CN114160160A - Ternary metal catalyst for synthesizing lower carboxylic acid alkenyl ester and preparation method and application thereof - Google Patents
Ternary metal catalyst for synthesizing lower carboxylic acid alkenyl ester and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- -1 carboxylic acid alkenyl ester Chemical class 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 67
- 238000001035 drying Methods 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 51
- 238000005406 washing Methods 0.000 claims abstract description 27
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 238000007598 dipping method Methods 0.000 claims abstract description 19
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims abstract 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 54
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 235000011056 potassium acetate Nutrition 0.000 claims description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 49
- 238000002390 rotary evaporation Methods 0.000 description 40
- 239000010949 copper Substances 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 23
- 239000002994 raw material Substances 0.000 description 22
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 16
- 239000007788 liquid Substances 0.000 description 14
- 229910052911 sodium silicate Inorganic materials 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 11
- 238000007654 immersion Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000010926 purge Methods 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/896—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a ternary metal catalyst for synthesizing alkenyl lower carboxylic acid ester, and a preparation method and application thereof, wherein the ternary metal catalyst comprises an active component, a carrier, an auxiliary active component and a modification component, and the active component comprises metal Pd, Cu and Zn; the preparation method comprises (a) impregnating the carrier into a mixed impregnation solution containing salts of Pd, Cu and Zn and a modified metal compound to obtain a catalyst precursor I; (b) converting the salts containing Pd, Cu and Zn from the solution into a precipitate type by using an alkaline solution to obtain a catalyst precursor II; (c) washing the catalyst precursor II in step (b) with water to neutrality; (d) the combined Pd, Cu, Zn and modified metal in the precipitation type are reduced to be in a metal state, and a catalyst precursor III is obtained; (e) dipping the auxiliary active component solution; (f) drying to obtain the catalyst. The three-way metal catalyst can improve the activity and the selectivity of the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to a ternary metal catalyst for synthesizing low-carbon alkenyl carboxylate, and a preparation method and application thereof.
Background
In the synthesis method of the lower alkenyl carboxylate, the lower alkenyl carboxylate is mainly obtained by carrying out gas phase reaction on lower olefin, lower chain carboxylic acid and oxygen, wherein a supported noble metal catalyst is widely used, and an active component Pd and alkali metal/alkaline earth metal of an auxiliary active component are supported on a carrier.
The invention patent EP0361484A2 discloses a preparation method of a catalyst loaded with a main active component and an auxiliary active component. The specific manufacturing process is as follows: adding the prepared mixed solution of the noble metal and the auxiliary active component, drying, treating with an alkaline precipitator such as sodium silicate and the like to precipitate the original water-soluble metal salt into palladium and copper in a hydroxide state, reducing into the palladium and copper in a metal state in a reducing atmosphere to obtain a palladium and copper catalyst, washing, drying, soaking with potassium acetate, and drying to obtain the catalyst. The space-time yield and selectivity of the catalyst obtained by the method are low.
The invention patent CN101657259 discloses a preparation method of a catalyst loaded with a main active component noble metal and an auxiliary active component metal. The specific manufacturing process of the auxiliary active component is as follows: (1) adding the prepared mixed solution of the noble metal and the auxiliary active component into a rotating dipping tank, and introducing hot air for drying; (2) adding a certain amount of alkaline solution such as sodium silicate and the like into the dried catalyst, and converting the original water-soluble palladium and gold salts into water-insoluble palladium and gold in a hydrogen oxidation state; (3) reducing the palladium and gold catalysts in a hydrogen oxidation state in a reducing gas, namely the palladium and gold catalysts in a metal state; (4) washing until no chloride ion exists, and drying; (5) and (4) soaking potassium acetate, and drying to obtain the catalyst. The space-time yield and selectivity of the catalyst obtained by the method are low.
Disclosure of Invention
In order to improve the activity and selectivity of the catalyst, the invention provides a ternary metal catalyst for synthesizing lower carboxylic acid alkenyl ester, and a preparation method and application thereof.
A large number of experiments show that three metals of Pd, Cu and Zn can play a better synergistic effect when preparing the catalyst for synthesizing the lower carboxylic acid alkenyl ester, so that the invention is developed by a ternary metal catalyst for synthesizing the lower carboxylic acid alkenyl ester, and the components of the ternary metal catalyst comprise an active component, a carrier, an auxiliary active component and a modification component, wherein the active component is the ternary metal of Pd, Cu and Zn.
Further, the content of Pd in the catalyst is preferably 1.0-10 g/L; the content of Cu is preferably 0.1-5.0 g/L; the preferable content of Zn is 0.1-5.0 g/L.
Optionally, the modified metal element is at least one of IIIA element and VIII element, the IIIA element is preferably at least one of B, Ga and In, the VIII element is preferably at least one of Fe, Co, Ni, Ru and Pt, and most preferably at least one of Ga, Fe and Co; the content of the modified component is 0.1-1.00 g/L.
The modified metal element has better synergistic effect on the aspects of catalyst activity and selectivity, and when at least one modified metal element of IIIA element and VIII element is simultaneously used as the catalyst carrier, more outstanding technical effect is achieved (specifically, see examples 5-8).
Optionally, the carrier is a porous material, and the porous material is preferably one of silica, alumina and silica-alumina; the shape of the porous material is any one of powder, sphere or granule, and the sphere is preferable.
The silica is not limited to SiO2Including silica containing impurities.
Optionally, the auxiliary active component is alkali metal acetate, and the alkali metal acetate is preferably potassium acetate; the content is preferably 10-120 g/L.
The specific surface of the carrier substrate is 100-500 m2The pore volume is 0.85-1.40 ml/g.
Secondly, the preparation method of the ternary metal catalyst for synthesizing the lower carboxylic acid alkenyl ester comprises the following specific steps:
(a) dipping the carrier into a mixed dipping solution containing salts of Pd, Cu and Zn and a modified metal compound to obtain a catalyst precursor I;
(b) converting the salts containing Pd, Cu and Zn from the solution into a precipitate type by using an alkaline solution to obtain a catalyst precursor II;
(c) washing the catalyst precursor II in step (b) with water to neutrality;
(d) reducing the combined Pd, Cu, Zn and modified metal in the precipitation type into a metal state to obtain a catalyst precursor III;
(e) dipping the auxiliary active component solution;
(f) drying to obtain the catalyst.
The alkaline solution in the step (b) is Na2SiO3·9H2O、NaOH、KOH、Na2CO3Is preferably Na2SiO3·9H2O。
Optionally, in the step (d), the reduction mode is one of hydrazine hydrate reduction, propylene gas phase reduction and hydrogen gas phase reduction, and hydrazine hydrate reduction is preferred.
Finally, the preparation method of the lower alkenyl carboxylate comprises the following steps: filling a catalyst into a microreactor, adopting nitrogen to test leakage, introducing olefin and nitrogen after no leakage point exists, simultaneously heating to a catalyst bed layer temperature of 120 ℃, introducing organic acid and water, adding oxygen after twenty minutes, and introducing oxygen after thirty minutes to prepare the low-carbon alkenyl carboxylate.
The oxygen feeding refers to the stage before the reaction, the oxygen flow is slowly increased to the flow required by the reaction, and the temperature runaway of the reactor caused by the reaction of a large amount of instantly introduced oxygen and olefin is prevented.
The amount of the catalyst loaded into the micro-reactor is 10ml, the flow rate of olefin is 0.5-1.0 mol/h, the flow rate of nitrogen is 0.5-1.0 mol/h, the amount of the introduced organic acid is 0.05-0.5 mol/h, the amount of water is 0.1-0.5 mol/h, and the amount of the introduced oxygen is 0.05-0.3 mol/h.
The reaction temperature in the reaction process is 120-180 ℃, and preferably 150-180 ℃; the reaction pressure is 0.1-1.0 MPa, preferably 0.5-0.9 MPa; the olefin is preferably present in a molar ratio: organic acid: oxygen: water 1: (0.1-0.3): (0.1-0.2): (0.2-0.4).
Optionally, the olefin is an olefin with a carbon number of less than 6, preferably an unsaturated hydrocarbon with 2-4 carbon atoms, and more preferably ethylene and propylene.
Optionally, the organic acid is one of aliphatic organic acids with a carbon number of <4, preferably a linear organic acid with 1-4 carbon atoms, and more preferably acetic acid and propionic acid.
Analyzing the content of each component in the reaction product by gas chromatography, and calculating the activity and selectivity of the catalyst according to the following formula:
activity (g/L ×) reaction time (g/L ×) per volume of catalyst;
selectivity (moles of acetic acid reacted to produce alkenyl lower carboxylate/moles of acetic acid consumed by the reaction) 100%.
Advantageous effects
The catalyst prepared by using three metals of Pd, Cu and Zn has the activity of 377.17 g/L.h and the selectivity of 97.67%; when the three-way metal catalyst simultaneously uses at least one modified metal element of IIIA element and VIII element, more outstanding technical effects are obtained, the activity can reach 377.77 g/L.h, the selectivity can reach 98.23 percent, and more outstanding technical effects are obtained.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2、0.20g Cu(NO3)2And 0.25g Zn (NO)3)2To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water to be neutral, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The catalyst has Pd content of 4.36g/L, Cu content of 0.39g/L, Zn content of 0.87g/L and potassium acetate content of 23.5g/L as measured by ICP.
Synthesis of allyl acetate:
10ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 377.17 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 97.67%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Example 2
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2、0.40g Cu(NO3)2And 0.25g Zn (NO)3)2To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water, and drying at 40 ℃ by rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The catalyst has Pd content of 4.38g/L, Cu content of 0.81g/L, Zn content of 0.83g/L and potassium acetate content of 23.7g/L as measured by ICP.
Synthesis of allyl acetate:
10ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating to 120 deg.C, adding acetic acid and water, heating, adding oxygen, and controlling reactionThe temperature is 172 ℃, and the reaction pressure is 0.70 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 376.75 g/L.multidot.h, and the selectivity to allyl acetate was 97.65%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Example 3
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2、0.20g Cu(NO3)2And 0.50g Zn (NO)3)2To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water, and drying at 40 ℃ by rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The catalyst has Pd content of 4.41g/L, Cu content of 0.40g/L, Zn content of 1.59g/L and potassium acetate content of 23.7g/L through ICP determination.
Synthesis of allyl acetate:
10ml of catalyst was packed in a fixed bed reactorIn the middle, with N2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.69 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 376.28 g/L.multidot.h, and the selectivity to allyl acetate was 97.12%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Example 4
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2、0.40g Cu(NO3)2And 0.50g Zn (NO)3)2To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water, and drying at 40 ℃ by rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The catalyst has Pd content of 4.37g/L, Cu content of 0.78g/L, Zn content of 1.62g/L and potassium acetate content of 23.9g/L as measured by ICP.
Synthesis of vinyl acetate:
10ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of ethylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.69 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with ethylene/acetic acid/oxygen/water (molar ratio) 1/0.18/0.2/0.3 and stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 375.91 g/L.multidot.h, with a selectivity to vinyl acetate of 97.36%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Example 5
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2、0.20g Cu(NO3)2、0.25g Zn(NO3)2And 0.12g Ga (NO)3)3To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water, and drying at 40 ℃ by rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O in weight ratio) of 90ml of hydrazine hydrateReducing, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The catalyst has Pd content of 4.40g/L, Cu content of 0.39g/L, Zn content of 0.84g/L, Ga content of 0.35g/L and potassium acetate content of 23.8g/L through ICP determination.
Synthesis of allyl acetate:
10ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 377.65 g/L.multidot.h, and the selectivity to allyl acetate was 97.98%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Example 6
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2、0.20g Cu(NO3)2、0.25g Zn(NO3)2And 0.15g Fe (NO)3)3To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water, and drying at 40 ℃ by rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The catalyst has Pd content of 4.39g/L, Cu content of 0.41g/L, Zn content of 0.86g/L, Fe content of 0.41g/L and potassium acetate content of 24.0g/L through ICP determination.
Synthesis of allyl acetate:
10ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 377.77 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 98.23%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Example 7
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2、0.20g Cu(NO3)2、0.25g Zn(NO3)2And 0.10g In (NO)3)3、0.15g Fe(NO3)2To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water, and drying at 40 ℃ by rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The catalyst has Pd content of 4.43g/L, Cu content of 0.42g/L, Zn content of 0.85g/L, In content of 0.29g/L, Fe content of 0.39g/L and potassium acetate content of 24.1g/L through ICP determination.
Synthesis of allyl acetate:
10ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 377.21 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 98.14%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Example 8
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2、0.20g Cu(NO3)2、0.25g Zn(NO3)2And 0.12g Ga (NO)3)3、0.20g Co(NO3)2To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water, and drying at 40 ℃ by rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The catalyst has Pd content of 4.41g/L, Cu content of 0.39g/L, Zn content of 0.86g/L, Ga content of 0.33g/L, Co content of 0.57g/L and potassium acetate content of 24.2g/L through ICP determination.
Synthesis of vinyl acetate:
10ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of ethylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: ethylene/acetic acid/oxygen/water (molar ratio) ═ 1/0.18/0.2/0.3, holdAfter the reaction is continued for 100h, the reaction is stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 377.53 g/L.multidot.h, with a selectivity to vinyl acetate of 97.97%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Example 9
(1) Using particulate SiO2BET specific surface area of 356m2The pore volume is 1.87 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2、0.20g Cu(NO3)2And 0.25g Zn (NO)3)2To obtain 90ml of an immersion liquid. Dipping the catalyst precursor on a carrier in a beaker, and drying the carrier in an oven at 100 ℃ for 12 hours to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water, and drying in an oven at 100 ℃ for 12h to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying in an oven at 100 ℃ for 12h to obtain a catalyst precursor III;
(5) and dissolving 2.5g of potassium acetate in pure water to obtain 90ml of impregnation liquid, impregnating the impregnation liquid on the precursor III, and drying the impregnation liquid in an oven at 100 ℃ for 12 hours to obtain the catalyst.
The catalyst has Pd content of 4.38g/L, Cu content of 0.41g/L, Zn content of 0.82g/L and potassium acetate content of 24.0g/L as measured by ICP.
Synthesis of allyl acetate:
10ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, and putting the mixture into the reactorContinuously heating acetic acid and water, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 376.78 g/L.multidot.h, and the selectivity to allyl acetate was 97.69%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Comparative example 1
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2And 0.20g Cu (NO)3)2To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3·9H2Adding the solution of O into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4h, washing with water, and drying at 40 ℃ by rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The catalyst has Pd content of 4.33g/L, Cu content of 0.40g/L and potassium acetate content of 23.9g/L as measured by ICP.
Synthesis of allyl acetate:
10ml of catalyst was packed in a fixed bed reactorIn the middle, with N2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 362.28 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.58%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
Comparative example 2
(1) Spherical SiO used2BET specific surface area of 210m2The pore volume is 1.10 ml/g.
(2) The preparation contained 1.0g of Pd (NO)3)2And 0.25g Zn (NO)3)2To obtain 90ml of an immersion liquid. Dipping the catalyst precursor I on a carrier in a rotary single-mouth bottle, and drying the carrier at 40 ℃ by using rotary evaporation to obtain a catalyst precursor I;
(3)150ml contain 13.6g Na2SiO3Adding the 9H2O solution into a rotary single-mouth bottle, fully mixing with the catalyst precursor I, aging for 4H, washing with water, and drying at 40 ℃ by rotary evaporation to obtain a catalyst precursor II;
(4) with a solubility of 5% (in N)2H4·H2O weight ratio) of 90ml of hydrazine hydrate, washing with water, and drying at 40 ℃ by using rotary evaporation to obtain a catalyst precursor III;
(5) the catalyst was obtained by dissolving 2.5g of potassium acetate in pure water to obtain 90ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 40 ℃ by rotary evaporation.
The Pd content of the catalyst is 4.42g/L, the Zn content is 0.82g/L and the potassium acetate content is 24g/L through ICP determination.
Synthesis of vinyl acetate:
10ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of ethylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to 172 ℃ and the reaction pressure to 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with ethylene/acetic acid/oxygen/water (molar ratio) 1/0.18/0.2/0.3 and stopped.
And (3) product analysis: and cooling, decompressing and separating a reaction mixture obtained by the reaction, and analyzing a liquid phase by adopting a gas chromatography-mass spectrometer.
The activity of the catalyst was calculated to be 358.07 g/L.multidot.h, with a selectivity to vinyl acetate of 95.19%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
TABLE 1 catalyst preparation, modification data
TABLE 2 physical Properties and evaluation data of catalysts
The comparative examples show that the activity and selectivity of the separately impregnated Pd, Zn and Pd, Cu binary metal catalyst are greatly different from those of the Pd, Cu, Zn ternary metal catalyst of the invention, and the activity and selectivity of the catalyst are further improved after the modified metal is added on the basis of the Pd, Cu, Zn ternary metal catalyst. This shows that Pd, Cu and Zn have good synergistic effect, and can be used as synergistic active component to play the role of catalysis, and the modified metal element also has the promotion effect in the aspects of catalyst activity and selectivity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents and the like included in the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A ternary metal catalyst for synthesizing alkenyl lower carboxylic acid ester comprises an active component, a carrier, an auxiliary active component and a modification component, and is characterized in that the active component comprises metals Pd, Cu and Zn.
2. The three-way metal catalyst for synthesizing alkenyl lower carboxylic acid ester is characterized in that the content of Pd in the catalyst is preferably 1.0-10 g/L; the content of Cu is preferably 0.1-5.0 g/L; the preferable content of Zn is 0.1-5.0 g/L.
3. The three-way metal catalyst for synthesizing alkenyl lower carboxylates according to claim 1, characterized In that the modifying metal element is at least one of IIIA, preferably B, Ga and In, and VIII, preferably at least one of Fe, Co, Ni, Ru and Pt, most preferably at least one of Ga, Fe and Co; the content of the modified component is 0.1-1.00 g/L.
4. The three-way metal catalyst for synthesizing alkenyl lower carboxylic acids according to claim 1, wherein the carrier is a porous material, and the porous material is preferably one of silica, alumina and silica-alumina; the shape of the porous material is one of powder, sphere and granule, and the sphere is preferred.
5. The ternary metal catalyst for the synthesis of alkenyl lower carboxylates according to claim 1, characterized in that said co-active component is an alkali metal acetate, preferably potassium acetate; the content is preferably 10-120 g/L.
6. A preparation method of a ternary metal catalyst for synthesizing alkenyl lower carboxylate is characterized by comprising the following specific steps:
(a) dipping the carrier into a mixed dipping solution containing salts of Pd, Cu and Zn and a modified metal compound to obtain a catalyst precursor I;
(b) converting the salts containing Pd, Cu and Zn from the solution into a precipitate type by using an alkaline solution to obtain a catalyst precursor II;
(c) washing the catalyst precursor II in step (b) with water to neutrality;
(d) reducing the combined state Pd, Cu, Zn and modified metal in the precipitation type into a metal state,
obtaining a catalyst precursor III;
(e) dipping the auxiliary active component solution;
(f) drying to obtain the catalyst.
7. The method of claim 6, wherein the alkaline solution in step (b) is Na2SiO3·9H2O、NaOH、KOH、Na2CO3Is preferably Na2SiO3·9H2O; in the step (d), the reduction mode is one of hydrazine hydrate reduction or propylene gas phase reduction and hydrogen gas phase reduction, and hydrazine hydrate reduction is preferred.
8. A preparation method of alkenyl lower carboxylate is characterized in that a catalyst is filled in a microreactor, leakage test is carried out by adopting nitrogen, olefin and nitrogen are introduced after no leakage point exists, simultaneously, the temperature is raised, organic acid and water are introduced, oxygen is introduced firstly, and then oxygen is introduced to prepare the alkenyl lower carboxylate.
9. The method of claim 8, wherein the amount of the catalyst charged into the microreactor is 10ml, the flow rate of the olefin is 0.5 to 1.0mol/h, the flow rate of the nitrogen is 0.5 to 1.0mol/h, the temperature is raised until the temperature of the catalyst bed reaches 120 ℃, the amount of the organic acid introduced is 0.05 to 0.5mol/h, the amount of the water is 0.1 to 0.5mol/h, and the amount of the oxygen introduced is 0.05 to 0.3 mol/h; controlling the reaction temperature to be 120-180 ℃ in the reaction process, and preferably 150-180 ℃; the reaction pressure is 0.1-1.0 MPa, preferably 0.5-0.9 MPa; preferably the olefin: organic acid: oxygen: the molar ratio of water is 1: (0.1-0.3): (0.1-0.2): (0.2-0.4).
10. The process for the preparation of alkenyl lower carboxylates according to claim 8, characterized in that the alkene is an alkene with a carbon number <6, preferably an unsaturated hydrocarbon with 2 to 4 carbon atoms, more preferably ethylene, propylene; the organic acid is aliphatic organic acid containing carbon number <4, preferably straight chain organic acid containing 1-4 carbon atoms, and more preferably acetic acid and propionic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582855A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing allyl acetate |
| CN106582822A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for synthesizing allyl acetate |
| 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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2021
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582855A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing allyl acetate |
| CN106582822A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for synthesizing allyl acetate |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116550383A (en) * | 2023-07-12 | 2023-08-08 | 中国天辰工程有限公司 | Preparation method of unsaturated acetate and catalyst thereof |
| CN116550383B (en) * | 2023-07-12 | 2023-10-31 | 中国天辰工程有限公司 | Preparation method of unsaturated acetate and catalyst thereof |
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