CN111822003A - Iron-based catalyst and preparation method and application thereof - Google Patents
Iron-based catalyst and preparation method and application thereof Download PDFInfo
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- CN111822003A CN111822003A CN201910314492.4A CN201910314492A CN111822003A CN 111822003 A CN111822003 A CN 111822003A CN 201910314492 A CN201910314492 A CN 201910314492A CN 111822003 A CN111822003 A CN 111822003A
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- based catalyst
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 239000003054 catalyst Substances 0.000 title claims abstract description 167
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 48
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 62
- 239000011701 zinc Substances 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000002243 precursor Substances 0.000 claims description 43
- 239000011572 manganese Substances 0.000 claims description 41
- 239000002244 precipitate Substances 0.000 claims description 39
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 35
- 229910052748 manganese Inorganic materials 0.000 claims description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 34
- 229910052725 zinc Inorganic materials 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 33
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 22
- 238000010335 hydrothermal treatment Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 235000006408 oxalic acid Nutrition 0.000 claims description 19
- 229910052700 potassium Inorganic materials 0.000 claims description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 15
- 238000001556 precipitation Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 229910001868 water Inorganic materials 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 14
- 239000011591 potassium Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 13
- 239000012266 salt solution Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 6
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- 239000011686 zinc sulphate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000001914 filtration Methods 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
- 239000011777 magnesium Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 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
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 methane hydrocarbon Chemical class 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of Fischer-Tropsch synthesis and discloses an iron-based catalyst, a preparation method and application thereof, wherein the catalyst contains Fe element, Mn element, Zn element, S element and auxiliary agent, and the auxiliary agent is selected from at least one of alkali metal and alkaline earth metal; wherein, based on the total amount of the iron-based catalyst, the content of the S element is 0.02-0.5 wt%, and the content of the auxiliary agent is 0.1-10 wt% calculated by the element; fe: mn: the molar ratio of Zn is 1: (0.1-4): (0.01-1). Compared with the conventional precipitation method, the iron-based catalyst prepared by the method has the advantages of high BET specific surface area and large pore volume, and has the advantages of high reaction activity, low-carbon alkane selectivity and high low-carbon olefin selectivity when the iron-based catalyst is used in high-temperature Fischer-Tropsch synthesis reaction.
Description
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis, in particular to an iron-based catalyst, and a preparation method and application thereof.
Background
Coal indirect liquefaction is to obtain synthesis gas (CO + H) by converting coal through gasification process2) The synthesis gas is converted into hydrocarbons and oxygenates by the catalyst. The coal indirect liquefaction is generally divided into two process routes of low-temperature Fischer-Tropsch synthesis and high-temperature Fischer-Tropsch synthesis, wherein the former industrially mainly uses cobalt catalysts and iron catalysts, the reaction temperature is 200 ℃ and 280 ℃, and the main process is to produce hydrocarbons such as gasoline, diesel oil, paraffin and the like; the latter uses iron catalyst, the reaction temperature is 300-350 ℃, and the product can produce a large amount of oxygen-containing organic substances and olefin and other chemical products besides the oil product.
With the rapid fall-back of petroleum prices in recent years, the coal-to-liquid industry is seriously impacted, and the improvement of the added value of products becomes the way of the development of the coal-to-liquid technology under the current situation, so that the high-temperature Fischer-Tropsch synthesis technology for producing more chemical products as by-products has the characteristics of high added value of the products, consideration of oil products, chemical industry and the like, and shows certain advantages under the current market environment.
Iron-based fischer-tropsch catalysts have been commercialized in 50 s by Sasol corporation of south africa mainly for the production of fuels and waxes, etc. There have been many studies on low temperature synthesis of fischer-tropsch catalysts, but few studies on high temperature fischer-tropsch catalysts. At present, the industrial application adopts a molten iron catalyst, raw material iron is added into K2And smelting the O and the auxiliary agent in an electric arc furnace to obtain the alloy. However, the molten iron catalyst has the defects of lower specific surface area, uneven auxiliary agent content, more impurity content and the like. In addition Yan mine also developed a precipitated iron based high temperature Fischer-Tropsch catalyst, and the results of pilot tests were less than 10% methane selectivity and about 25% C2-C4 olefin selectivity.
CN1695803A disclosesThe preparation method comprises dissolving ferric nitrate, adding ammonia water solution to form precipitate slurry, filtering, washing to obtain coprecipitation filter cake, adding water, pulping, adding Na-containing solution+、K+、Cr3+、Cu2+The solution is directly added into the slurry, the slurry is obtained after a certain time of dipping, and then the high-temperature Fischer-Tropsch synthesis catalyst is obtained through drying and roasting. The catalyst contains Fe 50-70 wt%, Cu 0.01-10 wt%, Cr 0.01-10 wt%, and K20.01-8 wt% of O and Na2The weight percentage of O is 0.01-8.
CN1817451A discloses a microspheric iron-based catalyst for Fischer-Tropsch synthesis at high temperature and a preparation method thereof, wherein the catalyst comprises the following components in percentage by weight: cu: cr: k2O：Na2O100: 0.01-10: 0.03-10: 0.01-6: 0.01-5. The preparation method comprises the steps of dissolving iron powder in nitric acid to obtain an iron nitrate solution, diluting, adding an ammonium bicarbonate solution, precipitating to obtain a slurry, filtering and washing to obtain a filter cake, adding a certain amount of water and an auxiliary agent for pulping, soaking for a certain time to obtain a slurry, and performing centrifugal spray drying and roasting to obtain the microspheric Fischer-Tropsch synthesis catalyst.
CN101024192A discloses a preparation method of a catalyst for preparing low-carbon olefins from synthesis gas, which comprises the following steps: (1) mixing Fe (NO)3)3·9H2O and Mn (NO)3)2Preparing a uniform mixed solution of 0.2-1.0 mol/L; (2) by NH4OH is a precipitator and is (Fe + Mn)/NH according to the molar weight of the substance4Measuring OH as 1: 2-3, and weighing NH4OH and preparing NH with the same volume as (1)4The OH solution and the Fe/Mn mixed solution prepared in the step (1) are dripped into a container in a parallel flow mode, the mixture is continuously stirred for 4-8 hours after precipitation is finished, and the mixture is stood for 8-12 hours at normal temperature and normal pressure; (3) filtering and washing the precipitate obtained in the step (2), and then drying at 30-80 ℃ to obtain a dried precipitate A; (4) roasting the obtained substance A at the roasting temperature of 400-550 ℃ for 60-120 min, and recording the obtained product as B; (5) weighing K according to the composition of the catalyst2CO3Mixing ofPreparing a solution having the same volume as the obtained product B, and immersing the obtained product B in K2CO3Stirring and standing the solution for 4 to 8 hours, drying the solution at the temperature of 80 to 120 ℃, tabletting and molding the obtained dried substance, and crushing the dried substance to 40 to 60 meshes to obtain the catalyst.
It can be seen that the prior art adopts alkaline precipitant (such as ammonia water, sodium carbonate and ammonium hydroxide) to precipitate the iron-based catalyst for Fischer-Tropsch synthesis at high temperature, and then the iron-based catalyst is filtered, washed and re-pulped, and then the auxiliary agent salt solution is added into the slurry, and after the slurry is soaked for a period of time, the catalyst is prepared by drying and roasting.
In view of this, it is necessary to provide an iron-based catalyst suitable for high temperature fischer-tropsch synthesis and a preparation method thereof, so that the catalyst has the advantages of high CO activity, low methane hydrocarbon selectivity, high low carbon olefin selectivity, high strength and the like when being used for high temperature fischer-tropsch synthesis.
Disclosure of Invention
The invention aims to overcome the defect that the prior art adopts an iron-based catalyst prepared by alkaline precipitator (such as ammonia water, sodium carbonate and ammonium hydroxide), C2-C4Low selectivity to olefin, CH4The iron-based catalyst has the advantages of high reaction activity, low selectivity of low-carbon alkane and high selectivity of low-carbon olefin when being used for high-temperature Fischer-Tropsch synthesis reaction.
In the method for producing the iron-based catalyst of the present invention, the catalyst C2-C4The dicarboxylic acid can form a coordination precursor solution with a solution containing a ferrous salt, a manganese source, a zinc source and optionally an auxiliary precursor, wherein at least one of the ferrous salt, the manganese source, the zinc source and the auxiliary precursor is a sulfate; thereby simplifying the flow, shortening the time, simultaneously obtaining the iron-based catalyst with specific sulfur content through hydrothermal treatment, and when the iron-based catalyst is used for high-temperature Fischer-Tropsch synthesis reaction, the iron-based catalyst has high reaction activity, low selectivity of low-carbon alkane and low-carbon olefinHigh selectivity.
In order to achieve the above object, a first aspect of the present invention provides an iron-based catalyst containing an Fe element, an Mn element, a Zn element, an S element, and an auxiliary agent selected from at least one of alkali metals and alkaline earth metals;
wherein, based on the total amount of the iron-based catalyst, the content of the S element is 0.02-0.5 wt%, and the content of the auxiliary agent is 0.1-10 wt% calculated by the element;
fe: mn: the molar ratio of Zn is 1: (0.1-4): (0.01-1).
In a second aspect, the present invention provides a method of preparing an iron-based catalyst, the method comprising:
1) mixing a solution containing a ferrous salt, a manganese source and a zinc source, and optionally a promoter precursor, with C2-C4Mixing the dicarboxylic acids to obtain a mixed material;
2) carrying out hydrothermal treatment on the mixed material to obtain a precipitate;
3) sequentially carrying out first drying and first roasting on the precipitate to obtain a composite oxide;
optionally, the method further comprises: dipping the composite oxide by adopting an auxiliary agent precursor solution, and then sequentially carrying out second drying and second roasting;
wherein at least one of the ferrous salt, the manganese source, the zinc source and the auxiliary agent precursor is sulfate;
the auxiliary agent is selected from at least one of alkali metal and alkaline earth metal;
the dosage of the auxiliary agent precursor is 0.1-10 wt% of the prepared catalyst calculated by elements.
In a third aspect, the invention provides an iron-based catalyst prepared by the method of the second aspect of the invention.
In a fourth aspect, the invention provides the use of an iron-based catalyst according to the invention in fischer-tropsch synthesis.
In the preparation method of the iron-based catalyst of the invention, C2-C4Can be reacted with a compound containingAnd (2) forming a coordination precursor solution by using a solution of a ferrous salt, a manganese source, a zinc source and optionally an auxiliary agent precursor, wherein at least one of the ferrous salt, the manganese source, the zinc source and the auxiliary agent precursor is sulfate, and obtaining the iron-based catalyst with a specific composition by hydrothermal treatment. Through the technical scheme, the iron-based catalyst is particularly suitable for Fischer-Tropsch synthesis reaction, and particularly has the advantages of high catalytic activity, high selectivity of low-carbon olefin and low selectivity of methane when being used for high-temperature Fischer-Tropsch synthesis reaction of a fixed bed. In addition, the preparation method of the iron-based catalyst provided by the invention has simple process and shortens the time required by preparation.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
As described above, the first aspect of the present invention provides an iron-based catalyst containing an Fe element, an Mn element, a Zn element, an S element, and an auxiliary agent selected from at least one of an alkali metal and an alkaline earth metal;
wherein, based on the total amount of the iron-based catalyst, the content of the S element is 0.02-0.5 wt%, and the content of the auxiliary agent is 0.1-10 wt% calculated by the element; fe: mn: the molar ratio of Zn is 1: (0.1-4): (0.01-1).
In order to further improve the selectivity of the low-carbon olefin and reduce the selectivity of the low-carbon alkane, the content of the S element is preferably 0.05 to 0.45 wt% and the content of the auxiliary agent is preferably 0.5 to 4 wt% calculated on the element basis, based on the total amount of the iron-based catalyst.
According to a preferred embodiment of the present invention, Fe: mn: the molar ratio of Zn is 1: (0.25-1.3): (0.09-0.15).
In the present invention, preferably, the auxiliary is at least one selected from Na, K, Ca and Mg, and more preferably, the auxiliary is Na and/or K. When Na and/or K are/is selected as the auxiliary agent, the catalytic performance of the iron-based catalyst can be better improved.
In the present invention, the form in which the auxiliary is present is not particularly limited, and may be present in an oxidized state, for example.
In the present invention, it is preferable that the iron-based catalyst has a BET specific surface area of 300-580m2(ii)/g, more preferably 400-2Per g, pore volume of 0.3-0.8m3A ratio of 0.5 to 0.8 m/g is more preferable3/g。
The BET specific surface area and pore volume of the iron-based catalyst of the invention may be measured according to conventional means in the art, such as nitrogen physisorption.
In a second aspect, the present invention provides a method of preparing an iron-based catalyst, the method comprising:
1) mixing a solution containing a ferrous salt, a manganese source and a zinc source, and optionally a promoter precursor, with C2-C4Mixing the dicarboxylic acids to obtain a mixed material;
2) carrying out hydrothermal treatment on the mixed material to obtain a precipitate;
3) sequentially carrying out first drying and first roasting on the precipitate to obtain a composite oxide; optionally, the method further comprises: dipping the composite oxide by adopting an auxiliary agent precursor solution, and then sequentially carrying out second drying and second roasting;
wherein at least one of the ferrous salt, the manganese source, the zinc source and the auxiliary agent precursor is sulfate;
the auxiliary agent is selected from at least one of alkali metal and alkaline earth metal;
the dosage of the auxiliary agent precursor is 0.1-10 wt% of the prepared catalyst calculated by elements.
According to the invention, the "optional" in step 1) and step 2) can be explained as follows: namely, the auxiliary agent can be introduced by the following three methods:
first, the auxiliaries, i.e. the solution containing the divalent iron, manganese and zinc salts and the auxiliary precursor and C, are introduced only in step 1)2-C4Mixing the dicarboxylic acids to obtain a precipitate; sequentially carrying out first drying and first roasting on the precipitate to obtain composite oxideSubstance (iron-based catalyst).
Secondly, the auxiliaries, i.e. the solution containing the ferrous salt, the manganese source and the zinc source and C, are introduced only in step 2)2-C4Mixing the dicarboxylic acids to obtain a precipitate; sequentially carrying out first drying and first roasting on the precipitate to obtain a composite oxide; and then, dipping the composite oxide by adopting an auxiliary agent precursor solution, and sequentially carrying out second drying and second roasting to obtain the iron-based catalyst.
Thirdly, the addition agent is introduced in the step 1) and the step 2), namely, the solution containing ferrous salt, manganese source, zinc source and addition agent precursor and C2-C4Mixing the dicarboxylic acids to obtain a precipitate; sequentially carrying out first drying and first roasting on the precipitate to obtain a composite oxide; and then, dipping the composite oxide by adopting an auxiliary agent precursor solution, and sequentially carrying out second drying and second roasting to obtain the iron-based catalyst.
According to the invention, no matter what way the auxiliary agent is introduced, the amount of the auxiliary agent precursor is required to be enough to enable the content of the auxiliary agent in the prepared catalyst to be 0.1-10 wt% calculated by elements.
In order to obtain an iron-based catalyst with higher catalytic performance, the promoter precursor is preferably used in an amount such that the content of the promoter in the obtained catalyst is 0.5 to 4 wt% on an elemental basis.
According to a preferred embodiment of the invention, the auxiliary is introduced in the second way described above. When the promoter is introduced by the second method, i.e. only in step 2), an iron-based catalyst with higher catalytic performance can be obtained better.
In order to further improve the selectivity of the low-carbon olefin and reduce the selectivity of the low-carbon alkane, preferably, the metal calculated by elements in the solution is mixed with C2-C4In a molar ratio of 1: (0.1-2), more preferably 1: (0.7-1.2). That is, when the solution in step 1) contains a divalent iron salt, a manganese source, a zinc source, and an auxiliary precursor, the total amount of the divalent iron salt, the manganese source, the zinc source, and the auxiliary precursor, and C are preferably calculated on the basis of the metal element2-C4In a molar ratio of 1: (0.1-2), more preferably 1: (0.7-1.2); when the solution in the step 1) contains ferrous salt, a manganese source and a zinc source, the molar ratio of the total amount of the ferrous salt, the manganese source and the zinc source to the dicarboxylic acid with the carbon number of 2-4 is preferably 1: (0.1-2), more preferably 1: (0.7-1.2).
Preferably, in the step 1), the molar ratio of the ferrous salt to the manganese source to the zinc source is 1: (0.1-4): (0.01-1), more preferably 1: (0.5-1.3): (0.09-0.15).
In the present invention, the concentration of the solution in step 1) is not particularly limited, and in the case where the contents of the above components are satisfied, it is preferable that the concentration of the solution in step 1) may be 0.01 to 0.1 g/ml.
According to the invention, in a particular embodiment, C2-C4The dicarboxylic acid(s) may be introduced in the form of a solution, for example in step 1), a solution containing the divalent iron, manganese and zinc salts and optionally the promoter precursor is mixed with a solution containing C2-C4The dicarboxylic acid solution of (2) is mixed. The invention is to the compound containing C2-C4The concentration of the dicarboxylic acid (C) solution is not particularly limited as long as the metal and dicarboxylic acid charging relationship of the present invention is satisfied, and for example, the solution contains C2-C4The concentration of the solution of the dicarboxylic acid(s) of (2) may be 0.01 to 0.1 g/ml.
According to the present invention, preferably, the step 2) further comprises washing the material obtained after the hydrothermal treatment to obtain the precipitate. The washing may be performed by a method conventional in the art, and for example, the material obtained after the hydrothermal treatment may be washed with a mixed solution of water and ethanol or ethanol.
According to the present invention, the ferrous salt, the manganese source, the zinc source and the promoter precursor are preferably used in such amounts that the content of the S element in the resulting iron-based catalyst is 0.02 to 0.5 wt%, more preferably 0.05 to 0.45 wt%, based on the total amount of the iron-based catalyst. By adopting the preferred embodiment, the sulfur content in the iron-based catalyst is controlled, so that the selectivity of the low-carbon olefin is further improved, and the selectivity of the low-carbon alkane is reduced. When the content of the sulfur element in the iron-based catalyst is too low, the low-carbon olefin selectivity of the iron-based catalyst is reduced, and the low-carbon alkane selectivity is increased, and when the content of the sulfur element is too high, the low-carbon olefin selectivity of the iron-based catalyst is reduced, the low-carbon alkane selectivity of the iron-based catalyst is increased, and even the iron-based catalyst is completely inactivated. At least one of the ferrous salt, the manganese source, the zinc source and the auxiliary agent precursor is sulfate, and the sulfur content in the prepared catalyst can be regulated and controlled by controlling the using amounts of the ferrous salt, the manganese source, the zinc source and the auxiliary agent precursor and washing, and the person skilled in the art can know how to control the sulfur content in the catalyst through the above description.
According to the present invention, in order to further increase the pore volume and specific surface area of the prepared catalyst, preferably, the hydrothermal treatment in step 2) is performed in the presence of a surfactant.
Preferably, the volume ratio of the surfactant to the mixed material is (0.1-9) based on the total amount of the solution used in the hydrothermal treatment process: 1, preferably (0.3-2): 1.
preferably, the surfactant is selected from C2-C6Monohydric alcohol of (A) and (C)2-C6At least one of the polyols of (A), C2-C6The monohydric alcohol of (b) may be, for example, ethanol, n-propanol, 2-propanol, n-butanol, etc.; said C is2-C6The polyol (b) may be ethylene glycol, glycerin, etc., and more preferably is ethanol or glycerin.
According to the present invention, preferably, the conditions of the hydrothermal treatment include: the temperature is 60-180 deg.C, preferably 80-120 deg.C, and the time is 1-24 hr, preferably 6-12 hr. According to the present invention, the hydrothermal treatment process is not particularly limited, and specifically, a solution containing a divalent iron salt, a manganese source, and a zinc source, and optionally a promoter precursor, and C2-C4The materials obtained after the dicarboxylic acid is mixed are subjected to hydrothermal treatment under the condition of hydrothermal treatment, and the precipitate is obtained after suction filtration and washing. Thus, the method can better obtain high low-carbon olefin selectivity and low carbonAn alkane-selective iron-based catalyst.
According to the present invention, in the case where at least one of the ferrous salt, the manganese source, the zinc source, and the auxiliary precursor is a sulfate, the species of the ferrous salt, the manganese source, and the zinc source are not particularly limited as long as the corresponding ferrous iron, manganese, and zinc can be provided, and preferably, the ferrous salt, the manganese source, and the zinc source are each independently selected from at least one of a sulfate, a nitrate, and a carbonate; further preferably, the ferrous salt, the manganese source and the zinc source are all sulfates. The above-mentioned substances are all conventional in the art and are commercially available.
In the present invention, the above-mentioned C is preferable2-C4The dicarboxylic acid of (a) is oxalic acid and/or tartaric acid. When oxalic acid and/or tartaric acid are selected, the iron-based catalyst with high catalytic performance can be better obtained. The oxalic acid and tartaric acid are all conventional choices in the art and are all commercially available.
In a particularly preferred embodiment of the present invention, when the ferrous salt, the manganese source and the zinc source are all sulfates, and the dicarboxylic acid is oxalic acid, not only can the introduction of impurities in the catalyst be avoided, but also the sulfate solutions of the ferrous salt, the manganese source and the zinc source can better form a coordination precursor solution with the dicarboxylic acid, so as to obtain an iron-based catalyst with more excellent catalytic performance.
In the invention, the solution of ferrous salt, manganese source and zinc source and optional auxiliary agent precursor and C2-C4The mixing method of the dicarboxylic acid (2) is not particularly limited.
According to a preferred embodiment of the present invention, the mixing process may be slowly adding the solution of the ferrous salt, the manganese source and the zinc source and optionally the promoter precursor to the solution containing C under the action of magnetic stirring2-C4The dicarboxylic acid (b) is stirred for 0.5-4h, and precipitation occurs.
According to the method of the present invention, preferably, the conditions of the first drying include: the temperature is 90-120 ℃, and the time is 4-24 h.
According to the method of the present invention, preferably, the conditions of the first firing include: the temperature is 300 ℃ and 500 ℃, and the time is 2-4 h.
According to the method of the present invention, preferably, the conditions of the second drying include: the temperature is 90-120 ℃, and the time is 4-24 h.
According to the method of the present invention, preferably, the conditions of the second firing include: the temperature is 300 ℃ and 500 ℃, and the time is 2-4 h.
The drying and calcining processes can be performed according to conventional procedures in the art and are not described herein.
In the invention, under the condition that the dosage of the auxiliary agent precursor is satisfied to enable the content of the auxiliary agent in the prepared catalyst to be 0.1-10 wt% in terms of elements, the concentration of the auxiliary agent precursor solution is not particularly limited, and a person skilled in the art can determine the concentration of the auxiliary agent precursor solution according to the water absorption rate of the composite oxide and the content of the auxiliary agent in the prepared catalyst, which is not repeated herein.
In the present invention, the kind of the precursor of the additive is not particularly limited as long as the corresponding additive element can be provided, and the precursor of the additive is a substance capable of obtaining an oxide of the corresponding additive element through subsequent processing. For example, at least one selected from nitrate, carbonate, acetate and sulfate of an auxiliary agent. Specifically, the auxiliary may contain at least one selected from Na, K, Ca, and Mg, more preferably Na and/or K. When Na and/or K are/is selected, the catalytic performance of the iron-based catalyst can be better improved.
In a third aspect, the invention provides an iron-based catalyst prepared by the method of the second aspect of the invention.
In the present invention, the BET specific surface area of the iron-based catalyst is 300-580m2(ii)/g, more preferably 400-2Per g, pore volume of 0.3-0.8m3A ratio of 0.5 to 0.8 m/g is more preferable3/g。
The iron-based catalyst provided by the invention has the advantages of high reaction activity, low selectivity of low-carbon alkane and high selectivity of low-carbon olefin when being used in high-temperature Fischer-Tropsch synthesis reaction. Therefore, the fourth aspect of the invention also provides the application of the iron-based catalyst in Fischer-Tropsch synthesis.
The iron-based catalyst has the advantages of high reaction activity, low selectivity of low-carbon alkane and high selectivity of low-carbon olefin when used in high-temperature Fischer-Tropsch synthesis reaction, and preferably, the temperature of the high-temperature Fischer-Tropsch synthesis reaction is 300-350 ℃.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, all materials used were commercially available unless otherwise specified;
the pore diameter and the BET specific surface area pore volume of the catalyst are measured by nitrogen physical adsorption;
the composition of the catalyst was determined by XRF.
Example 1
(1) 6.4g of FeSO are taken4·7H2O, 3.5g of MnSO4·H2O and 0.67g of ZnSO4·7H2Dissolving O in 200ml deionized water to prepare a mixed salt solution; 6.6g of H2C2O4·2H2Dissolving O in 200ml of deionized water to obtain oxalic acid solution; slowly adding the mixed salt solution into an oxalic acid solution under magnetic stirring to obtain a mixed material, continuously stirring for 0.5h, adding 200ml of ethanol into the mixed material after yellow precipitates appear, uniformly stirring, transferring into a reaction kettle, carrying out hydrothermal treatment for 12h at the temperature of 80 ℃, carrying out suction filtration at room temperature after the reaction is finished, and washing filter residues for 2 times by using a mixed solution of water and ethanol (the water and the ethanol are mixed according to a volume ratio of 1: 1) to obtain precipitates.
(2) Drying the precipitate at 80 deg.C for 12h, and calcining the dried sample at 400 deg.C for 1.5h to obtain composite oxide;
(3) 0.022g of K with the concentration of 0.011g/ml is used2CO32g of the composite oxide, then drying for 12 hours at the temperature of 110 ℃, and roasting a sample obtained after drying for 4 hours at the temperature of 300 ℃ to obtain the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.18 wt% and the content of the potassium was 1.5 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 0.9: 0.1;
the BET specific surface area of the catalyst is 470m2Per g, pore volume 0.62m3/g。
Example 2
(1) 6.7g of FeSO are taken4·7H2O, 2.1g of MnSO4·H2O and 0.86g of ZnSO4·7H2Dissolving O in 200ml deionized water to prepare a mixed salt solution; 6.1g of H2C2O4·2H2Dissolving O in 200ml of deionized water to obtain oxalic acid solution; slowly adding the mixed salt solution into an oxalic acid solution under magnetic stirring to obtain a mixed material, continuously stirring for 1h, adding 300ml of ethanol into the mixed material after yellow precipitates appear, uniformly stirring, transferring into a reaction kettle, carrying out hydrothermal treatment for 8h at the temperature of 110 ℃, carrying out suction filtration at room temperature after the reaction is finished, and washing filter residues for 2 times by using a mixed solution of water and ethanol (the volume ratio of the water to the ethanol is 1: 1) to obtain precipitates.
(2) Drying the precipitate at 110 deg.C for 12h, and calcining the dried sample at 350 deg.C for 2h to obtain composite oxide;
(3) 0.022g of K with the concentration of 0.011g/ml is used2CO3The solution (2 g) is impregnated with the above composite oxide, and then dried at a temperature of 110 ℃ for 12 hours, and the dried sample is calcined at 350 ℃ for 1 hour to obtain the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.42 wt% and the content of the potassium was 1.7 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 0.5: 0.125;
the BET specific surface area of the catalyst is 562m2Per g, pore volume 0.71m3/g。
Example 3
(1) 5.8g of FeSO are taken4·7H2O, 4.6g of MnSO4·H2O and 0.6g of ZnSO4·7H2Dissolving O in 100ml deionized water to prepare a mixed salt solution; 4.6g of H2C2O4·2H2Dissolving O in 100ml of deionized water to obtain oxalic acid solution; slowly adding the mixed salt solution into an oxalic acid solution under magnetic stirring to obtain a mixed material, continuously stirring for 2h, adding 300ml of ethanol into the mixed material after yellow precipitates appear, uniformly stirring, transferring into a reaction kettle, carrying out hydrothermal treatment for 11h at the temperature of 90 ℃, carrying out suction filtration at room temperature after the reaction is finished, and washing filter residues for 3 times by using a mixed solution of water and ethanol (the water and the ethanol are mixed according to a volume ratio of 1: 1) to obtain precipitates.
(2) Drying the precipitate at 90 deg.C for 11h, and roasting the dried sample at 350 deg.C for 2h to obtain composite oxide;
(3) using 0.026g NaNO with concentration of 0.011g/ml32g of the composite oxide, drying the composite oxide at the temperature of 120 ℃ for 12 hours, and roasting a sample obtained after drying at the temperature of 350 ℃ for 1 hour to obtain the iron-based catalyst.
By analyzing the obtained catalyst, in this example, the content of the S element is 0.05 wt% based on the total amount of the iron-based catalyst, and the content of the sodium is 1.5 wt% in terms of elements; fe: mn: the molar ratio of Zn is 1: 1.3: 0.1;
the BET specific surface area of the catalyst was 445m2Per g, pore volume 0.51m3/g。
Example 4
(1) 6.95g of FeSO were taken4·7H2O, 0.51g MnSO4·H2O and 5.2g of ZnSO4·7H2Dissolving O in 200ml deionized water to prepare a mixed salt solution; 7.1g of H2C2O4·2H2Dissolving O in 200ml of deionized water to obtain oxalic acid solution; slowly adding the mixed salt solution into oxalic acid solution under magnetic stirring to obtain a mixtureAnd (2) continuously stirring for 1h, adding 300ml of glycerol into the mixture after yellow precipitates appear, uniformly stirring, transferring into a reaction kettle, carrying out hydrothermal treatment for 7h at the temperature of 110 ℃, carrying out suction filtration, and washing filter residues for 2 times by using a mixed solution of water and ethanol (the water and the ethanol are mixed according to a volume ratio of 2: 1) to obtain precipitates.
(2) Drying the precipitate for 8h at the temperature of 110 ℃, and roasting a sample obtained after drying for 2h at the temperature of 350 ℃ to obtain a composite oxide;
(3) with 0.06g Mg (NO) at a concentration of 0.11g/ml3)22g of the composite oxide, drying the composite oxide at the temperature of 120 ℃ for 12 hours, and roasting a sample obtained after drying at the temperature of 350 ℃ for 1 hour to obtain the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.2 wt% and the content of the magnesium element was 0.9 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 0.13: 0.71;
the BET specific surface area of the catalyst is 460m2Per g, pore volume 0.61m3/g。
Example 5
The procedure is as in example 1, except that, in step (1), 11.7g of H are introduced2C2O4·2H2O is dissolved in 200ml of deionized water to obtain an oxalic acid solution. And preparing the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.1 wt% and the content of the potassium was 1.2 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 0.2: 0.05;
the BET specific surface area of the catalyst is 390m2Per g, pore volume 0.58m3/g。
Example 6
The procedure is as in example 1, except that, in step (1), 6.4g of FeSO are taken4·7H2O, 15.5g of MnSO4·H2O and 0.0.7gZnSO4·7H2O is dissolved in 200ml deionized water to prepare a mixed salt solution. And preparing the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.1 wt% and the content of the potassium was 3 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 4: 0.01;
the BET specific surface area of the catalyst was 412m2Per g, pore volume 0.58m3/g。
Example 7
According to the method of example 1, except that the residue obtained after completion of the hydrothermal reaction in step (1) by suction filtration was washed 5 times to obtain a precipitate. And preparing the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.02 wt% and the content of the potassium was 1.4 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 1: 0.1;
the BET specific surface area of the catalyst is 475m2Per g, pore volume 0.65m3/g。
Example 8
The procedure is as in example 1, except that, in step (1), 6.6g of H are introduced2C2O4·2H2Replacing O with tartaric acid in an equimolar amount. And preparing the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.08 wt% and the content of the potassium was 2 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 1: 0.1;
the BET specific surface area of the catalyst is 380m2Per g, pore volume 0.58m3/g。
Example 9
The procedure of example 1 was followed except that 200ml of ethanol was replaced with 200ml of water in the step (1), to obtain a precipitate. And preparing the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.12 wt% and the content of the potassium was 1.7 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 1: 0.1;
the BET specific surface area of the catalyst is 320m2Per g, pore volume 0.45m3/g。
Example 10
The procedure is as in example 1, except that the potassium adjuvant is introduced in step (1), in particular,
(1) 6.4g of FeSO are taken4·7H2O, 3.5g of MnSO4·H2O and 0.67g of ZnSO4·7H2O and 1.056g of K2SO4Dissolving in 200ml deionized water to prepare mixed salt solution; 6.6g of H2C2O4·2H2Dissolving O in 200ml of deionized water to obtain oxalic acid solution; slowly adding the mixed salt solution into an oxalic acid solution under magnetic stirring to obtain a mixed material, continuously stirring for 1h, adding 200ml of ethanol into the mixed material after yellow precipitates appear, uniformly stirring, transferring into a reaction kettle, carrying out hydrothermal treatment for 12h at the temperature of 80 ℃, carrying out suction filtration at room temperature after the reaction is finished, and washing filter residues for 2 times by using a mixed solution of water and ethanol (the water and the ethanol are mixed according to a volume ratio of 1: 1) to obtain precipitates.
(2) And drying the precipitate for 8h at the temperature of 120 ℃, and roasting a sample obtained after drying for 1.5h at the temperature of 400 ℃ to obtain the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.08 wt% and the content of the potassium was 0.2 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 0.25: 0.1;
the catalyst has a BET specific surface area of 368m2Per g, pore volume 0.61m3/g。
Comparative example 1
By adopting a conventional precipitation method, specifically, 8.1g of ferric nitrate and 3.3g of manganese nitrate are dissolved in 400ml of deionized water, the mixture is heated to 70 ℃ in a constant-temperature water bath and is uniformly stirred, then 5 wt% of ammonia water solution is added into the mixed solution to form precipitation slurry, the pH value is adjusted to 6, a precipitation filter cake is obtained after filtration and washing, the precipitation filter cake is moved into a beaker and is added with 400g of deionized water for pulping, then 1.1g of zinc nitrate and 0.25 g of potassium nitrate are dissolved in 50ml of deionized water to prepare a mixed solution, the mixed solution is added into the slurry, the heating is carried out to 60 ℃, the stirring is carried out continuously for 0.5h, then the impregnation slurry is dried at 110 ℃, and the impregnation slurry is heated to 450 ℃ for roasting for 3 h.
The obtained catalyst was analyzed, and in this example, the content of potassium was 1.2% by weight in terms of element; fe: mn: the molar ratio of Zn is 1: 1: 0.1;
the BET specific surface area of the catalyst is 220m2Per g, pore volume 0.41m3/g。
Comparative example 2
According to the method of example 1, except that, in the step (1), 7.7g of ferrous acetate, 1.9g of manganese acetate and 1.2g of zinc acetate were dissolved in 300ml of deionized water to prepare a mixed salt solution, and an iron-based catalyst was prepared.
The obtained catalyst was analyzed, and in this example, the content of potassium was 1.2% by weight in terms of element based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 1: 0.1;
the BET specific surface area of the catalyst is 480m2Per g, pore volume 0.57m3/g。
Comparative example 3
The procedure is as in example 1, except that 6.6g of H are added2C2O4·2H2O is replaced by ammonia water in an equimolar amount to the O. And preparing the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.03 wt% and the content of the potassium was 1.3 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 1.1: 0.1;
the BET specific surface area of the catalyst is 280m2Per g, pore volumeIs 0.32m3/g。
Comparative example 4
According to the method of example 1, except that in step 1), after yellow precipitate appears, the filtrate is directly filtered at room temperature without hydrothermal treatment, and the filter residue is filtered with a mixed solution of water and ethanol (water and ethanol in a volume ratio of 1:1 mixing) and washing for 2 times to obtain a precipitate. And preparing the iron-based catalyst.
By analyzing the obtained catalyst, in this example, the content of the S element is 0.04 wt% and the content of the potassium element is 0.9 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 0.4: 0.08;
the BET specific surface area of the catalyst is 320m2Per g, pore volume 0.45m3/g。
Comparative example 5
According to the method of example 1, except that the filter residue obtained by suction filtration after the hydrothermal reaction in step (1) is not washed, the filter residue obtained by suction filtration is directly used as a precipitate. And preparing the iron-based catalyst.
The obtained catalyst was analyzed, and in this example, the content of the S element was 0.7 wt% and the content of the potassium was 1.4 wt% in terms of elements, based on the total amount of the iron-based catalyst; fe: mn: the molar ratio of Zn is 1: 1: 0.1;
the BET specific surface area of the catalyst is 480m2Per g, pore volume 0.68m3/g。
Comparative example 6
The procedure is as in example 1, except that, in step (1), 6.95g of FeSO are introduced4·7H2Replacing O with ferric sulfate which is equivalent to the iron element.
In this comparative example, a clear solution was obtained instead of a precipitate, and the oxide catalyst could not be prepared by this method since ferric sulfate could not form a precursor precipitate with oxalic acid.
Test example
0.5g of the catalysts prepared in examples 1 to 10 and comparative examples 1 to 6 were placed in fixed bed reactors, respectively,at the airspeed of 6000ml/g/H, the reaction temperature of 330 ℃, the reaction pressure of 2MPa and H2The Fischer-Tropsch synthesis reaction was carried out under the condition of 2/CO, and the results of the reaction for 50h are shown in Table 1.
TABLE 1
As can be seen from Table 1, when the catalyst provided by the invention is used in the high-temperature Fischer-Tropsch reaction of a fixed bed, the C content in the Fischer-Tropsch reaction process can be remarkably increased2-C4Olefin selectivity, lowering CH4And C2-C4Alkane selectivity. Particularly, in the preparation process of the iron-based catalyst, by performing hydrothermal treatment on a mixed solution of a metal and oxalic acid in a solution containing a surfactant, a catalyst having a high BET specific surface area and a large pore volume can be obtained, and the C can be significantly increased when the catalyst is used in a Fischer-Tropsch reaction process2-C4Olefin selectivity, lowering CH4And C2-C4Alkane selectivity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. An iron-based catalyst, which contains Fe element, Mn element, Zn element, S element and an auxiliary agent, wherein the auxiliary agent is at least one of alkali metal and alkaline earth metal;
wherein, based on the total amount of the iron-based catalyst, the content of the S element is 0.02-0.5 wt%, and the content of the auxiliary agent is 0.1-10 wt% calculated by the element;
fe: mn: the molar ratio of Zn is 1: (0.1-4): (0.01-1).
2. The iron-based catalyst according to claim 1, wherein the content of the S element is 0.05-0.45 wt% and the content of the promoter is 0.5-4 wt% in terms of element, based on the total amount of the iron-based catalyst;
fe: mn: the molar ratio of Zn is 1: (0.5-1.3): (0.09-0.15).
3. The iron-based catalyst of claim 1 or 2, wherein the promoter is selected from at least one of Na, K, Ca and Mg.
4. The iron-based catalyst according to any one of claims 1-3, wherein the iron-based catalyst has a BET specific surface area of 300-580m2Per g, preferably 400-580m2Per g, pore volume of 0.3-0.8m3A/g, preferably of 0.5 to 0.8m3/g。
5. A method of preparing an iron-based catalyst, the method comprising:
1) mixing a solution containing a ferrous salt, a manganese source and a zinc source, and optionally a promoter precursor, with C2-C4Mixing the dicarboxylic acids to obtain a mixed material;
2) carrying out hydrothermal treatment on the mixed material to obtain a precipitate;
3) sequentially carrying out first drying and first roasting on the precipitate to obtain a composite oxide; optionally, the method further comprises: dipping the composite oxide by adopting an auxiliary agent precursor solution, and then sequentially carrying out second drying and second roasting;
wherein at least one of the ferrous salt, the manganese source, the zinc source and the auxiliary agent precursor is sulfate;
the auxiliary agent is selected from at least one of alkali metal and alkaline earth metal;
the dosage of the auxiliary agent precursor is 0.1-10 wt% of the prepared catalyst calculated by elements.
6. The method as claimed in claim 5, wherein, in the step 1), the amount of the auxiliary agent precursor is such that the content of the auxiliary agent in the prepared catalyst is 0.5-4 wt% calculated on element;
preferably, the metals in the solution are in elemental form with C2-C4In a molar ratio of 1: (0.1-2), preferably 1: (0.7-1.2);
preferably, in the step 1), the molar ratio of the ferrous salt to the manganese source to the zinc source is 1: (0.1-4): (0.01-1), preferably 1: (0.5-1.3): (0.09-0.15);
preferably, in step 1), the concentration of the solution is 0.01-0.1 g/ml.
7. The process according to claim 5 or 6, wherein the amount of the divalent iron salt, the manganese source, the zinc source and the promoter precursor is such that the S element is contained in the obtained iron-based catalyst in an amount of 0.02 to 0.5 wt%, preferably 0.05 to 0.45 wt%, based on the total amount of the iron-based catalyst.
8. The process according to any one of claims 5 to 7, wherein the hydrothermal treatment in step 2) is carried out in the presence of a surfactant;
preferably, the volume ratio of the surfactant to the mixed material is (0.1-9): 1, preferably (0.3-2): 1;
preferably, the surfactant is selected from C2-C6Monohydric alcohol of (A) and (C)2-C6At least one of the polyols of (a);
preferably, the conditions of the hydrothermal treatment include: the temperature is 60-180 deg.C, preferably 80-120 deg.C, and the time is 1-24 hr, preferably 6-12 hr.
9. The method according to any one of claims 5 to 8, wherein in step 1), the ferrous salt, the manganese source and the zinc source are each independently selected from at least one of a sulfate, a nitrate and a carbonate;
preferably, in the step 1), the ferrous salt, the manganese source and the zinc source are all sulfates;
preferably, in step 1), the dicarboxylic acid is selected from oxalic acid and/or tartaric acid, more preferably oxalic acid;
preferably, the auxiliary agent is selected from at least one of Na, K, Ca and Mg.
10. The method according to any one of claims 5-9,
the conditions of the first drying include: the temperature is 90-120 ℃, and the time is 4-24 h;
the conditions of the first firing include: the temperature is 300-500 ℃ and the time is 2-4 h;
the conditions of the second drying include: the temperature is 90-120 ℃, and the time is 4-24 h;
the conditions of the second roasting include: the temperature is 300 ℃ and 500 ℃, and the time is 2-4 h.
11. An iron-based catalyst prepared by the method of any one of claims 5 to 10;
preferably, the iron-based catalyst has a BET specific surface area of 300-580m2Per g, preferably 400-580m2Per g, pore volume of 0.3-0.8m3A/g, preferably of 0.5 to 0.8m3/g。
12. Use of an iron-based catalyst according to any one of claims 1 to 4 and 11 in fischer-tropsch synthesis.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275997A (en) * | 2011-07-14 | 2011-12-14 | 浙江大学 | Porous ferric oxide constructed by nanocrystalline and preparation method thereof |
| CN103418407A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst converting synthesis gas into low carbon alkene, preparation method and applications |
| CN104096564A (en) * | 2013-04-02 | 2014-10-15 | 北京化工大学 | Fischer-Tropsch synthesis iron-based catalyst, preparation method and application thereof |
| CN105195189A (en) * | 2015-10-29 | 2015-12-30 | 江南大学 | Catalyst facilitating direct preparation of light olefins from syngas as well as preparation and application of catalyst |
| WO2016011841A1 (en) * | 2014-07-22 | 2016-01-28 | 北京化工大学 | Unsupported catalyst and preparation method therefor and application thereof |
| CN105562026A (en) * | 2014-10-24 | 2016-05-11 | 中国石油化工股份有限公司 | Sulfur-containing Fe-based catalyst as well as preparation method and application thereof |
| CN105727961A (en) * | 2016-02-02 | 2016-07-06 | 中科合成油技术有限公司 | Fischer-Tropsch synthesis iron-based catalyst with special microtopography and preparation method |
| CN106311269A (en) * | 2015-07-03 | 2017-01-11 | 中国科学院大连化学物理研究所 | Iron-based catalyst prepared by sol-gel combustion method, and preparation method and applications of iron-based catalyst |
-
2019
- 2019-04-18 CN CN201910314492.4A patent/CN111822003B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275997A (en) * | 2011-07-14 | 2011-12-14 | 浙江大学 | Porous ferric oxide constructed by nanocrystalline and preparation method thereof |
| CN103418407A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst converting synthesis gas into low carbon alkene, preparation method and applications |
| CN104096564A (en) * | 2013-04-02 | 2014-10-15 | 北京化工大学 | Fischer-Tropsch synthesis iron-based catalyst, preparation method and application thereof |
| WO2016011841A1 (en) * | 2014-07-22 | 2016-01-28 | 北京化工大学 | Unsupported catalyst and preparation method therefor and application thereof |
| CN105562026A (en) * | 2014-10-24 | 2016-05-11 | 中国石油化工股份有限公司 | Sulfur-containing Fe-based catalyst as well as preparation method and application thereof |
| CN106311269A (en) * | 2015-07-03 | 2017-01-11 | 中国科学院大连化学物理研究所 | Iron-based catalyst prepared by sol-gel combustion method, and preparation method and applications of iron-based catalyst |
| CN105195189A (en) * | 2015-10-29 | 2015-12-30 | 江南大学 | Catalyst facilitating direct preparation of light olefins from syngas as well as preparation and application of catalyst |
| CN105727961A (en) * | 2016-02-02 | 2016-07-06 | 中科合成油技术有限公司 | Fischer-Tropsch synthesis iron-based catalyst with special microtopography and preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114308092A (en) * | 2021-12-23 | 2022-04-12 | 北京中海前沿材料技术有限公司 | Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
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