝分子筛和/或高硅分子筛载体,活性组分以Fe为主要成分,还包含活性组分Mn和Cu以及碱性助剂,改性分子筛为40%~80 wt %。改性分子筛上铈盐和/或镨盐的质量百分比为分子筛的1%~20%。铈盐和/或镨盐改性分子筛载体是将硅铝分子筛和/或高硅分子筛经酸溶液处理得到氢型的分子筛,将氢型的分子筛在铈盐和/或镨盐溶液中浸渍,然后干燥、焙烧后得到铈和/或镨改性分子筛。将铈盐和/或镨盐改性分子筛在活性组分的盐溶液中浸渍;然后干燥、焙烧得到合成气制低碳烯烃的费托合成催化剂。
Description
技术领域
本发明涉及一种合成气制低碳烯烃的费托合成催化剂、改性分子筛载体及制备方法,特别是由合成气通过费托合成反应一步法生产低碳烯烃的催化剂及制备方法。
背景技术
低碳烯烃是重要的基本有机化工原料。通常低碳烯烃由原油衍生的石脑油经蒸汽裂解生产,但是目前迫切需要有替代原料及过程以突破供应限制和环境问题。目前,合成气经甲醇两步法制烯烃已经实现工业化应用,但存在流程复杂,工艺路线长,一次性投资大等问题。费托合成一步法制烯烃可以较好的解决上述问题,但低碳烯烃选择性往往较低,限制了其工业化应用。
多年来,一些研究团队已经尝试开发高温熔铁催化剂,用于提高费托合成直接生产低碳烯烃(FTO)的产品的选择性,并且已经取得可喜的成果。但是,熔铁催化剂在高温下的机械性能不佳,可能会导致固定床操作中催化剂床层的堵塞,或造成流化床过程分离设备的积垢,限制了熔铁催化剂在费托合成生产低碳烯烃反应过程的应用。
专利CN1040397C采用MgO等ⅡA族碱土金属氧化物或高硅沸石分子筛(或磷铝沸石)负载的Fe—Mn催化剂体系,在强碱(ⅠA族金属)K或Cs离子助剂作用下,具有良好的合成低碳烯烃选择性,反应在300~400℃的条件下,CO转化率90%,低碳烯烃占气相产物烃类质量含量的66%以上,但气相产物中CH4选择性较高。
专利CN101219384A使用真空浸渍的制备方法,使主催化剂组分Fe以及助剂高度分散到载体活性炭上,从而获得很高的催化活性和良好的催化效果。在300~400℃,压力1~2MPa,合成气空速400~1000h-1的工艺条件下,CO转化率达95%,低碳烯烃占气相产物烃类质量含量的68%以上,但在高温下易积碳失活。
专利CN1065026A公开了合成气制乙烯的催化剂及制备方法,添加Nb,Ga,Pr,Sc,In,Yb,Ce,La等十余种化学元素,乙烯选择性可达90%以上,但CO转化率较低,合成气的循环势必增加设备和运行成本。
De Jong等(Krijn P. de Jong et al. Science, 2012, 335,835.)将铁纳米颗粒均匀分散在弱***互式α—氧化铝或碳纳米纤维载体上,使合成气直接转化制取C2~C4轻烯烃,在CO转化率80%时,低碳烯烃占烃类产物质量含量50%,并拥有相对良好的抗结焦性能。但制备过程复杂难以实现工业化应用。
发明内容
为了解决上述技术问题,本发明的目的是给出一种合成气制低碳烯烃的费托合成催化剂、改性分子筛载体及制备方法,具体为能工业化应用的铈盐和/或镨盐改性分子筛载体和催化剂的制备方法,使催化剂的催化活性和稳定性明显改善。
本发明采用的技术方案如下:本发明的一种合成气制低碳烯烃的费托合成催化剂,其组分为分子筛载体和活性组分,分子筛为经铈盐和/或镨盐改性的硅铝分子筛和/或高硅分子筛载体。
所述的活性组分以Fe为主要成分,还包含活性组分Mn和Cu以及碱性助剂,所述的碱性助剂选自K;各组分的质量百分比为Fe:10%~35 wt%,Mn:1%~20 wt %,Cu:1%~20 wt %,K:1%~10 wt %,改性分子筛为40%~80 wt %。
所述铈盐和/或镨盐占改性分子筛上铈盐和/或镨盐质量百分比为分子筛的1%~20%。
优选地,所述铈盐和/或镨盐占改性分子筛上铈盐和/或镨盐质量百分比为分子筛的10%~20%。
本发明的铈盐和/或镨盐改性分子筛载体的制备方法,步骤如下:
1)将硅铝分子筛SSZ-13、SAPO-34和/或高硅分子筛ZSM-5置于选自硫酸铵、硝酸铵、氯化铵、醋酸中的一种酸溶液中在温度为26~99℃的条件下回流3~6h,酸溶液的浓度为0.05~5mol/L,然后过滤,洗涤,干燥后,在温度400~700℃焙烧1~8h ,得到氢型的分子筛;
2)将步骤1)中得到的氢型分子筛浸渍在铈盐和/或镨盐溶液中,铈盐和/或镨盐溶液浓度为0.1~1mol/L ,在温度为25~85℃,真空度为10-1~10-4Pa条件下浸渍15~30h;
3)将步骤2)中浸渍得到的分子筛在温度在为70~150℃下干燥15~30h,在温度为400~700℃下焙烧1~8h,制备得铈和/或镨改性分子筛。
优选地,所述铈盐或镨盐为碳酸盐或甲酸盐。
优选地,所述的改性分子筛干燥温度为80~130℃;干燥时间为20~30h。所述的改性分子筛焙烧处理温度为500~700℃;焙烧时间为4~8h。
本发明的一种合成气制低碳烯烃的费托合成催化剂的制备方法,包括以下步骤:
1)按质量百分比为Fe:10%~35 wt %,Mn:1%~20 wt %,Cu:1%~20 wt %,K:1%~10 wt %,称取Fe、Mn、Cu的无机盐及含助剂K元素的碱或盐,完全溶于定量水溶剂中,边搅拌边加入一定量表面活性剂月桂醇硫酸钠,继续搅拌得均匀溶液,在真空度为10-1~10-4Pa条件下将铈盐和/或镨盐改性分子筛浸渍于所得均匀溶液中;
2)在30~70℃下干燥混合溶液1~8h,将干燥后的物质在400~600℃温度进行焙烧3~8h;
优选地,所述的铁盐为硝酸铁、草酸铁、柠檬酸铁;所述的锰盐、铜盐、碱金属助剂盐为为草酸盐、醋酸盐、碳酸盐。
优选地,所述的合成气制低碳烯烃的费托合成催化剂的制备方法中步骤2)溶液干燥温度为50~65℃;干燥时间为为6~8h;焙烧温度为500~600℃;焙烧时间为6~8h。
优选地,所述的合成气制低碳烯烃的费托合成催化剂的制备方法中步骤1)质量百分比为Fe:10%~35 wt %,Mn:1%~10 wt %,Cu:1%~10 wt %,K:1%~10 wt %,控制催化剂中改性分子筛为60%~80 wt %。
本发明的优点是:
通过载体改性手段简单方便,成本低;本发明通过浸渍法制备催化剂相对于熔铁需要在高温炉中制备,降低了能耗;制备过程简单易行,易工业化生产。
该催化剂在费托合成制取烯烃的反应过程中,催化活性和稳定性明显改善,CO转化率达到93%以上;产物中低碳烯烃选择性和烯烷比提高,低碳烯烃占C2~C4烃含量的85%以上;同时抑制甲烷选择性。
具体实施方式
以下用具体实施例来说明本发明的技术方案,但本发明的保护范围不限于此:
本发明的合成气制低碳烯烃的费托合成催化剂的分子筛载体为Ce、Pr的一种或两种改性的硅铝分子筛(SSZ-13、SAPO-34),高硅分子筛(ZSM-5)或它们的混合物。
改性分子筛的制备,包括以下步骤:
(1)将SSZ-13、SAPO-34硅铝分子筛或ZSM-5等高硅分子筛与选自硫酸铵、硝酸铵、氯化铵、醋酸中的一种在温度为26~99℃的条件下回流3~6h,酸溶液的浓度为0.05~5mol/L,过滤,洗涤,干燥后,在温度700℃焙烧6h,得到氢型的分子筛;
(2)将步骤(1)中得到的氢型分子筛与浓度为0.1~1mol/L铈盐(或镨盐)溶液充分混合均匀,在温度为25~85℃,真空度为10-1~10-4Pa条件下浸渍15~30h;
(3.)将步骤(2)中得到的分子筛在温度为70~150℃下,干燥15~30h,在温度为400~700℃下,焙烧1~8h。制备得所需的铈(或镨)改性分子筛;
所述铈盐(或镨盐)占改性分子筛质量百分比为:1%~20%,更优选为10~20%。
所述铈盐(或镨盐)为硝酸盐、甲酸盐、碳酸盐和硫酸盐,更优选为碳酸盐、甲酸盐。
所述的改性分子筛干燥温度为70~150℃,更优选为80~130℃;干燥时间为15~30h,更优选为20~30h。
所述的改性分子筛焙烧处理温度为400~700℃,更优选为500~700℃;焙烧时间为1~8h,更优选为4~8h。
本发明的费托合成催化剂以Fe为主要成分,还包含活性组分Mn和Cu以及碱性助剂和结构助剂,所述的碱性助剂选自K,所述的结构助剂选自Ce(或Pr)改性的SSZ-13、SAPO-34、ZSM-5或它们的混合物。
本发明的催化剂可采用本领域的常规制备方法,优选浸渍法。
本发明的催化剂的制备过程按下述步骤进行:
①.制备Ce、Pr改性分子筛载体;
②.按一定质量比称取Fe、Mn、Cu的无机盐及含助剂K元素的碱或盐,溶于定量水溶剂中,边搅拌边加入一定量表面活性剂,继续搅拌,得均匀溶液。在真空度为10-1~10-4Pa条件下将所得均匀溶液浸渍于步骤①中制得的改性分子筛上。
③.在30~70℃下干燥混合溶液1~8h,将干燥后的物质在400~600℃温度进行焙烧3~8h;
所述的铁盐为硝酸铁、草酸铁、柠檬酸铁、硫酸铁等,更优选为硝酸铁、草酸铁、柠檬酸铁。
所述的锰盐、铜盐、碱金属助剂盐为草酸盐、醋酸盐、柠檬酸盐、硝酸盐、硫酸盐、碳酸盐,更优选为草酸盐、醋酸盐、碳酸盐。
溶液干燥温度为30~70℃,更优选为50~65℃;干燥时间为3~8h,更优选为6~8h;焙烧温度为400~600℃,更优选为500~600℃;焙烧时间为3~8h,更优选为6~8h。
此催化剂的特点在于其各组分的质量百分比为Fe:10%~35 wt %,Mn:1%~10 wt%,Cu:1%~10 wt%,K:1%~10 wt%,改性分子筛:40%~80 wt%。
优选地,步骤1)质量百分比为Fe:10%~35 wt %,Mn:1%~10 wt%,Cu:1%~10 wt %,K:1%~10 wt %,更有利于控制催化剂中改性分子筛为优选比例60%~80 wt %。
将催化剂按如下方法应用于合成气制低碳烯烃的反应中:
在内径为8mm的固定床反应器中加入1ml催化剂于恒温区,反应前用空速为1500h-1氢气在380℃下将催化剂还原8h。还原完成后,在340℃,2MPa的条件下,以1000h-1的空速向反应器中连续通入氢碳体积比为2的合成气进行反应。
实施例1:
按质量比Ce:分子筛=1:9称取硝酸铈和SSZ-13硅铝分子筛,将分子筛与0.1mol/L硝酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸铈溶液混合均匀,在85℃、10-4Pa真空度下浸渍24h,然后在130℃下干燥20h,最后在550℃下焙烧6h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=28:5:5:5称取草酸铁、硝酸锰、柠檬酸铜和碳酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=7:15定量称取Ce改性的SSZ-13硅铝分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,在65℃条件下干燥4h,然后在600℃下焙烧3h,得到粉末状的FTO催化剂A,催化剂的具体组成见表1。将FTO催化剂 A经压片成型,破碎过筛,然后取30~60目的催化剂1ml,装入固定床反应器中,在380℃条件下用空速为1500h-1氢气还原8h,而后切换为空速1000h-1的合成气(体积比H2:CO =2: 1),在340℃、2.0MPa的条件下连续反应。每小时在气相色谱在线检测一次气相产物,C5+、含氧化合物和CO2不计入产物选择性。催化剂A的反应结果见表2,其中,CO转化率为96.1%,低碳烯烃在低碳烃(不包括甲烷)中选择性为90.1%。
实施例2:
按质量比Ce:分子筛=1:19称取硝酸铈,SSZ-13硅铝分子筛,将分子筛与0.1mol/L硫酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸铈溶液混合均匀,在25℃、10-1Pa真空度下浸渍30h,然后在150℃下干燥15h,最后在700℃下焙烧6h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=22:6:6:2称取硝酸铁、硝酸锰、硝酸铜和硝酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=22:65定量称Ce改性的SSZ-13硅铝分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,30℃条件下干燥8h。然后在500℃下焙烧5h,得到粉末状的FTO催化剂B,催化剂B的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂B的反应结果见表2,其中,CO转化率为95.6%,低碳烯烃在低碳烃(不包括甲烷)中选择性为86.9%。
实施例3:
按质量比Ce:分子筛=1:99称取硝酸铈,SAPO-34硅铝分子筛,将分子筛与0.1mol/L硝酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸铈溶液混合均匀,在50℃、10-3Pa真空度下浸渍26h,然后在70℃下干燥30h,最后在650℃下焙烧2h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=18:6:3:1称取柠檬酸铁、草酸锰、硫酸铜和碳酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=1:4定量称Ce改性的SAPO-34硅铝分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,40℃条件下干燥7h。然后在400℃下焙烧8h,得到粉末状的FTO催化剂C,催化剂C的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂C的反应结果见表2,其中,CO转化率为94.7%,低碳烯烃在低碳烃(不包括甲烷)中选择性为84.7%。
实施例4:
按质量比Pr:分子筛=1:4称取硝酸镨,SAPO-34硅铝分子筛,将分子筛与0.1mol/L硫酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸镨溶液混合均匀,在60℃、10-3Pa真空度下浸渍22h,然后在100℃下干燥24h,最后在500℃下焙烧5h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=39:10:9:2称取草酸铁、硫酸锰、柠檬酸铜和碳酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=39:40定量称取Pr改性的SAPO-34硅铝分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,60℃条件下干燥6h。然后在550℃下焙烧4h,得到粉末状的FTO催化剂D,催化剂D的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂D的反应结果见表2,其中,CO转化率为94.9%,低碳烯烃在低碳烃(不包括甲烷)中选择性为88.8%。
实施例5:
按质量比Pr:分子筛=1:9称取硝酸铈,ZSM-5分子筛,将分子筛与0.1mol/L硝酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸镨溶液混合均匀,在70℃、10-2Pa下浸渍20h,然后在120℃下干燥22h,最后在600℃下焙烧3h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=11:3:2:1称取柠檬酸铁、硝酸锰、草酸铜和碳酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=1:3定量称取Pr改性的ZSM-5分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,50℃条件下干燥5h。然后在600℃下焙烧7h,得到粉末状的FTO催化剂E,催化剂E的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂E的反应结果见表2,其中,CO转化率为93.3%,低碳烯烃在低碳烃(不包括甲烷)中选择性为87.2%。
实施例6:
按质量比Pr:分子筛=1:19称取硝酸铈,ZSM-5分子筛,将分子筛与0.1mol/L硫酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸镨溶液混合均匀,在40℃、10-1Pa真空度下浸渍28h,然后在80℃下干燥26h,最后在700℃下焙烧1h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=18:6:3:1称取硫酸铁、硝酸锰、柠檬酸铜和碳酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=1:4定量称取Pr改性的ZSM-5分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,70℃条件下干燥3h。将干燥后得到的物质在450℃下焙烧6h,得到粉末状的FTO催化剂F,催化剂F的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂F的反应结果见表2,其中,CO转化率为94.5%,低碳烯烃在低碳烃(不包括甲烷)中选择性为85.6%。
实施例7
按质量比Ce:Pr:分子筛=0.5:0.5:99称取硝酸铈,硝酸镨和SSZ-13硅铝分子筛,将分子筛与0.1mol/L硝酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸铈溶液混合均匀,在85℃、10-4Pa真空度下浸渍24h,然后在130℃下干燥20h,最后在550℃下焙烧6h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=15:10:5:5称取草酸铁、硝酸锰、柠檬酸铜和碳酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=3:13定量称取Ce改性的SSZ-13硅铝分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,在65℃条件下干燥4h,然后在600℃下焙烧3h,得到粉末状的FTO催化剂G,催化剂的具体组成见表1。催化剂G的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂G的反应结果见表2,其中,CO转化率为95.2%,低碳烯烃在低碳烃(不包括甲烷)中选择性为88.5%。
实施例8
按质量比Ce:Pr:分子筛=1: 1:18称取硝酸铈,硝酸镨和SSZ-13硅铝分子筛,将分子筛与0.1mol/L硫酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸铈溶液混合均匀,在25℃、10-1Pa真空度下浸渍30h,然后在150℃下干燥15h,最后在700℃下焙烧6h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=35:1:5:4称取硝酸铁、硝酸锰、硝酸铜和硝酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=7:11定量称Ce改性的SSZ-13硅铝分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,30℃条件下干燥8h。然后在500℃下焙烧5h,得到粉末状的FTO催化剂H,催化剂H的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂H的反应结果见表2,其中,CO转化率为96.3%,低碳烯烃在低碳烃(不包括甲烷)中选择性为89.3%。
实施例9:
按质量比Ce:Pr:分子筛=1:1:8称取硝酸铈,硝酸镨和SAPO-34硅铝分子筛,将分子筛与0.1mol/L硝酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸铈溶液混合均匀,在50℃、10-3Pa真空度下浸渍26h,然后在70℃下干燥30h,最后在650℃下焙烧2h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=20:10:5:2称取柠檬酸铁、草酸锰、硫酸铜和碳酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=20:63定量称Ce改性的SAPO-34硅铝分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,40℃条件下干燥7h。然后在400℃下焙烧8h,得到粉末状的FTO催化剂I,催化剂I的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂I的反应结果见表2,其中,CO转化率为96.3%,低碳烯烃在低碳烃(不包括甲烷)中选择性为87.6%。
实施例10:
按质量比Ce:分子筛=1:4称取硝酸铈,SAPO-34硅铝分子筛,将分子筛与0.1mol/L硫酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸镨溶液混合均匀,在60℃、10-3Pa真空度下浸渍22h,然后在100℃下干燥24h,最后在500℃下焙烧5h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=10:5:3:2称取草酸铁、硫酸锰、柠檬酸铜和碳酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=1:8定量称取Pr改性的SAPO-34硅铝分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,60℃条件下干燥6h。然后在550℃下焙烧4h,得到粉末状的FTO催化剂J,催化剂J的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂J的反应结果见表2,其中,CO转化率为95%,低碳烯烃在低碳烃(不包括甲烷)中选择性为85.8%。
实施例11:
按质量比Pr:分子筛=1:99称取硝酸铈,ZSM-5分子筛,将分子筛与0.1mol/L硝酸铵溶液在80℃下回流5h,过滤、洗涤、干燥后,在700℃焙烧6h,将所得氢型分子筛与硝酸镨溶液混合均匀,在70℃、10-2Pa下浸渍20h,然后在120℃下干燥22h,最后在600℃下焙烧3h,制得改性分子筛。
按质量比Fe:Mn:Cu:K=23:1:9:7称取柠檬酸铁、硝酸锰、草酸铜和碳酸钾,以水作为溶剂配成溶液,加入占溶液质量0.1%的表面活性剂月桂醇硫酸钠,搅拌。按质量比Fe:分子筛=23:60定量称取Pr改性的ZSM-5分子筛,在真空条件下,将溶液浸入分子筛,混合搅拌均匀,50℃条件下干燥5h。然后在600℃下焙烧7h,得到粉末状的FTO催化剂K,催化剂K的具体组成见表1。催化剂的活性评价过程同实施例1。催化剂K的反应结果见表2,其中,CO转化率为94.2%,低碳烯烃在低碳烃(不包括甲烷)中选择性为86.3%。
表1 催化剂A~F具体组成
催化剂 | 改性载体质量组成 | 催化剂质量组成 |
A | 10%Ce | 28Fe:5Mn:5Cu:5K:60改性分子筛 |
B | 5%Ce | 22Fe:6Mn:5Cu:2K:65改性分子筛 |
C | 1%Ce | 18Fe:6Mn:3Cu:1K:72改性分子筛 |
D | 20%Pr | 39Fe:10Mn:9Cu:2K:40改性分子筛 |
E | 10%Pr | 22Fe:6Mn:4Cu:2K:66改性分子筛 |
F | 5%Pr | 18Fe:6Mn:3Cu:1K:72改性分子筛 |
G | 0.5%Ce+0.5% Pr | 15Fe:10Mn:5Cu:5K:65改性分子筛 |
H | 5%Ce+5%Pr | 35Fe:1Mn:5Cu:4K:55改性分子筛 |
I | 10%Ce+10%Pr | 20Fe:10Mn:5Cu:2K:63改性分子筛 |
J | 20%Ce | 10Fe:5Mn:3Cu:2K:80改性分子筛 |
K | 1%Pr | 23Fe:1Mn:9Cu:7K:60改性分子筛 |
表2 催化剂的反应性能评价结果
Claims (11)
1.一种合成气制低碳烯烃的费托合成催化剂,组分为分子筛载体和活性组分,其特征在于:分子筛为经铈盐和/或镨盐改性的硅铝分子筛和/或高硅分子筛载体。
2.根据权利要求1所述的合成气制低碳烯烃的费托合成催化剂,其特征在于:活性组分以Fe为主要成分,还包含活性组分Mn和Cu以及碱性助剂,所述的碱性助剂选自K;各组分的质量百分比为Fe:10%~35 wt %,Mn:1%~20 wt %,Cu:1%~20 wt %,K:1%~10 wt %,改性分子筛为40%~80 wt %。
3.根据权利要求1或2所述的合成气制低碳烯烃的费托合成催化剂,其特征在于:所述铈盐和/或镨盐占改性分子筛上铈盐和/或镨盐质量百分比为分子筛的1%~20%。
4.根据权利要求1或2所述的合成气制低碳烯烃的费托合成催化剂,其特征在于:所述铈盐和/或镨盐占改性分子筛上铈盐和/或镨盐质量百分比为分子筛的10%~20%。
5.一种铈盐和/或镨盐改性分子筛载体的制备方法,步骤如下:
1)将硅铝分子筛SSZ-13、SAPO-34和/或高硅分子筛ZSM-5置于选自硫酸铵、硝酸铵、氯化铵、醋酸中的一种酸溶液中在温度为26~99℃的条件下回流3~6h,酸溶液的浓度为0.05~5mol/L,然后过滤,洗涤,干燥后,在温度400~700℃焙烧1~8h ,得到氢型的分子筛;
2)将步骤1)中得到的氢型分子筛浸渍在铈盐和/或镨盐溶液中,铈盐和/或镨盐溶液浓度为0.1~1mol/L ,在温度为25~85℃,真空度为10-1~10-4Pa条件下浸渍15~30h;
3)将步骤2)中浸渍得到的分子筛在温度在为70~150℃下干燥15~30h,在温度为400~700℃下焙烧1~8h,制备得铈和/或镨改性分子筛。
6.根据权利要求5所述的铈盐和/或镨盐改性分子筛载体的制备方法,其特征在于:所述铈盐或镨盐为碳酸盐或甲酸盐。
7.根据权利要求5或6所述的铈盐和/或镨盐改性分子筛载体的制备方法,其特征在于:所述的改性分子筛干燥温度为80~130℃;干燥时间为20~30h。所述的改性分子筛焙烧处理温度为500~700℃;焙烧时间为4~8h。
8.一种合成气制低碳烯烃的费托合成催化剂的制备方法,包括以下步骤:
1)按质量百分比为Fe:10%~35 wt %,Mn:1%~20 wt %,Cu:1%~20 wt %,K:1%~10 wt %,称取Fe、Mn、Cu的无机盐及含助剂K元素的碱或盐,完全溶于定量水溶剂中,边搅拌边加入一定量表面活性剂月桂醇硫酸钠,继续搅拌得均匀溶液,在真空度为10-1~10-4Pa条件下将铈盐和/或镨盐改性分子筛浸渍于所得均匀溶液中;
2)在30~70℃下干燥混合溶液1~8h,将干燥后的物质在400~600℃温度进行焙烧3~8h。
9.根据权利要求8所述的合成气制低碳烯烃的费托合成催化剂的制备方法,其特征在于:所述的铁盐为硝酸铁、草酸铁、柠檬酸铁;所述的锰盐、铜盐、碱金属助剂盐为为草酸盐、醋酸盐、碳酸盐。
10.根据权利要求8或9所述的合成气制低碳烯烃的费托合成催化剂的制备方法,其特征在于:步骤2)溶液干燥温度为50~65℃;干燥时间为为6~8h;焙烧温度为500~600℃;焙烧时间为6~8h。
11.根据权利要求8或9所述的合成气制低碳烯烃的费托合成催化剂的制备方法,其特征在于:步骤1)质量百分比为Fe:10%~35 wt %,Mn:1%~10 wt %,Cu:1%~10 wt %,K:1%~10 wt %,控制催化剂中改性分子筛为60%~80 wt %。
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US20160045903A1 (en) | 2016-02-18 |
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