CN113457690A - 用于甲醇氧化制甲醛的催化剂及其制备方法和应用 - Google Patents
用于甲醇氧化制甲醛的催化剂及其制备方法和应用 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 230000003647 oxidation Effects 0.000 title claims description 8
- 238000007254 oxidation reaction Methods 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- HZNPCLUBXJLRAA-UHFFFAOYSA-N iron;oxomolybdenum Chemical compound [Fe].[Mo]=O HZNPCLUBXJLRAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 81
- 238000003756 stirring Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001844 chromium Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 229910015667 MoO4 Inorganic materials 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910052804 chromium 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
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims 2
- 239000011609 ammonium molybdate Substances 0.000 claims 2
- 229940010552 ammonium molybdate Drugs 0.000 claims 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000423 chromium oxide Inorganic materials 0.000 abstract 1
- 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 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 6
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 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
- 239000011148 porous material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 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 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- YKWDCIUWHLJNCF-UHFFFAOYSA-N oxo(oxomethylidene)iron Chemical compound O=C=[Fe]=O YKWDCIUWHLJNCF-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002023 wood 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8878—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明目的是提供一种工业生产用甲醇氧化制甲醛的催化剂,在铁钼氧化物体系中引入铬和钒的氧化物,形成四组分的催化剂,通过共沉淀方法制备前驱体,再将前驱体碾碎并在其中加入成型剂,通过压片或挤条的方法进行成型,成品催化剂外形为圆柱环形或齿轮环柱形颗粒,最后将成型后的颗粒在350℃~500℃温度下焙烧,即得催化剂成品。本发明提供的工业生产用甲醇氧化制甲醛的催化剂,该催化剂装填在固定床管式反应器中,具有床层阻力低、甲醇转化率高和甲醛收率高的特点,甲醇转化率达99%以上,甲醛收率达93%以上,并且催化剂的热稳定性好、使用寿命长。
Description
技术领域
本发明属化工催化剂领域,具体涉及一种用于甲醇氧化制甲醛的催化剂及其制备方法和应用。
背景技术
甲醛是一种重要的有机化工原料,广泛用于化工、医药、纺织、木材加工以及石油化工,具体可用于脲醛胶、酚醛胶、三聚氰胺甲醛胶、二苯基甲烷二异氰酸酯、季戊四醇和聚甲醛的生产,工业上主要通过甲醇氧化法生产。以甲醇和空气为原料生产甲醛的工艺按催化剂的不同分为银法和铁钼法。其中铁钼法具有反应温度低、催化剂活性和选择性高、寿命长、对毒物不敏感、单耗低、产品浓度高等特点,在现代甲醛生产中被广泛应用。
USP3,408,309首先公开了两组份的铁钼氧化物催化剂,但其机械强度、活性及寿命均不理想,后来在其中引入金属氧化物助剂进行了改善。
USP3,846,341提供了一种催化剂,采用凝胶法,在其中引入钨和钴的氧化物作为助剂,改善了催化剂的性能。USP3,978,136采用共沉淀法,在其中加入TiO2来改善催化剂性能。
USP4420421公开了一种钼铁催化剂的制备方法,其中活性金属钼源由氢氧化钠水溶液与含三氧化钼的废催化剂制备的钼酸钠提供,在催化剂制备过程中,由于引入的钠离子 很 难 完 全 除 去 ,进 而 在 催 化 剂 应 用 过 程 中 影 响 催 化 剂 的 活性 和 选 择 性 。
CN201110106337 .7公开了一种铁钼法甲醇氧化制甲醛催化剂的无污染制备方法,该方法是将多元醇、水和钼酸配制成混合溶液为底液,在搅拌条件下,向反应罐中通入羰基氧化铁饱和空气。
CN93117583 .6公开了一种用于甲醇氧化制甲醛的催化剂,该方法是将金属硝酸盐水溶液加入到已采用氢氧化铵调整pH值的七钼酸铵水溶液中进行沉淀反应,以上两种方法在反应过程中不能同时沉淀,易导致催化剂前驱物晶粒大小不均一、易导致催化剂孔径分布不集中,进而影响催化剂选择性。
CN1792443B提供了一种用于将甲醇氧化为甲醛的催化剂,其包括一种其中Mo/Fe原子比在1.5至5范围内的催化混合物Fe2(MoO4)3/MoO3,以及一种以铈的重量计其含量为0.1至10%的铈、钼和氧的化合物,虽然其甲醛收率可达到93%,但其操作温度较高,这样会影响催化剂的使用寿命。
发明内容
本发明目的是提供一种工业生产用甲醇氧化制甲醛的催化剂,该催化剂装填在固定床管式反应器中,具有床层阻力低、甲醇转化率高和甲醛收率高的特点,并且催化剂的热稳定性好、使用寿命长。
本发明的技术目的通过以下技术方案实现。
本发明用于甲醇氧化制甲醛的催化剂,其特征在于所述催化剂其主要成分为Fe2(MoO4)3、MoO3、Cr2(MoO4)3、V2O5及烯土金属氧化物;催化剂采用共沉淀方法制备:在铁钼氧化物体系中引入铬和钒的氧化物,形成四组分的催化剂。
本发明所述催化剂按照以下方法制备:将钼酸盐与偏钒酸盐加入去离子水中,配成溶液A,将铁盐、铬盐和助剂加入去离子水中配成溶液B,然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在30℃~80℃,用氨水调节混合液pH在1.0~3.0,经老化、洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入成型剂成型,最后将成型后的粒子在350℃~500℃温度下活化,即得催化剂成品。
优选地,所述催化剂的制备方法,将钼酸盐与偏钒酸盐加入去离子水中,配成溶液A,将铁盐、铬盐和助剂加入去离子水中配成溶液B,然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在30℃~80℃,用氨水调节混合液pH在1.0~3.0,然后老化0.5小时,再经过洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入成型剂,通过压片或挤条的方法进行成型。
所用偏钒酸盐为偏钒酸铵或偏钒酸钠,优选偏钒酸铵。
所用铁盐为硝酸铁、氯化铁或硫酸铁,优选硝酸铁。
所用铬盐为硝酸铬或三氧化二铬。
所用助剂为烯土金属,选自铈或镧中的一种或两种。
进一步地,本发明成品催化剂外形为圆柱环形或齿轮环形。
优选地,所述圆柱环形的规格为外径为Φ5 mm、内径为Φ2mm、长度为3~6mm;齿轮柱环形的规格为齿顶直径Φ6 mm、齿根直径Φ5 mm、内孔径Φ2 mm、长度3~6mm。
本发明提供的催化剂在使用前需在350℃~500℃温度下活化,最佳活化温度为380℃~450℃。
本发明提供的催化剂用于甲醇氧化制甲醛,在固定床管式反应器中,温度为240℃,甲醇/空气摩尔比为0.02,气体空速为10000~20000h-1时,甲醇转化率大于99%,甲醛收率大于93%。
本发明提供的工业生产用甲醇氧化制甲醛的催化剂,该催化剂装填在固定床管式反应器中,具有床层阻力低、甲醇转化率高和甲醛收率高的特点,甲醇转化率达99%以上,甲醛收率达93%以上,并且催化剂的热稳定性好、使用寿命长。
具体实施方式
本发明是按照以上步骤进行实施的,下面通过实施例进行详细说明。
列举这些实施例的目的只是为了解释本发明,而不是对本发明的限制。
实施例1
取270g七钼酸铵加入1000mL的去离子水中,配成溶液,然后再将24g的偏钒酸铵加入其中,在强力搅拌下配成溶液A;取200g九水硝酸铁加入500mL的去离子水中配成溶液,然后再将20g九水硝酸铬加入其中,在强力搅拌下配成溶液B;然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在50℃,用氨水调节混合液pH在2.0,然后老化0.5小时,再经过洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入6g硬脂酸混合均匀,通过压片方法进行成型,成品催化剂外形为圆柱环形,圆柱环形的规格为Φ5(外径)×2(内径)×5(长度),最后将成型后的颗粒在430℃温度下焙烧,即得催化剂成品F1。
实施例2
取270g七钼酸铵加入1000mL的去离子水中,配成溶液,然后再将24g的偏钒酸铵加入其中,在强力搅拌下配成溶液A;取200g九水硝酸铁加入500mL的去离子水中配成溶液,然后再将20g九水硝酸铬、5g硝酸铈加入其中,在强力搅拌下配成溶液B;然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在80℃,用氨水调节混合液pH在3.0,然后老化0.5小时,再经过洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入20g田菁粉混合均匀,通过压片方法进行成型,成品催化剂外形为圆柱环形,圆柱环形的规格为Φ5(外径)×2(内径)×5(长度),最后将成型后的颗粒在350℃温度下焙烧,即得催化剂成品F2。
实施例3
取400g七钼酸铵加入1000mL的去离子水中,配成溶液,然后再将30g的偏钒酸铵加入其中,在强力搅拌下配成溶液A;取220g九水硝酸铁加入500mL的去离子水中配成溶液,然后再将20g九水硝酸铬、5g硝酸铈加入其中,在强力搅拌下配成溶液B;然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在60℃,用氨水调节混合液pH在2.0,然后老化0.5小时,再经过洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入6g硬脂酸混合均匀,通过剂条的方法进行成型,成品催化剂外形为六齿轮环形,齿轮环形的规格为Φ6(齿顶直径)×4.5(齿根直径)×2(内孔径)×6(长度),最后将成型后的颗粒在450℃温度下焙烧,即得催化剂成品F3。
实施例4
取400g七钼酸铵加入1000mL的去离子水中,配成溶液,然后再将30g的偏钒酸铵加入其中,在强力搅拌下配成溶液A;取220g九水硝酸铁加入500mL的去离子水中配成溶液,然后再将20g九水硝酸铬、5g硝酸镧加入其中,在强力搅拌下配成溶液B;然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在60℃,用氨水调节混合液pH在2.0,然后老化0.5小时,再经过洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入20g甲基纤维素混合均匀,通过剂条的方法进行成型,成品催化剂外形为六齿轮环形,齿轮环形的规格为Φ6(齿顶直径)×4.5(齿根直径)×2(内孔径)×4(长度),最后将成型后的颗粒在500℃温度下焙烧,即得催化剂成品F4。
实施例5
取540g七钼酸铵加入1000mL的去离子水中,配成溶液,然后再将30g的偏钒酸铵加入其中,在强力搅拌下配成溶液A;取220g九水硝酸铁加入500mL的去离子水中配成溶液,然后再将20g九水硝酸铬、5g硝酸铈加入其中,在强力搅拌下配成溶液B;然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在60℃,用氨水调节混合液pH在1.0,然后老化0.5小时,再经过洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入6g硬脂酸混合均匀,通过剂条的方法进行成型,成品催化剂外形为六齿轮环形,齿轮环形的规格为Φ6(齿顶直径)×4.5(齿根直径)×2(内孔径)×3(长度),最后将成型后的颗粒在450℃温度下焙烧,即得催化剂成品F5。
实施例6
取540g七钼酸铵加入1000mL的去离子水中,配成溶液,然后再将30g的偏钒酸铵加入其中,在强力搅拌下配成溶液A;取220g九水硝酸铁加入500mL的去离子水中配成溶液,然后再将20g九水硝酸铬、5g硝酸铈加入其中,在强力搅拌下配成溶液B;然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在60℃,用氨水调节混合液pH在2.0,然后老化0.5小时,再经过洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入6g硬脂酸混合均匀,通过压片方法进行成型,成品催化剂外形为圆柱环形,圆柱环形的规格为Φ5(外径)×2(内径)×4(长度),最后将成型后的颗粒在350℃温度下焙烧,即得催化剂成品F6。
实施例7
取290g钼酸钠加入1000mL的去离子水中,配成溶液,然后再将24g的偏钒酸铵加入其中,在强力搅拌下配成溶液A;取250g硫酸铁加入500mL的去离子水中配成溶液,然后再将20g三氧化二铬加入其中,在强力搅拌下配成溶液B;然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在50℃,用氨水调节混合液pH在2.0,然后老化0.5小时,再经过洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入6g硬脂酸混合均匀,通过压片方法进行成型,成品催化剂外形为圆柱环形,圆柱环形的规格为Φ5(外径)×2(内径)×5(长度),最后将成型后的颗粒在430℃温度下焙烧,即得催化剂成品F7。
实施例8
取290g钼酸钠加入1000mL的去离子水中,配成溶液,然后再将24g的偏钒酸铵加入其中,在强力搅拌下配成溶液A;取230g氯化铁加入500mL的去离子水中配成溶液,然后再将20g三氧化二铬加入其中,在强力搅拌下配成溶液B;然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在50℃,用氨水调节混合液pH在2.0,然后老化0.5小时,再经过洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入6g硬脂酸混合均匀,通过压片方法进行成型,成品催化剂外形为圆柱环形,圆柱环形的规格为Φ5(外径)×2(内径)×5(长度),最后将成型后的颗粒在480℃温度下焙烧,即得催化剂成品F8。
比较例
按照CN1792443B提供的方法制备催化剂。取238g三氧化钼和400g二水钼酸钠溶解于去离子水中得溶液A,将352g六水氯化铁配成溶液加入上述溶液A中,在60℃下持续搅拌,待洗涤冷却后过滤得浆料B,再浆料B中加入计算量的钼酸铈悬浮液,搅拌均匀后,过滤、干燥得粉末,将得到的粉末制备成具有三叶状截面并且叶上具有通孔的圆柱状颗粒,在500℃下焙烧4小时得催化剂F9,该催化剂中以重量计含铈0.3%。
对比试验
将催化剂成品加入固定床管式反应器中,在一定温度下通入甲醇和空气,在催化剂床层甲醇被空气氧化成甲醛,反应条件及催化剂性能测试结果见下表。
样品名 | 甲醇/空气,mol | 空速,h-1 | 进口温度,℃ | 甲醇转化率,% | 甲醛收率,% |
F1 | 0.02 | 20000 | 240 | 97.6 | 91.3 |
F2 | 0.02 | 15000 | 240 | 98.8 | 93.1 |
F3 | 0.01 | 20000 | 240 | 99.2 | 92.7 |
F4 | 0.01 | 20000 | 240 | 99.3 | 93.4 |
F5 | 0.02 | 15000 | 240 | 98.5 | 92.8 |
F6 | 0.01 | 20000 | 240 | 99.4 | 93.3 |
F7 | 0.02 | 20000 | 240 | 97.3 | 90.6 |
F8 | 0.02 | 15000 | 240 | 97.5 | 90.2 |
F9 | 0.02 | 20000 | 240 | 98.1 | 90.9 |
Claims (10)
1.一种用于甲醇氧化制甲醛的催化剂,其特征在于所述催化剂其主要成分为Fe2(MoO4)3、MoO3、Cr2(MoO4)3、V2O5及烯土金属氧化物;催化剂采用共沉淀方法制备:在铁钼氧化物体系中引入铬和钒的氧化物,形成四组分的催化剂。
2.如权利要求1所述催化剂的制备方法,其特征在于催化剂按照以下方法制备:将钼酸盐与偏钒酸盐加入去离子水中,配成溶液A,将铁盐、铬盐和助剂加入去离子水中配成溶液B,然后将溶液B缓慢加入溶液A中,并不断搅拌,保持温度在30℃~80℃,用氨水调节混合液pH在1.0~3.0,经老化、洗涤、过滤、干燥得催化剂前驱体,再将前驱体碾碎并在其中加入成型剂成型,最后将成型后的粒子在350℃~500℃温度下活化,即得催化剂成品。
3.如权利要求1所述催化剂的制备方法,其特征在于所用钼酸盐为钼酸铵或钼酸钠,优选钼酸铵。
4.如权利要求1所述催化剂的制备方法,其特征在于所用偏钒酸盐为偏钒酸铵或偏钒酸钠,优选偏钒酸铵。
5.如权利要求1所述的催化剂制备方法,其特征在于所用铁盐为硝酸铁、氯化铁或硫酸铁,优选硝酸铁;所用铬盐为硝酸铬或三氧化二铬。
6.如权利要求1所述催化剂的制备方法,其特征在于所用助剂为烯土金属,选自铈或镧中的一种或两种。
7.如权利要求1所述催化剂,其特征在于成品催化剂外形为圆柱环形或齿轮环形。
8.如权利要求7所述催化剂,其特征在于圆柱环形的规格为外径为Φ5 mm、内径为Φ2mm、长度为3~6mm;齿轮柱环形的规格为齿顶直径Φ6 mm、齿根直径Φ5 mm、内孔径Φ2 mm、长度3~6mm。
9.如权利要求1所述催化剂,其特征在于催化剂在使用前需在350℃~500℃温度下活化,最佳活化温度为380℃~450℃。
10.如权利要求1所述催化剂的应用,其特征在于将制备的催化剂用于甲醇氧化制甲醛,在固定床管式反应器中,温度为240℃,甲醇/空气摩尔比为0.02,气体空速为10000~20000h-1时,甲醇转化率大于99%,甲醛收率大于93%。
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