CN109569623B - 合成气直接制烯烃的催化剂、制备方法及使用方法 - Google Patents
合成气直接制烯烃的催化剂、制备方法及使用方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 46
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000003321 amplification Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 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 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 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 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- -1 ethylene, propylene, butadiene Chemical class 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- B01J23/70—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
- B01J23/80—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 zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/83—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 rare earths or actinides
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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
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- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
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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
- B01J23/70—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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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
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- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
一种合成气直接制烯烃的催化剂、制备方法及使用方法，该催化剂由第一金属组分、第二金属组分和碱性助剂组成。其制备方法为：首先将第一金属组分的盐和第二金属组分的盐配成水溶液，进入混合，并滴加碱性助剂前驱体溶液，通过控制温度、pH值与搅拌速率，以及经过抽滤，干燥与焙烧等步骤，获得催化剂。其使用方法为：用H2或合成气将所得催化剂还原后，通入H2/CO摩尔比为1:1‑8:1的混合气体，在0.1‑5MPa(绝对压力)、250‑450℃、体积空速为500‑10000h‑1下进行烯烃合成反应。本发明方法制备的催化剂可将合成气一步转化为高烯烃含量的烃类产物，具有原料转化率高，烯烃收率高，成本低，易放大的特性。
Description
技术领域
本发明属于化工技术领域，特别涉及一种合成气直接制烯烃的催化剂、制备方法及使用方法。
背景技术
烯烃(乙烯、丙烯、丁二烯)是重要的有机化工基础原料，是生产合成树脂、合成纤维和合成橡胶等的重要原料，芳纶、高性能纤维PTT、光伏PET膜等多种被定义为高端石化产品的材料，也都是以烯烃为基础原料生产的。长期以来，制备烯烃的路线主要包括石油脑裂解，乙烷裂解与甲醇催化转化。我国石油资源短缺，进口依赖度大。所以，近来甲醇直接制备烯烃成为新的技术增长点，目前这条路线的产能已经接近1000万吨/年。
但这些技术均以煤炭为原料，经过合成气，以甲醇作为中间产物来合成烯烃。甲醇生成的压力高，反应器复杂，生成的水与甲醇分离能耗高。因此直接利用合成气制备烯烃的技术对于缩短工艺流程，减化水与甲醇的分离单元与降低分享能耗，以及减少含醇废水的生成，降低处理成本至关重要。合成气制备芳烃过程，相当于将合成气制备烃类(费托过程)-烃类芳构化耦合，或合成气制备甲醇-甲醇芳构化耦合。这两个过程的温位、压力、催化剂种类均不一样，给过程的耦合以及催化剂的开发造成了极大的困难。比如，基于Zr-Zn催化剂及SAPO-34催化剂，在400℃下，0.5MPa，1MPa与2MPa下，空速为3600ml合成气/g催化剂/小时，CO转化率约在0.5％-11％，烯烃在烃类的选择性在36％-68％，CO2选择性约为43％。基于Co基催化剂，在220℃及2MPa下，空速为5.1g催化剂*小时/mol，CO转化率达80％，烯烃选择性降到12％以下，C5以上的汽油类烃的选择性达到80％。基于ZnCrOx-ZSM-5体系，350℃及4MPa下，空速1500ml/g催化剂/小时，烃中烯烃选择性7.1％,芳烃选择性73.9％。CO2选择性47％。基于Fe-Zn-Na催化剂，350℃及2MPa下，空速60000ml/g催化剂/小时，烃中烯烃选择性25.5％，C5以上烃类的选择性58％。CO2选择性27.3％。总之，普遍存在着如果想提高烯烃选择性，对应于低CO转化率，与高的CO2选择性。给分离与物料循环，造成了巨大困难，成本居高不下。
发明内容
为了克服上述催化剂制备方法复杂，反应流程太长，或烯烃收率太低的问题，本发明的目的在于提供一种合成气一步法直接高效合成烯烃的催化剂、制备方法及使用方法。
为了实现上述目的，本发明采用的技术方案是：
一种合成气直接制烯烃的催化剂，由第一金属组分、第二金属组分和碱性助剂组成，所述第一金属组分为铁、镍、钴中的一种或多种，若为多种，则为任意质量百分比混合，第一金属组分的含量占催化剂的质量百分比为10％-50％；所述第二金属组分为锌、铬、锰、铜、镓、银、镓、镧、铈中的一种或多种，若为多种，则为任意质量百分比混合，第二金属组分的含量占催化剂的质量百分比为10％-50％；所述碱性助剂为钠型、钾型、钙型氧化物中的一种或多种，若为多种，则为任意质量百分比混合，碱性助剂的含量占催化剂的质量百分比为20％-40％。
本发明还提供了所述合成气直接制烯烃的催化剂的制备方法，包括如下步骤：
(1)、取第一金属组分前驱体，用去离子水配成0.01-0.1Mol/L溶液，取第二金属组分前驱体，用去离子水配成0.01-1Mol/L的溶液，取碱性助剂前驱体，用去离子水配成0.01-1Mol/L溶液；
(2)、将两种金属的盐溶液混合，在40-90℃及300-600rpm搅拌下，向金属盐溶液中滴加碱性助剂的溶液，维持温度不变与PH不变，滴加1-10小时，滴加结束后，将搅拌速度升至700-1200rpm，调节pH值为8-11并保持3-16小时。然后，将所得絮沉物抽滤；
(3)、将抽滤所得滤饼在60-100℃的条件下烘干3-24小时，在200-400℃下焙烧3-24小时。
所述第一金属组分前驱体为该金属的一种可溶性盐或多种可溶性盐的混合物，所述第二金属组分前驱体为该金属的一种可溶性盐或多种可溶性盐的混合物。
所述可溶性盐为硝酸盐、硫酸盐或氯化物。
所述碱性助剂前驱体为该助剂的一种可溶性化合物。
所述可溶性化合物为碳酸盐、碳酸氢盐、碱式碳酸盐或氢氧化物。
本发明还提供了所述催化剂的应用：将所述催化剂装入反应器中，在250-450℃下，用H2或H2/CO合成气还原1-4小时后，通入H2/CO摩尔比为1:1-8:1的混合气体，在0.1-5MPa、250-450℃、体积空速为500-10000h-1下进行烯烃合成反应。
所述H2/CO合成气中，H2与CO的摩尔比为2:1。
在CO转化率为40-90％时，烯烃选择性为50-95％。
与现有技术相比，本发明的有益效果是：
1)本发明所述的催化剂，制备工艺简单，降低催化剂成本约80％。
2)使用本发明所述的催化剂可将合成气一步转化为高烯烃含量的烃类产物，由于烯烷比高，分离能耗低60％。
3)在本发明所述催化剂上进行的合成气转化过程中，CO2选择性或收率比现有技术低50％。
具体实施方式
下面结合实施例详细说明本发明的实施方式。
实施例1
取硝酸铁，用去离子水配成1Mol/L溶液，取氯化锌，用去离子水配成0.01Mol/L溶液。取碳酸钠，用去离子中配成1Mol/L溶液。将硝酸铁溶液和氯化锌溶液混合，在80℃及600rpm搅拌条件下，向其中滴加碳酸钠溶液，维持温度与PH不变，滴加4小时。滴加结束后，将搅拌速度升至700rpm，调节pH值为9-9.2并保持3小时。然后，将所得絮沉物抽滤，将滤饼在60℃烘干24小时，在300℃焙烧3小时。所得催化剂成分为：50％Fe-10％Zn-40％Na2O。
将所述催化剂装入反应器中，在250℃下，用合成气(H2/CO＝2:1)还原4小时后，通入H2/CO摩尔比为2:1的混合气体，在2MPa、350℃、体积空速为5000h-1下进行烯烃合成反应。在CO转化率为90％时，烯烃选择性为60％。
实施例2
取硝酸镍，用去离子水配成0.5Mol/L溶液，取硝酸镧与硝酸镓，用去离子水配成0.5Mol/L溶液。取碳酸氢钾，用去离子中配成1Mol/L溶液。将硝酸镍溶液、硝酸镧与硝酸镓溶液混合，在60℃及600rpm搅拌条件下，向其中滴加碳酸氢钾溶液，维持温度不变与PH不变，滴加5小时。滴加结束后，将搅拌速度升至1000rpm，调节pH值为10.5-11并保持10小时。然后，将所得絮沉物抽滤，将滤饼在90℃烘干3小时，在300℃焙烧24小时。所得催化剂成分为：50％Ni-10％La-10％Ga-30％K2O。
将所述催化剂装入反应器中，在250℃下，用H2还原2小时。然后通入H2/CO摩尔比为1:1的混合气体，在5MPa、250℃、体积空速为5000h-1下进行烯烃合成反应。在CO转化率为90％时，烯烃选择性为50％。
实施例3
取硝酸钴，用去离子水配成0.01Mol/L溶液，取硝酸银与硝酸锰，用去离子水配成1Mol/L溶液。取碳酸氢钙用去离子配成0.01Mol/L溶液。将硝酸钴、硝酸银、硝酸锰溶液混合，在70℃及600rpm搅拌条件下，并向其中滴加碳酸氢钙溶液，维持温度不变与PH不变，滴加10小时。滴加结束后，将搅拌速度升至720rpm，调节pH值为8-8.5并保持10小时。然后，将所得絮沉物进行抽滤，并将滤饼在80℃干燥12小时，在400℃焙烧12小时。所得催化剂成分为：7％Co-3％Ag-50％Mn-40％CaO。
将所述催化剂装入反应器中，在450℃下，用合成气还原1小时后，通入H2/CO摩尔比为5:1的混合气体，在0.5MPa，450℃、体积空速为3000h-1下进行烯烃合成反应。在CO转化率为60％时，烯烃选择性为75％。
实施例4
取硫酸铁与硫酸镍，用去离子水配成0.7Mol/L溶液。取硝酸铬与硝酸铈，用去离子水配成1Mol/L溶液。取碱式碳酸钠，用去离子水配成1Mol/L溶液。将硫酸铁、硫酸镍溶液、硝酸铬及硝酸铈溶液混合，在40℃及300rpm搅拌下，并向其中滴加碱式碳酸钠溶液，维持温度不变与PH不变，滴加1小时。滴加结束后，将搅拌速度升至1080rpm，调节pH值为10.6-11并保持6小时。然后，将所得絮沉物抽滤。将滤饼在80℃烘干15小时，在200℃焙烧5小时。所得催化剂成分为：20％Fe-30％Ni-11％Cr-9％Ce-30％Na。
将所述催化剂装入反应器中，在250℃下，用H2还原2小时后，通入H2/CO摩尔比为8:1的混合气体，在0.1MPa、450℃、体积空速为7500h-1下进行烯烃合成反应。在CO转化率为40％时，烯烃选择性为95％。
实施例5
取硫酸铁与硫酸钴，用去离子水配成0.3Mol/L溶液，取氯化锰与氯化铈，用去离子水配成0.4Mol/L溶液。取氢氧化钠，用去离子配成0.2Mol/L溶液。将硫酸铁、硫酸钴溶液、氯化锰及氯化铈溶液混合，在90℃及450rpm搅拌下，向其中缓慢滴加氢氧化钠溶液，维持温度不变与PH不变，滴加8小时。滴加结束后，将搅拌速度升至1200rpm，调节pH值为9-9.5并保持16小时。然后，将所得絮沉物抽滤。将滤饼在90℃烘干8小时，在400℃焙烧3小时。所得催化剂成分为：25％Fe-25％Co-20％Mn-10％Ce-20％Na2O。
将所述催化剂装入反应器中，在450℃下，用H2还原4小时后，通入H2/CO摩尔比为3:1的混合气体，在1MPa、380℃、体积空速为10000h-1下进行烯烃合成反应。在CO转化率为60％时，烯烃选择性为85％。
实施例6
取氯化铁，用去离子水配成0.2Mol/L溶液，取氯化锌，用去离子水配成0.4Mol/L溶液。取氢氧化钠与酸酸钾，用去离子配成0.5Mol/L溶液。将氯化铁、氧化锌溶液混合，在40℃及450rpm搅拌下，向其中缓慢滴加氢氧化钠和碳酸钾溶液，维持温度不变与PH不变，滴加5小时。滴加结束后，将搅拌速度升至900rpm，调节pH值为9.5-10.2并保持10小时。然后，将所得絮沉物抽滤。将滤饼在80℃烘干8小时，在280℃焙烧15小时。所得催化剂成分为：50％Fe-20％Zn-10％K2O-20％Na2O。
将所述催化剂装入反应器中，在280℃下，用H2还原3小时后，通入H2/CO摩尔比为2.5:1的混合气体，在3MPa、360℃、体积空速为10000h-1下进行烯烃合成反应。在CO转化率为80％时，烯烃选择性为85％。
Claims (8)
1.一种合成气直接制烯烃的催化剂，其特征在于，由第一金属组分、第二金属组分和碱性助剂组成，所述第一金属组分为铁、镍、钴中的一种或多种，若为多种，则为任意质量百分比混合，第一金属组分的含量占催化剂的质量百分比为10％-50％；所述第二金属组分为锌、铬、锰、铜、银、镓、镧、铈中的一种或多种，若为多种，则为任意质量百分比混合，第二金属组分的含量占催化剂的质量百分比为10％-50％；所述碱性助剂为钠型、钾型、钙型氧化物中的一种或多种，若为多种，则为任意质量百分比混合，碱性助剂的含量占催化剂的质量百分比为20％-40％，所述合成气直接制烯烃的催化剂的制备方法包括如下步骤：
(1)、取第一金属组分前驱体，用去离子水配成0.01-0.1Mol/L溶液，取第二金属组分前驱体，用去离子水配成0.01-1Mol/L的溶液，取碱性助剂前驱体，用去离子水配成0.01-1Mol/L溶液；
(2)、将两种金属的盐溶液混合，在40-90℃及300-600rpm搅拌下，向金属盐溶液中滴加碱性助剂的溶液，维持温度不变与pH不变，滴加1-10小时，滴加结束后，将搅拌速度升至700-1200rpm，调节pH值为8-11并保持3-16小时，然后，将所得絮沉物抽滤；
(3)、将抽滤所得滤饼在60-100℃的条件下烘干3-24小时，在200-400℃下焙烧3-24小时。
2.根据权利要求1所述合成气直接制烯烃的催化剂，其特征在于，所述第一金属组分前驱体为该金属的一种可溶性盐或多种可溶性盐的混合物，所述第二金属组分前驱体为该金属的一种可溶性盐或多种可溶性盐的混合物。
3.根据权利要求2所述合成气直接制烯烃的催化剂，其特征在于，所述可溶性盐为硝酸盐、硫酸盐或氯化物。
4.根据权利要求1所述合成气直接制烯烃的催化剂，其特征在于，所述碱性助剂前驱体为该助剂的一种可溶性化合物。
5.根据权利要求4所述合成气直接制烯烃的催化剂，其特征在于，所述可溶性化合物为碳酸盐、碳酸氢盐、碱式碳酸盐或氢氧化物。
6.权利要求1所述催化剂的使用方法，其特征在于：将所述催化剂装入反应器中，在250-450℃下，用H2或H2/CO合成气还原1-4小时后，通入H2/CO摩尔比为1:1-8:1的混合气体，在0.1-5MPa、250-450℃、体积空速为500-10000h-1下进行烯烃合成反应。
7.根据权利要求6所述催化剂的使用方法，其特征在于，所述H2/CO合成气中，H2与CO的摩尔比为2:1。
8.根据权利要求6所述催化剂的使用方法，其特征在于，在CO转化率为40-90％时，烯烃选择性为50-95％。
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