CN113893879B - Heteropoly acid catalyst and preparation method and application thereof - Google Patents
Heteropoly acid catalyst and preparation method and application thereof Download PDFInfo
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- CN113893879B CN113893879B CN202111300566.2A CN202111300566A CN113893879B CN 113893879 B CN113893879 B CN 113893879B CN 202111300566 A CN202111300566 A CN 202111300566A CN 113893879 B CN113893879 B CN 113893879B
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- acid
- heteropoly acid
- alcohol
- catalyst
- keggin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- -1 aromatic alcohols Chemical class 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 18
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 11
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 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 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 235000011837 pasties Nutrition 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007527 glass casting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011572 manganese Substances 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
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Provides a Keggin structure heteropoly acid or heteropoly acid salt catalyst applied to a process for preparing methacrylic acid by oxidizing methacrolein and a preparation method thereof. Wherein the catalyst is synthesized in an alcohol-water azeotrope, and Na in the catalyst 2 The O content is not higher than 10ppm. The catalyst is used for the oxidation reaction of the methacrolein, can obviously improve the catalytic performance, greatly improves the conversion activity of the methacrolein to more than 92%, and keeps the selectivity of the methacrylic acid to more than 90%.
Description
Technical Field
The invention belongs to the technical field of industrial catalysts; in particular to a heteropoly acid or heteropoly acid salt catalyst with a Keggin structure applied to a process for preparing methacrylic acid by oxidizing methacrolein and a preparation method thereof.
Background
Methyl methacrylate is an organic compound, also called MMA, which is an important chemical raw material and is a monomer for producing transparent plastic polymethyl methacrylate (organic glass, PMMA). Methyl methacrylate is used primarily for the production of organic glass casting, extruded sheets and molding compounds, followed by surface coatings. In recent years, the world information industry has been developing at a high speed, and computers and flat panel televisions have been increasingly adopting Liquid Crystal Displays (LCDs) instead of conventional Cathode Ray Tube (CRT) displays, so that the consumption of LCDs has been continuously increasing. In addition, the demands of PVC impact modifiers ACR and MBS, billboard articles, automobile parts, artificial marble and the like in the asia-pacific area are rapidly increased, so that the demands of MMA and PMMA are driven, and the MMA and PMMA become investment hotspots in the asia-pacific area in the future. All manufacturers in the world have very good market prospect of Asian MMA, and newly build and expand MMA projects in Asia in a dispute way.
The selective oxidation of Methacrolein (MAL) to methacrylic acid (MAA) is a key step in the clean MMA production process, and the heteropolyacid catalyst based on phosphomolybdic acid and phosphomolybdic vanadic acid is used as a process core technology.
Although the phosphomolybdic vanadate heteropolyacid catalyst is successfully developed in the last 80 th century in Japan, and the industrial production of MAA is realized, the problems of low selectivity, low utilization rate of active components and poor thermal stability still exist.
The oxidation of methacrolein to methacrylic acid catalysts is known in the art, e.g. US20150105583, US20140316160, CN101175569A, CN108290143a etc. disclose the oxidation of MAL to MAA using heteropolyacid/salt catalysts, which have the disadvantage of low yields and short lifetimes.
The preparation of heteropolyacid salt catalysts is reported in patent application CN102105223a, mainly reporting the influence of the addition sequence of phosphorus elements on MAA selectivity in the catalyst preparation process, resulting in MAL conversion of more than 70% and MAA selectivity of more than 80%. However, the specific surface area of the catalyst is small and the catalytic efficiency is not high.
Patent application CN1126718A reports the preparation of a heteropolyacid catalyst, wherein the activity of the catalyst is increased by introducing a solid super acid containing sulfate radical during the preparation process of the catalyst, so as to obtain a high-activity catalyst, and the catalyst can react at a lower reaction temperature, but the selectivity of the catalyst is still lower.
Therefore, a new preparation method of the heteropolyacid (salt) catalyst needs to be developed, the selectivity of the catalyst is further improved, the stability of the catalyst is improved, the service life is prolonged, and meanwhile, the preparation process of the catalyst is ensured to be excessively complicated as much as possible, so that the catalyst is suitable for large-scale industrial production.
Disclosure of Invention
To this end, the present invention provides a heteropolyacid (salt) type catalyst, which is directed to the deficiencies of the prior art. The catalyst is suitable for selective oxidation process, especially for preparing methacrylic acid by oxidizing methacrolein.
In order to achieve the above purpose, the invention provides a preparation method of a heteropoly acid or heteropoly acid salt catalyst with a Keggin structure, which comprises the following steps:
(1) Mixing and introducing corresponding compounds of elements forming the heteropoly acid or heteropoly acid salt catalyst with the Keggin structure into water, adding a certain amount of alcohol, and stirring and mixing uniformly to obtain a first mixture;
(2) Preparing an alcohol-treated acid;
(3) Adding the alcohol-treated acid obtained in the step (2) into the first mixture obtained in the step (1) to maintain the pH value at 0.1-3.0, and then stirring and aging for a period of time at 50-90 ℃;
(4) Adjusting the pH value to 4-7, condensing and refluxing for a period of time, and then spray drying to obtain a catalyst precursor;
(5) Pre-roasting the catalyst precursor obtained in the step (4) to obtain a pre-roasted product;
(6) Molding the pre-baked product obtained in the step (5) to obtain a molded product;
(7) And (3) activating the molded product obtained in the step (6) to obtain the heteropoly acid or heteropoly acid salt catalyst with the Keggin structure.
Wherein the heteropolyacid or heteropolyacid salt of Keggin structure has a composition represented by formula (i):
P a Mo b V c Cu d X e Y f Z g O h (i)
in the formula (i), P, mo, V, cu and O represent phosphorus, molybdenum, vanadium, copper and oxygen, respectively; x is at least one element selected from arsenic, antimony and tellurium; y is at least one element selected from silver, silicon, iron, zinc, chromium, magnesium, cobalt, manganese, barium and cerium; z is at least one element selected from hydrogen, potassium and cesium; a. b, c, d, e, f, g and h each represent an atomic ratio of each element, wherein if b=12, a=0.1 to 5, c=0.01 to 4, d=0.01 to 2.5, e is 0 to 3, f=0 to 3, g=0.01 to 3, and h is an atomic ratio of oxygen required to satisfy the atomic valence of each element.
Wherein in the step (1), the stirring time is 20-40min.
Wherein in the step (1) or (2), the alcohol is selected from one or more of monohydric alcohol, polyhydric alcohol, saturated alcohol, unsaturated alcohol and aromatic alcohol with C1-C9; preferably one or more selected from C3-C6 monohydric alcohol, polyhydric alcohol, saturated alcohol, unsaturated alcohol and aromatic alcohol, and most preferably one or more selected from isopropanol, tertiary butanol, isobutanol, ethylene glycol, propylene glycol, cyclohexanol, benzyl alcohol and the like.
Wherein, in the step (2), the preparing of the alcohol-treated acid comprises: mixing alcohol and acid, heating to 50-70deg.C, stirring for 0.5-2 hr, and cooling to room temperature, wherein the volume ratio of alcohol and acid is 0.5-1.5:1 (preferably 1:1).
Wherein in the step (2), the acid is at least one selected from sulfuric acid, acetic acid, oxalic acid, hydrochloric acid, hypochlorous acid, perchloric acid, tartaric acid, nitric acid, nitrous acid and hydrofluoric acid.
Wherein in the step (3), the stirring aging time is 1-10h.
In the step (4), the condensation reflux time is 3-9h.
Wherein in the step (5), the pre-roasting temperature is 250-300 ℃ and the pre-roasting time is 5-10h.
Wherein, in the step (6), the additive is added into the pre-roasting product and then the pre-roasting product is molded; wherein the additive comprises graphite and stearic acid.
Wherein in the step (7), the activation temperature is 350-450 ℃ and the activation time is 5-10h.
The invention also provides the heteropoly acid or heteropoly acid salt catalyst with the Keggin structure, which is prepared by the preparation method of the heteropoly acid or heteropoly acid salt catalyst with the Keggin structure.
Wherein the heat conductivity coefficient of the heteropoly acid or heteropoly acid salt catalyst with Keggin structure is 0.3-0.9W/(m DEG C) (preferably 0.4-0.6W/(m DEG C)), the grain size is 5-50 nm (preferably 10-25 nm), and the specific surface area is 10-200 m 2 Per gram (preferably 20-100 m) 2 Per g), pore volume of 0.1-1.0 mL/g (preferably 0.2-0.8 mL/g), na of the catalyst 2 The O content is not higher than 10ppm, preferably not higher than 5ppm.
The invention also provides application of the heteropoly acid or heteropoly acid salt catalyst with the Keggin structure in a selective oxidation process, preferably in a process for preparing methacrylic acid by oxidizing methacrolein.
The invention has the following beneficial technical effects:
compared with the prior art, the method for synthesizing the Keggin structure heteropolyacid or heteropolyacid salt catalyst in the alcohol-water azeotrope has the following characteristics:
(1) The temperature of the alcohol-water azeotrope can be adjusted according to the alcohol-water ratio and the type of alcohol, and the temperature of a Keggin structure heteropolyacid or heteropolyacid salt generating system can be controlled more precisely by the alcohol-water azeotrope, so that compared with a traditional water phase, the Keggin structure heteropolyacid or heteropolyacid salt obtained by adopting the alcohol-water azeotrope can be adjusted more precisely in terms of crystallinity, grain size and crystal form.
(2) In an alcohol-water azeotrope system, alcohol can play a role of a template agent, plays an important role in generating primary particles of heteropoly acid or heteropoly acid salt with a Keggin structure, and the obtained catalyst has larger performance than water phase difference, and can adjust the type of the alcohol according to the requirement, so that an ideal catalyst structure is obtained.
(3) In the alcohol-water azeotrope synthesis system, the alcohol can also play a role of a pore-forming agent, but the pore-forming agent is different from the traditional pore-forming agent, the pore-forming agent can be used for manufacturing structural pores in the initial stage of Keggin structural crystal generation, the size and the type of the obtained pore can be adjusted according to the proportion of the alcohol to the water and the type of the alcohol, and the performance of the generated catalyst is greatly improved.
(4) Compared with the traditional catalyst obtained by water phase synthesis, the physical property of the heteropoly acid (salt) catalyst obtained by synthesizing the heteropoly acid or heteropoly acid salt catalyst with the Keggin structure in an alcohol-water azeotrope is improved particularly obviously, the catalyst is used for the oxidation reaction of methacrolein, the catalytic performance is obviously improved, particularly the methacrolein conversion activity is greatly improved to more than 92%, and the methacrylic acid selectivity is kept to more than 90%.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Firstly, 410ml of isobutanol and 410ml of 85% nitric acid are mixed, heated to 50 ℃ under stirring, kept for 1h, and then cooled to room temperature;
secondly, 1000g of ammonium molybdate, 61g of ammonium metavanadate, 49g of copper nitrate, 29g of ferric nitrate, 100g of cesium nitrate and 65.4g of 85% phosphoric acid are added into 4000g of pure water, 4000mL of isobutanol is added, stirring is carried out for 30min, nitric acid after the alcohol treatment in the first step is added, heating is carried out to 84 ℃ and kept for 5h, cooling is carried out to room temperature to obtain a solution, 450mL of ammonia water with the concentration of 25% is added, stirring is carried out for 30min, heating is carried out to the reflux temperature and kept for 4h, and a pasty material is obtained. Spray drying the obtained slurry material, roasting at 250 ℃ for 10 hours to obtain catalyst precursor powder, adding a proper amount of graphite and stearic acid into the catalyst precursor powder, forming, and roasting at 410 ℃ for 8 hours to obtain a catalyst, wherein the composition is P 1.1 Mo 11 V 1.0 Cu 0.5 Cs 1.0 Fe 0.2 。
Example 2
Firstly, 410ml of benzyl alcohol and 410ml of 85% nitric acid are mixed, heated to 60 ℃ under stirring, kept for 1.5h, and then cooled to room temperature;
secondly, 1000g of ammonium molybdate, 60g of ammonium metavanadate, 26g of copper nitrate, 55g of ferric nitrate, 201g of cesium nitrate and 65.4g of 85% phosphoric acid are added into 4000g of pure water, 4000mL of benzyl alcohol is added, stirring is carried out for 30min, nitric acid after the alcohol treatment in the first step is added, heating is carried out to 96 ℃ and kept for 5h, cooling is carried out to room temperature to obtain a solution, 400mL of ammonia water with the concentration of 25% is added, stirring is carried out for 30min, heating is carried out to the reflux temperature and kept for 4h, and a pasty material is obtained. Spray drying the obtained slurry material, roasting at 250 deg.c for 10 hr to obtain active catalyst component powder, adding proper amount of graphite and stearic acid into the catalyst precursor powder, forming, and roasting at 415 deg.cBurning for 8h to obtain catalyst with composition P 1.1 Mo 11 V 1.0 Cu 0.27 Cs 2.0 Fe 0.4 。
Example 3
Firstly, mixing 403ml of cyclohexanol and 403ml of 85% nitric acid, heating to 55 ℃ under stirring, maintaining for 1.5h, and then cooling to room temperature;
in the second step, 955g of ammonium molybdate, 90.5g of ammonium metavanadate, 51g of copper nitrate, 63g of antimony nitrate, 57.7g of potassium hydroxide and 65.4g of 85% phosphoric acid are added into 4000g of pure water, then 4000mL of cyclohexanol is added, stirring is carried out for 30min, nitric acid after the first alcohol treatment is added, the temperature is raised to 92 ℃ and kept for 5h, cooling is carried out to room temperature to obtain a solution, then 410mL of ammonia water with the concentration of 25% is added, stirring is carried out for 30min, the temperature is raised to the reflux temperature and kept at reflux for 4h, and a pasty material is obtained. Spray drying the obtained slurry material, roasting at 250 ℃ for 10 hours to obtain catalyst active component powder, adding a proper amount of graphite and stearic acid into the catalyst precursor powder, forming, and roasting at 410 ℃ for 8 hours to obtain a catalyst with the composition of P 1.1 Mo 10.5 V 1.52 Cu 0.53 K 2.0 Sb 0.4 。
Example 4
Firstly, 403ml of isopropanol and 399ml of 85% nitric acid are mixed, heated to 50 ℃ under stirring, kept for 1h, and then cooled to room temperature;
secondly, 927g of ammonium molybdate, 108.5g of ammonium metavanadate, 51g of copper nitrate, 18g of manganese nitrate, 151g of cesium nitrate and 59.5g of 85% phosphoric acid are added into 4000g of pure water, then 4000mL of isopropanol is added, stirring is carried out for 30min, nitric acid after the first alcohol treatment is added, the temperature is raised to 88 ℃ and kept for 5h, cooling is carried out to room temperature to obtain a solution, then 424mL of ammonia water with the concentration of 25% is added, stirring is carried out for 30min, the temperature is raised to the reflux temperature and kept for 4h, and a pasty material is obtained. Spray drying the obtained slurry material, roasting at 250 ℃ for 10 hours to obtain catalyst active component powder, adding a proper amount of graphite and stearic acid into the catalyst precursor powder, forming, and roasting at 410 ℃ for 8 hours to obtain a catalyst with the composition of P 1.0 Mo 10.2 V 1.8 Cu 0.53 Mn 0.2 Cs 1.5 Sb 0 .3 。
Example 5
Firstly, 391ml of tertiary butanol and 399ml of 85% nitric acid are mixed, heated to 60 ℃ under stirring, kept for 1h, and then cooled to room temperature;
secondly, 955g of ammonium molybdate, 91g of ammonium metavanadate, 51g of copper nitrate, 63g of antimony nitrate, 57.7g of potassium hydroxide, 41.5g of 85% phosphoric acid and 29g of 80% arsenic acid are added into 5500g of pure water, 4000mL of isopropanol is then added, stirring is carried out for 30min, nitric acid after the first alcohol treatment is added, the temperature is raised to 90 ℃ and kept for 5h, cooling is carried out to room temperature to obtain a solution, 412mL of ammonia water with the concentration of 25% is then added, stirring is carried out for 30min, the temperature is raised to the reflux temperature and kept at reflux for 4h, and a pasty material is obtained. Spray drying the obtained slurry material, roasting at 250 ℃ for 10 hours to obtain catalyst active component powder, adding a proper amount of graphite and stearic acid into the catalyst precursor powder, forming, and roasting at 420 ℃ for 8 hours to obtain a catalyst, wherein the composition is P 0.7 As 0.3 Mo 10. 5 V 1.52 Cu 0.53 K 2.0 Sb 0.4 。
Comparative example 1
1000g of ammonium molybdate, 61g of ammonium metavanadate, 49g of copper nitrate, 29g of ferric nitrate, 100g of cesium nitrate and 65.4g of 85% phosphoric acid are added to 4000g of pure water, stirred for 30min, 410mL of 85% nitric acid is added, the temperature is raised to 84 ℃ and kept for 5h, the mixture is cooled to room temperature to obtain a solution, 450mL of 25% ammonia water is added, stirred for 30min, the mixture is heated to a reflux temperature and kept at reflux for 4h, and a pasty material is obtained. Spray drying the obtained slurry material, roasting at 250 ℃ for 10 hours to obtain catalyst precursor powder, adding a proper amount of graphite and stearic acid into the catalyst precursor powder, forming, and roasting at 410 ℃ for 8 hours to obtain a catalyst, wherein the composition is P 1.1 Mo 11 V 1.0 Cu 0.5 Cs 1.0 Fe 0.2 。
Comparative example 2
1000g of ammonium molybdate, 60g of ammonium metavanadate, 26g of copper nitrate, 55g of ferric nitrate, 201g of cesium nitrate and 65.4g of 8 are added to 4000g of pure water5% phosphoric acid, stirring for 30min, adding 410mL of 85% nitric acid, heating to 96 ℃ and keeping for 5h, cooling to room temperature to obtain a solution, then adding 400mL of 25% ammonia water, stirring for 30min, heating to reflux temperature and keeping reflux for 4h, and obtaining a pasty material. Spray drying the obtained slurry material, roasting at 250 ℃ for 10 hours to obtain catalyst active component powder, adding a proper amount of graphite and stearic acid into the catalyst precursor powder, forming, and roasting at 415 ℃ for 8 hours to obtain a catalyst with the composition of P 1.1 Mo 11 V 1.0 Cu 0.27 Cs 2.0 Fe 0.4 。
Catalytic reaction
The catalyst prepared above was used for the preparation of methacrylic acid by oxidation of methacrolein.
The reaction conditions are as follows: the fixed bed process evaluation shows that the diameter of the reactor is 2mm, the length of the reactor is 80mm, the catalyst loading is 15mL, and the volume percentage of the raw material gas is as follows: 1% of methacrolein, 3% of oxygen, 5% of water vapor, 20% of nitrogen, the reaction temperature is 300-330 ℃, and the airspeed is 1000h -1 。
The liquid fraction in the product was detected by using a FID detector gas chromatograph, the gas fraction was detected by using a TCD detector gas chromatograph, and the methacrolein conversion, methacrylic acid selectivity and methacrylic acid yield were calculated from the detection results, and the results are shown in table 1.
Table 1 results of catalyst performance tests for examples and comparative examples
Catalyst | MAL conversion/% | MAA selectivity/% | MAA yield/% |
Example 1 | 93.1 | 92.5 | 86.1 |
Example 2 | 92.0 | 91.1 | 83.8 |
Example 3 | 94.3 | 89.7 | 84.6 |
Example 4 | 91.4 | 93.4 | 85.4 |
Example 5 | 90.5 | 91.8 | 83.1 |
Comparative example 1 | 87.7 | 82.3 | 72.2 |
Comparative example 2 | 86.9 | 81.3 | 70.6 |
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (6)
1. A preparation method of a heteropolyacid or heteropolyacid salt catalyst with a Keggin structure comprises the following steps:
(1) Mixing and introducing corresponding compounds of elements forming the heteropoly acid or heteropoly acid salt catalyst with the Keggin structure into water, adding a certain amount of alcohol, and stirring and mixing uniformly to obtain a first mixture;
(2) Preparing an alcohol treated acid comprising: mixing alcohol and acid, heating to 50-70 ℃, stirring for 0.5-2h, and cooling to room temperature, wherein the volume ratio of the alcohol to the acid is 0.5-1.5:1;
(3) Adding the alcohol-treated acid obtained in the step (2) into the first mixture obtained in the step (1) to keep the pH value at 0.1-3.0, and then stirring and aging for 1-10h at 50-90 ℃;
(4) Regulating the pH value to 4-7, condensing and refluxing for 3-9h, and then spray drying to obtain a catalyst precursor;
(5) Pre-roasting the catalyst precursor obtained in the step (4) to obtain a pre-roasted product;
(6) Molding the pre-baked product obtained in the step (5) to obtain a molded product;
(7) And (3) activating the molded product obtained in the step (6) to obtain the heteropoly acid or heteropoly acid salt catalyst with the Keggin structure.
2. The method for producing a Keggin structured heteropoly acid or heteropoly acid salt catalyst according to claim 1, wherein the Keggin structured heteropoly acid or heteropoly acid salt has a composition represented by formula (i):
P a Mo b V c Cu d X e Y f Z g O h (i)
in the formula (i), P, mo, V, cu and O represent phosphorus, molybdenum, vanadium, copper and oxygen, respectively; x is at least one element selected from arsenic, antimony and tellurium; y is at least one element selected from silver, silicon, iron, zinc, chromium, magnesium, cobalt, manganese, barium and cerium; z is at least one element selected from hydrogen, potassium and cesium; a. b, c, d, e, f, g and h each represent an atomic ratio of each element, wherein if b=12, a=0.1 to 5, c=0.01 to 4, d=0.01 to 2.5, e is 0 to 3, f=0 to 3, g=0.01 to 3, and h is an atomic ratio of oxygen required to satisfy the atomic valence of each element.
3. The method for preparing a Keggin structured heteropolyacid or heteropolyacid salt catalyst according to claim 1, wherein in the step (1) or (2), the alcohol is one or more selected from monohydric alcohols, polyhydric alcohols, saturated alcohols, unsaturated alcohols and aromatic alcohols having 1 to 9 carbon atoms.
4. The method for preparing a Keggin structured heteropoly acid or heteropoly acid salt catalyst according to claim 1, wherein in the step (2), the acid is at least one selected from sulfuric acid, acetic acid, oxalic acid, hydrochloric acid, hypochlorous acid, perchloric acid, tartaric acid, nitric acid, nitrous acid, hydrofluoric acid.
5. The method for preparing a Keggin structured heteropoly acid or heteropoly acid salt catalyst according to claim 1, wherein in the step (6), the pre-baked product is molded after adding an additive; wherein the additive comprises graphite and stearic acid.
6. The method for preparing a Keggin structured heteropoly acid or heteropoly acid salt catalyst according to claim 1, wherein in the step (7), the activation temperature is 350-450 ℃ and the activation time is 5-10h.
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