CN106582871A - Catalyst for producing allyl acetate - Google Patents
Catalyst for producing allyl acetate Download PDFInfo
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- CN106582871A CN106582871A CN201510675445.4A CN201510675445A CN106582871A CN 106582871 A CN106582871 A CN 106582871A CN 201510675445 A CN201510675445 A CN 201510675445A CN 106582871 A CN106582871 A CN 106582871A
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- Prior art keywords
- catalyst
- carrier
- acetate
- reaction
- acetic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 285
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 120
- 238000006243 chemical reaction Methods 0.000 claims description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 86
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 71
- 239000007788 liquid Substances 0.000 claims description 65
- 238000002360 preparation method Methods 0.000 claims description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 50
- 239000001301 oxygen Substances 0.000 claims description 50
- 229910052760 oxygen Inorganic materials 0.000 claims description 50
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 43
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 43
- 239000002994 raw material Substances 0.000 claims description 37
- 238000005470 impregnation Methods 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical group [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 30
- 235000011056 potassium acetate Nutrition 0.000 claims description 22
- -1 alkali metal acetate Chemical class 0.000 claims description 19
- 229910052703 rhodium Inorganic materials 0.000 claims description 16
- 229910052718 tin Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052741 iridium Inorganic materials 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 229910052745 lead Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 42
- 238000012986 modification Methods 0.000 abstract description 21
- 230000004048 modification Effects 0.000 abstract description 21
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 239000004480 active ingredient Substances 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910021426 porous silicon Inorganic materials 0.000 abstract 1
- 206010013786 Dry skin Diseases 0.000 description 45
- 238000001035 drying Methods 0.000 description 45
- 239000010948 rhodium Substances 0.000 description 35
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 32
- 239000010949 copper Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000000376 reactant Substances 0.000 description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 16
- 229910020489 SiO3 Inorganic materials 0.000 description 16
- NDQKGYXNMLOECO-UHFFFAOYSA-N acetic acid;potassium Chemical compound [K].CC(O)=O NDQKGYXNMLOECO-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 16
- 229910052801 chlorine Inorganic materials 0.000 description 16
- 238000001816 cooling Methods 0.000 description 16
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 16
- 230000006837 decompression Effects 0.000 description 16
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical class O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 16
- 239000007791 liquid phase Substances 0.000 description 16
- 238000012856 packing Methods 0.000 description 16
- 239000002243 precursor Substances 0.000 description 16
- 230000004044 response Effects 0.000 description 16
- 238000000926 separation method Methods 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 230000002459 sustained effect Effects 0.000 description 16
- 238000010792 warming Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006137 acetoxylation reaction Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- XBBXDTCPEWHXKL-UHFFFAOYSA-N rhodium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Rh+3].[Rh+3] XBBXDTCPEWHXKL-UHFFFAOYSA-N 0.000 description 5
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- MOHVWRCMMMKFST-UHFFFAOYSA-N dioxosilane platinum Chemical compound [Si](=O)=O.[Pt] MOHVWRCMMMKFST-UHFFFAOYSA-N 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- SYBXSZMNKDOUCA-UHFFFAOYSA-J rhodium(2+);tetraacetate Chemical compound [Rh+2].[Rh+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O SYBXSZMNKDOUCA-UHFFFAOYSA-J 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- B01J35/19—
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/466—Osmium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a catalyst for producing allyl acetate. The catalyst is mainly used for solving the problem in the prior art that catalysts are not high in activity and selectivity. According to the catalyst, through adopting the technical scheme that the catalyst for producing the allyl acetate contains a carrier, an active ingredient and a cocatalyst, wherein the active ingredient comprises Pd and Cu, the cocatalyst is alkali metal acetate, the carrier comprises a carrier substrate and a surface coating, the substrate is porous silicon dioxide, the coating is prepared from modification metal elements and a silicon dioxide bonder which is used for bonding the modification metal elements to the surface of the substrate, the content of the modification metal elements is 0.10g/L to 1.00g/L, and the modification elements are at least one selected from platinum-family metal elements and IVA metal elements, the problem is better solved, so that the catalyst can be applied to the industrial production of the allyl acetate.
Description
Technical field
The present invention relates to the synthetic method of the preparation method of allyl acetate catalyst, catalyst and allyl acetate.
Background technology
Allyl acetate is a kind of colourless flammable liquid, is slightly soluble in water, is soluble in alcohol and ether, can be dissolved in acetone, it as a kind of important industrial chemicals, mainly for the production of propenyl and epoxychloropropane.
The eighties in 20th century, Japanese Showa electrician and academy of science of the former Soviet Union propose that, using acetoxylation technology, with propylene, oxygen and acetic acid as raw material, Fixed Bed Gas Phase reaction is prepared in the reaction of allyl acetate, with SiO in the presence of palladium and promoter2、Al2O3Or SiO2And Al2O3The mixture of composition is carrier, is loaded with Pd, Cu and potassium acetate, and catalyst of the Pd and Cu in eggshell type distribution has been well known to those of ordinary skill in the art.The preparation method of the catalyst is via US3, and 917,676 is (entitled：Process for producing ally acetate) it is disclosed, the mixed liquor that precious metals pd and Cu will be contained is immersed on carrier, after dried, the Pd and Cu of free state are solidificated in into carrier surface and the Pd and Cu of active metallic state is formed, then the catalyst is obtained Jing after promoter KOAc process is dried.The activity and selectivity of the catalyst that the method is obtained is relatively low.
Many scholars are studied the active component of the noble metal catalyst, promoter.Research thinks that the Main By product of the reaction is generated by propylene deep oxidation, and this was both relevant to the adsorpting type of reactant with catalyst, and related to the Active components distribution of catalyst.Zeng Xianjun etc. exists《Propylene aoxidizes the research of acetate propylene ester catalyst processed》Then think in one text, propylene is in Pd-K/SiO2On absorption and toluene in Pd-Sn-K/SiO2Oxidation on catalyst is similar, and Shu Qingyu etc. exists《Pd-Sn-K/SiO2Toluene gas phase Acetoxylation reaction on catalyst》Propose toluene gas phase Acetoxylation in one text to react in Pd-Sn-K/SiO2In activation process on catalyst, methyl c h bond is dissociated into ratedeterming step, and metallic state palladium becomes most important component in catalyst, the presence of KOAc improves the activation of c h bond.
Liang Zhong etc. exists《Adsorb the effect of oxygen and Lattice Oxygen in selective oxidation of n -butane》Think that Lattice Oxygen is conducive to the oxygen of selective oxidation, ADSORPTION STATE to be conducive to deep oxidation, therefore the concentration of catalytic surface Lattice Oxygen should be improved in the reaction of propylene Acetoxylation.Zhao Zhenxing etc. exists《Ethylene gas phase Acetoxylation reaction mechanism and dynamics research》In propose ethylene gas phase Acetoxylation reaction mechanism, they think the oxygen of absorption most advantageously molecular state of the oxygen on catalyst surface, and the oxygen of molecular state is to participate in acetylizad oxygen source, Pd-SiO2Catalyst activity component Pd, the acetic acid of physical absorption the acetic acid of chemisorbed is changed, so as to the oxygen with molecular state is combined generation allyl acetate.
In addition both at home and abroad many scholars think that allyl acetate selectivity of catalyst is relevant with the heat of adsorption of propylene, and for example Han Y F etc. exist《A kinetic study of acetate synthesis over Pd-based catalysts:kinetics of vinyl acetate synthesis over Pd-Au/SiO2catalysts》With during Li Ming etc.《Micro-matter tracer technical research Pd-Cu/SiO2Surface adsorption》In it is also proposed that, the oxidation activity that metallic copper, stannum etc. advantageously reduce Pd surface adsorbed oxygens is introduced, so as to improve the selectivity of oxidation.
The content of the invention
One of the technical problem to be solved is the not high problem of the allyl acetate catalyst activity and selectivity synthesized in prior art.There is provided a kind of allyl acetate production catalyst used, the characteristics of the catalyst has high-activity high-selectivity.
The two of the technical problem to be solved are the preparation methoies of one of technical problem catalyst.
The three of the technical problem to be solved are the methods for synthesizing allyl acetate using one of the technical problem catalyst.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：Allyl acetate production catalyst used, the catalyst includes carrier, active component and promoter；The active component includes metal Pd and Ni metal；The promoter is alkali metal acetate；The carrier includes carrier substrate and face coat；The base material is porous silica；The coating is constituted by modified metal element and by the silica binder that the modified metal element is bonded in the substrate surface；The modified metal constituent content is 0.1～1.00g/L；At least one of the modified metal element in platinum cluster metallic element and IVA metallic elements.
In above-mentioned technical proposal, the platinum cluster metallic element preferably is selected from least one in Ru, Rh, Os, Ir and Pt.
In above-mentioned technical proposal, the IVA metallic elements preferably are selected from least one in Ge, Sn and Pb.
In above-mentioned technical proposal, used as further preferred, the modified metal element includes Rh and Sn, or including Ir and Sn；More preferably described modified metal includes Rh, Ir and Sn, or bag Rh, Ir and Pb；Most preferably described modified metal includes Rh, Ir, Sn and Pb.With preferable synergism in terms of catalyst activity and selectivity between above-mentioned modified metal element.
In above-mentioned technical proposal, the alkali metal acetate is preferably potassium acetate.
In above-mentioned technical proposal, the content of Pd is preferably 1.0～10g/L in the catalyst.
In above-mentioned technical proposal, the content of Cu is preferably 0.1～5.0g/L in the catalyst.
In above-mentioned technical proposal, the content of potassium acetate is preferably 10～120g/L in the catalyst.
In above-mentioned technical proposal, the specific surface and pore volume of carrier substrate are not particularly limited, all can obtain can be good technique effect.But BET specific surfaces are 100～500m2/ g, pore volume is more excellent when being 0.85～1.40ml/g.
To solve the two of above-mentioned technical problem, technical scheme is as follows：Method for preparing catalyst described in the technical scheme of one of above-mentioned technical problem, comprises the steps：
(1) hydroxide or oxide of the modified metal element and Ludox are mixed to get into coating liquid；
(2) above-mentioned coating liquid is coated to into porous silica silicon face, dry, roasting obtains the catalyst carrier；
(3) the carrier impregnation compound containing Pd and impregnation liquid containing Cu compounds are obtained into catalyst precarsor I；
(4) make compound containing Pd and compound containing Cu be converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(5) compound state Pd and compound state Cu in the sedimentation type is reduced to into metal Pd and Ni metal obtains catalyst precarsor III；
(6) promoter solution is impregnated, is dried to obtain the catalyst.
In above-mentioned technical proposal, do not specially required based on the roasting of the understanding step (2) of those skilled in the art, sintering temperature is preferably 400～600 DEG C, and roasting time is preferably 1～5 hour.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of allyl acetate, with propylene, acetic acid, oxygen and water as raw material, reaction in the presence of catalyst any one of the technical scheme in one of above-mentioned technical problem obtains allyl acetate.
In above-mentioned technical proposal, the temperature of reaction be preferably 120～150 DEG C, the pressure of reaction be preferably 0.1～1.0MPa, propylene is preferably with molar ratio computing:Acetic acid:Oxygen:Water=1:(0.1～0.3):(0.1～0.3):(0.2～1), raw material volume air speed is preferably 1500～2500h-1。
Compared with prior art, key problem in technology of the invention be the carrier be that its surface of silicon dioxide platinum cluster metallic element and IVA metallic elements have carried out modification.Due to replacing conventional carriers using above-mentioned technical proposal, the activity and selectivity of allyl acetate catalyst is improve.For the method for preparing catalyst that the present invention is provided, its key problem in technology is to coat modified metal element in silica surface, and the method for coating has a lot, can spray, it is also possible to which, by colloid roller coating, this is well known for ordinary skill in the art.
The catalyst of said method synthesis and comparative catalyst are evaluated respectively and are calculated the activity and and selectivity of catalyst with laboratory microreactor.Evaluation methodology is the loading 30ml catalyst in microreactor, using nitrogen leak test, it is ensured that after system is without leak source, the flow of propylene is adjusted to into 0.82mol/h, the flow set of nitrogen is 0.86mol/h, heat up simultaneously, when reaction bed temperature reaches 120 DEG C, put into the acetic acid of 0.20mol/h and the water of 0.42mol/h, start to throw oxygen after 20 minutes, sufficient oxygen is thrown after 30 minutes, the amount of oxygen is 0.125mol/h, and air speed is 2000h-1, controlling reaction temperature is 142 DEG C in course of reaction, reaction pressure 0.68MPa.
The content of each component in gas chromatography analysis product, and calculate the activity and selectivity of catalyst by following equation：
Test result indicate that, the activity of the allyl acetate catalyst prepared by the present invention reaches 373.13g/Lh, and selectivity has reached 95.22%, achieves preferable technique effect.Especially catalyst carrier uses at least one modified metal element in platinum cluster metallic element and IVA metallic elements simultaneously when, more prominent technique effect is achieved.Below by embodiment, the present invention is further elaborated.
Specific embodiment
The ball SiO adopted in specific embodiment2BET specific surfaces be 198m2/ g, pore volume is 0.99ml/g.
【Embodiment 1】
The preparation of carrier：By the rhodium sesquioxide (Rh of 0.55g2O3) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.44g/L that Jing ICP determine Rh contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.13g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.22%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 2】
The preparation of carrier：By the stannous hydroxide (Sn (OH) of 0.57g2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.44g/L that Jing ICP determine Sn contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.28g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.95%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.The spherical SiO of a diameter of 5.6mm of 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 364.61g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.13%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Can be seen that by comparing with 2 with embodiment 1, the catalyst that the present invention is used, its carrier uses the catalyst of silica supported preparation, the activity of catalyst and the selectivity of allyl acetate to increase for the silicon dioxide ratio that surface scribbles modified metal element Rh or Sn.
【Comparative example 2】
For【Embodiment 1】Comparative example.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.The spherical SiO of a diameter of 5.6mm of 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates and 0.95g rhodium acetate (Rh will be contained2(OAc)4) pure water is dissolved in, obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L, Rh contents 0.44g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 364.54g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.09%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
By can be seen that compared with Example 1, the present invention impregnates catalyst made by metallic element compound containing Rh simultaneously using the catalyst that carrier is the silicon dioxide preparation that its surface scribbles modified metal element Rh than dipping potassium acetate, and the selectivity of the active and allyl acetate of catalyst increases.
【Comparative example 3】
For【Embodiment 1】Comparative example.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, containing 3.18gPd, the chlorine palladium acid containing 0.37gCu and containing 0.44gRh, copper chloride and rhodium acetate (Rh2(OAc)4) aqueous solution, obtain impregnation liquid 590ml.The spherical SiO of a diameter of 5.6mm of 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L, Rh contents 0.44g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 364.65g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.07%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
By can be seen that compared with Example 1, the present invention is increased using the catalyst that carrier is the silicon dioxide preparation that its surface scribbles modified metal element Rh than catalyst made by dipping metallic element compound containing Rh while dipping noble metal, the activity of catalyst and the selectivity of allyl acetate.From comparative example 2,3 and embodiment 1 as can be seen that only in SiO2Surface-coated contain improve metallic element Rh made by the activity and selectivity of catalyst just have good effect, the step of other or during add the activity and selectivity of modified metal element Rh catalyst and obtain good effect.
【Embodiment 3】
The preparation of carrier：By the ruthenic oxide (RuO of 0.58g2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.44g/L that Jing ICP determine Ru contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.19g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.25%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 4】
The preparation of carrier：(OsO is starved by the titanium dioxide of 0.52g2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.44g/L that Jing ICP determine Os contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.12g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.31%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 5】
The preparation of carrier：By the iridium dioxide (IrO of 0.52g2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.44g/L that Jing ICP determine Ir contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.18g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.33%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 6】
The preparation of carrier：By the platinum dioxide (PtO of 0.52g2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.44g/L that Jing ICP determine Pt contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.16g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.29%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 7】
The preparation of carrier：By the germanium dioxide (GeO of 0.15g2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.10g/L that Jing ICP determine Ge contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 372.81g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.80%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 8】
The preparation of carrier：Lead oxide (PbO) powder of 1.08g and 1.0g Ludox are sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 1.00g/L that Jing ICP determine Pb contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.39g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.97%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 9】
The preparation of carrier：By the rhodium sesquioxide (Rh of 0.30g and 0.26g2O3), stannous hydroxide (Sn (OH)2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.24g/L that Jing ICP determine Rh contents in the carrier, and Sn contents are 0.20g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.44g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.63%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 1 and embodiment 2 by embodiment 9, in terms of allyl acetate catalyst activity and selectivity is improved, the present invention is its surface at the use of carrier while catalyst prepared by the silicon dioxide for scribbling modified metal element Rh, Sn only scribbles modified metal element Rh or only scribbles catalyst made by modified metal element S n than carrier, and the selectivity of the active and allyl acetate of catalyst is high.This has absolutely proved that Rh, Sn have therebetween good synergy in terms of the activity and selectivity of catalyst is improved.
【Embodiment 10】
The preparation of carrier：By the iridium dioxide (IrO of 0.28g and 0.26g2), stannous hydroxide (Sn (OH)2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.24g/L that Jing ICP determine Ir contents in the carrier, and Sn contents are 0.20g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.50g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.51%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 11】
The preparation of carrier：By the rhodium sesquioxide (Rh of 0.15g, 0.14g and 0.26g2O3), iridium dioxide (IrO2) and stannous hydroxide (Sn (OH)2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.12g/L that Jing ICP determine Rh contents in the carrier, and Ir contents are 0.12g/L, and Sn contents are 0.20g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 376.83g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.84%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 9 and embodiment 10 by embodiment 11, in terms of allyl acetate catalyst activity and selectivity is improved, the present invention is its surface at the use of carrier metal element while the catalyst for scribbling the silicon dioxide preparation of modified metal element Rh, Ir, Sn only scribbles modified Rh, Sn or only scribbles catalyst made by modified metal element Ir, Sn than carrier, and the selectivity of the active and allyl acetate of catalyst is high.This has absolutely proved that Rh, Ir, Sn three has good synergy in terms of the activity and selectivity of catalyst is improved.
【Embodiment 12】
The preparation of carrier：By the rhodium sesquioxide (Rh of 0.15g, 0.14g and 0.22g2O3), iridium dioxide (IrO2) and powder and the 1.0g Ludox of lead oxide (PbO) be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.12g/L that Jing ICP determine Rh contents in the carrier, and Ir contents are 0.12g/L, and Pb contents are 0.20g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatogram-GC-MS (GC-MASS).
The activity for being computed the catalyst is 376.91g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.70%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 13】
The preparation of carrier：By the rhodium sesquioxide (Rh of 0.15g, 0.14g, 0.16g and 0.09g2O3), iridium dioxide (IrO2), stannous hydroxide (Sn (OH)2) and powder and the 1.0g Ludox of lead oxide (PbO) be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.12g/L that Jing ICP determine Rh contents in the carrier, and Ir contents are 0.12g/L, and Sn contents are 0.12g/L, and Pb contents are 0.08g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain impregnation liquid 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain impregnation liquid 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatogram-GC-MS (GC-MASS).
The activity for being computed the catalyst is 379.98g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 96.11%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 11 and embodiment 12 by embodiment 13, in terms of allyl acetate catalyst activity and selectivity is improved, the present invention is its surface at the use of carrier metal element while the catalyst for scribbling the silicon dioxide preparation of modified metal element Rh, Ir, Sn, Pb only scribbles modified Rh, Ir, Sn or only scribbles catalyst made by modified metal element Rh, Ir, Pb than carrier, and the selectivity of the active and allyl acetate of catalyst is high.This has absolutely proved that Rh, Ir, Sn, Pb have good synergy in terms of the activity and selectivity of catalyst is improved.
Table 1
The catalyst physical property of table 2 and evaluating data
Claims (10)
1. allyl acetate produces catalyst used, and the catalyst includes carrier, active component and promoter；It is described
Active component includes metal Pd and Ni metal；The promoter is alkali metal acetate；The carrier includes carrier substrate
And face coat；The base material is porous silica；The coating is by modified metal element and by the modified metal
Element is bonded in the silica binder composition of the substrate surface；The modified metal constituent content be 0.10～
1.00g/L；At least one of the modifying element in platinum cluster metallic element and IVA metallic elements.
2. catalyst according to claim 1, it is characterised in that the platinum cluster metallic element is selected from Ru, Rh, Os, Ir
With at least one in Pt.
3. catalyst according to claim 1, it is characterised in that the IVA metallic elements in Ge, Sn and Pb extremely
Few one kind.
4. catalyst according to claim 1, it is characterised in that the alkali metal acetate is potassium acetate.
5. catalyst according to claim 1, it is characterised in that the content of Pd is 1.0～10.0g/L in catalyst.
6. catalyst according to claim 1, it is characterised in that the content of Cu is 0.1～5.0g/L in catalyst.
7. catalyst according to claim 1, it is characterised in that the content of potassium acetate is 10.0～120.0 in the catalyst
g/L。
8., by the preparation method of the catalyst described in claim 1, comprise the steps：
(1) hydroxide or oxide of the modified metal element and Ludox are mixed to get into coating liquid；
(2) above-mentioned coating liquid is coated to into porous silica silicon face, dry, roasting obtains the catalyst carrier；
(3) the carrier impregnation compound containing Pd and impregnation liquid containing Cu compounds are obtained into catalyst precarsor I；
(4) make compound containing Pd and compound containing Cu be converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(5) compound state Pd and compound state Cu in the sedimentation type is reduced to into metal Pd and Ni metal obtains catalyst precarsor
III；
(6) promoter solution is impregnated, is dried to obtain the catalyst.
9. the synthetic method of allyl acetate, with propylene, acetic acid, oxygen and water as raw material, in claim 1～7 Arbitrary Term institute
State reaction in the presence of catalyst and obtain allyl acetate.
10. synthetic method according to claim 9, it is characterized in that the temperature reacted be 120～150 DEG C, the pressure of reaction be
0.1～1MPa, with molar ratio computing propylene:Acetic acid:Oxygen:Water=1:(0.1～0.3):(0.1～0.3):(0.2～1), raw material
Volume space velocity is 1500～2500h-1。
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| CN104549517A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
| CN106582854A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Allyl acetate catalyst and application thereof |
| CN106582868A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing allyl acetate |
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2015
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| CN1123527A (en) * | 1993-05-25 | 1996-05-29 | 恩格尔哈德公司 | Catalyst and process for using same for the preparation of unsaturated carboxylic acid esters |
| CN1268395A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司 | Catalyst for producing vinyl acetate |
| CN101056699A (en) * | 2004-10-15 | 2007-10-17 | 犹德有限公司 | Reactor and method for synthesizing vinyl acetate in gaseous phase |
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