CN100336593C - Preparation method of supported catalyst for synthesizing vinyl acetate - Google Patents
Preparation method of supported catalyst for synthesizing vinyl acetate Download PDFInfo
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- CN100336593C CN100336593C CNB2004100164351A CN200410016435A CN100336593C CN 100336593 C CN100336593 C CN 100336593C CN B2004100164351 A CNB2004100164351 A CN B2004100164351A CN 200410016435 A CN200410016435 A CN 200410016435A CN 100336593 C CN100336593 C CN 100336593C
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- palladium
- copper
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052737 gold Inorganic materials 0.000 claims abstract description 24
- 239000010931 gold Substances 0.000 claims abstract description 24
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 18
- -1 alkali metal acetate Chemical class 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 6
- 239000000470 constituent Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 150000002941 palladium compounds Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000012018 catalyst precursor Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000012267 brine Substances 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 229940117958 vinyl acetate Drugs 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 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 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 235000011056 potassium acetate Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 235000019795 sodium metasilicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 235000019351 sodium silicates Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- CHUYYOSIZBKMJD-UHFFFAOYSA-N acetic acid;gold Chemical compound [Au].CC(O)=O CHUYYOSIZBKMJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation method of a supported catalyst for synthesizing vinyl acetate, which is used for gas phase reaction of ethene, acetic acid and oxygen containing gas. A carrier comprises SiO2 or Al2O3 or a mixture of the two, and active constituents comprise metal palladium, metal gold, metal copper and alkali metal acetate. The method orderly comprises that the carrier is impregnated by a compound water solution containing copper and aged; the compound containing copper is converted to the metal copper; the catalyst precursor is made after washing and dryness; the catalyst precursor is calcined in inert gas, reducing gas, or a mixture of the inert gas and the reducing gas, the calcining temperature is 500 to 1000 DEG C, and the calcining time is 2 to 10 hours. The catalyst precursor is impregnated and aged in a compound containing palladium and a compound containing gold, and the compound containing palladium and the compound containing gold are converted to metal palladium and gold by reducing agent. The catalyst precursor is infiltrated by an alkali metal acetic acid brine solution, and the catalyst of a finished product is made after dryness. The selectivity of the made catalyst is enhanced, and the activity is extremely good.
Description
Technical field
The present invention relates to a kind of preparation method who is used for by the loaded catalyst of ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester, catalyst activity component contains Metal Palladium, metallic gold and metallic copper.
Background technology
In the presence of catalyst, be the method for the suitability for industrialized production vinylacetate of comparative maturity by ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester, the catalyst of employing is generally loaded catalyst, and carrier is generally SiO2 or Al2O
3, or be SiO
2With Al
2O
3Mixture, active component generally includes Metal Palladium, metallic gold and alkali metal acetate.Catalyst generally adopts infusion process to prepare, and the catalyst that this traditional preparation method obtains can obtain advantages of high catalytic activity, but also is attended by the generation of accessory substance carbon dioxide simultaneously.U.S. Pat 5,968,869 propose carrier first carried metal copper before other active constituent of load, and as if the catalyst that obtains can reduce the ratio of carbon dioxide in the product, lose but its shortcoming is an activity of such catalysts.
Summary of the invention
The invention provides a kind of preparation method who is used for by the loaded catalyst of ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester, its technical problem to be solved is to wish that the catalyst that makes possesses good activity and selectivity of product simultaneously.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of preparation method who is used for by the loaded catalyst of ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester, catalyst carrier is SiO
2Or Al
2O
3In a kind of, or both mixtures, the catalyst activity component comprises Metal Palladium, metallic gold, metallic copper and alkali metal acetate, the content of each active constituent is: Metal Palladium 1～12g/l; Metallic gold 0.5～10g/l; Metallic copper 0.5～5g/l, alkali metal acetate 10～80g/l, the preparation method may further comprise the steps successively:
1) carrier places the aqueous solution that contains water-soluble copper-containing compound to flood;
2) carrier contacts ageing with alkaline solution;
3) carrier floods in containing the liquid phase material of reducing agent and makes the copper-containing compound in the carrier be converted into metallic copper;
4) carrier is washed and is made catalyst precarsor after the drying in addition;
5) catalyst precarsor roasting under the mixture atmosphere of inert gas, reducibility gas or inert gas and reducibility gas, sintering temperature is 500～1000 ℃, roasting time is 2～10 hours;
6) catalyst precarsor places the solution that contains palladium compound and gold-containing compound to flood;
7) catalyst precarsor contacts ageing with alkaline solution;
8) catalyst precarsor in containing the liquid phase material of reducing agent, flood make in the catalyst precarsor contain palladium compound and gold-containing compound is converted into Metal Palladium and gold;
9) with alkali metal acetate solution immersion catalyst precarsor;
10) catalyst precarsor makes finished catalyst after the drying in addition.
Above-mentioned steps 5 described sintering temperatures are preferably 600～800 ℃; Described roasting time is preferably 3～6 hours; Described reducibility gas is preferably hydrogen or carbon monoxide, and inert gas is preferably nitrogen, carbon dioxide or helium.
Method for preparing catalyst provided by the invention in terms of existing technologies, its key problem in technology has been with load the catalyst precarsor roasting in addition of metallic copper, other step and prior art are basic identical, and are familiar with by those of ordinary skill in the art.Concrete preparation method can be:
1) carrier places the aqueous solution that contains water-soluble copper-containing compound to flood:
The compound of copper can be Schweinfurt green, copper sulphate, copper nitrate, copper chloride, preferred copper chloride.The dipping liquid measure is 95～100% of a carrier hygroscopicity value, and the amount of the required copper-containing compound of preparation maceration extract determines that according to the target content of copper in the content of copper in the corresponding compounds wherein and the catalyst both equate usually;
2) carrier contacts ageing with alkaline solution:
Alkali compounds can be NaOH, potassium hydroxide or sodium metasilicate, preferred sodium metasilicate.Be mixed with ageing liquid with alkali compounds and soak into carrier, the ageing liquid measure is 5～15% of a carrier hygroscopicity value, and the consumption of alkali compounds is that copper compound is converted into 1.1～1.8 times of the required reaction equivalent of copper hydroxide fully.Ageing is at room temperature carried out usually, and digestion time is no less than 24 hours;
3) carrier floods in containing the liquid phase material of reducing agent and makes the copper-containing compound in the carrier be converted into metallic copper:
Reduce and at room temperature carry out in the liquid phase, reducing agent is generally hydrazine hydrate, and the consumption of hydrazine hydrate is to make the hydroxide of copper be converted into 5～20 times of the required reaction equivalent of metallic copper fully;
4) catalyst precarsor is washed and made after the drying in addition to carrier:
Use the deionized water flush vehicle, to there not being Cl
-Till (checking) with silver nitrate.Carry out drying then, baking temperature is no more than 120 ℃;
5) catalyst precarsor roasting under the mixture atmosphere of inert gas, reducibility gas or inert gas and reducibility gas, sintering temperature is 500～1000 ℃, roasting time is 2～10 hours.Reducibility gas is preferably hydrogen or carbon monoxide, and inert gas is preferably nitrogen, carbon dioxide or helium;
6) catalyst precarsor places the solution that contains palladium compound and gold-containing compound to flood:
Containing palladium compound can be that palladium, palladium sulfate, palladium nitrate, palladium bichloride, the acid of Halogen palladium are as H
2PdCl
4Or Halogen palladate such as Na
2PdCl
4Or K
2PdCl
4, gold-containing compound can be selected chlorauride, acetic acid gold, HAuCl for use
4, NaAuCl
4Or KAuCl
4Solvent can be water, carboxylic acid, alcohol, benzene etc., and preferred solvent is water and acetic acid.The dipping liquid measure is 95～100% of a carrier hygroscopicity value, the required amount that contains palladium compound and gold-containing compound of preparation maceration extract, target content according to palladium or gold in the content of palladium in the corresponding compounds wherein or gold and the catalyst determines that both equate usually;
7) catalyst precarsor contacts ageing with alkaline solution:
Handle catalyst precarsor with the aqueous solution that contains alkali compounds, alkali compounds can be NaOH, potassium hydroxide or sodium metasilicate, preferred sodium metasilicate.The ageing liquid measure is 5～15% of a carrier hygroscopicity value, and the consumption of alkali compounds is that palladium, gold compound are converted into palladium, the required reaction equivalent of golden hydroxide 1.1～1.8 times fully.Ageing is at room temperature carried out usually, and digestion time is no less than 24 hours;
8) catalyst precarsor in containing the liquid phase material of reducing agent, flood make in the catalyst precarsor contain palladium compound and gold-containing compound is converted into Metal Palladium and gold:
Reduce and at room temperature carry out in the liquid phase, reducing agent is a hydrazine hydrate, and the consumption of hydrazine hydrate is to make palladium, golden hydroxide be converted into palladium, the required reaction equivalent of metal 5～20 times fully.Use the deionized water rinsing catalyst precarsor again, to there not being Cl
-Till (checking) with silver nitrate.Carry out drying then, baking temperature is no more than 120 ℃;
9) with alkali metal acetate solution immersion catalyst precarsor:
Alkali metal acetate solution is generally the aqueous solution of potassium acetate, and soaking into liquid measure is 90～100% of carrier hygroscopicity value, and the amount of the potassium acetate that the preparation infiltrate is required is determined according to the target content of potassium acetate in the catalyst.
10) catalyst precarsor in addition makes finished catalyst after the drying, and the temperature suggestion is no more than 120 ℃ when dry.
Compared with prior art, the present invention has just increased this step of roasting after carrier loaded copper, but can obtain beyond thought effect yet the inventor found through experiments this simple improvement, not only selection of catalysts increases, and activity of such catalysts is also very good.
Below will the invention will be further described by specific embodiment.
The specific embodiment
One, Preparation of catalysts:
[embodiment 1～4]
(4～6mm) 1.1 liters of particle diameters are with containing 2.92 gram CuCl to get the preparing spherical SiO 2 carrier
22H
2450 milliliters of dippings of the aqueous solution of O, dipping is 1 hour under the room temperature.
7.32g nine hydrated sodium silicates are made into the 100ml aqueous solution are added in the above-mentioned carrier, shake several, left standstill then 24 hours to avoid caking.
With concentration is that the hydrazine hydrate 10ml impregnated carrier of 85wt% reduces, and dip time is 5 hours.
Spend deionised water catalyst precarsor to water outlet and do not contain chlorion (checking) with silver nitrate, dry under 60 ℃ then, obtain catalyst precarsor.
Catalyst precarsor roasting under inertia or reducing atmosphere, the concrete roasting condition of each embodiment sees Table l.
With containing 4.21 gram H
2PdCl
4With 2.04 gram HAuCl
4450 milliliters of impregnation-calcinations of mixed aqueous solution after the Cu-contained catalyst precursor, under the room temperature dipping 1 hour.
27.5g nine hydrated sodium silicates are made into the 100ml aqueous solution are added in the above-mentioned catalyst precarsor, shake several, left standstill then 24 hours to avoid caking.
With concentration is that the hydrazine hydrate 30ml impregnated catalyst precursor of 85wt% reduces, and dip time is 5 hours.
Spend deionised water catalyst precarsor to water outlet and do not contain chlorion (checking) with silver nitrate, dry down in 60 ℃ then.
With the 450ml solution impregnating catalyst precursor that contains the 45g potassium acetate, flood after 5 hours in 60 ℃ of dry down catalyst finished products that get.
The composition of catalyst: palladium content 3.83g/l, gold content 1.85g/l, copper content 1.0g/l, potassium acetate content 30g/l.
[comparative example]
Load the carrier of copper without high-temperature roasting, all the other are with embodiment 1～4.
Two, the evaluation of catalyst:
The 900ml catalyst of in 900 milliliters of fixed bed reactors, packing into, with ethene pressure testing leak test, confirm not have leak after, the ethene flow is not transferred to 64.4mol/h, heat up simultaneously.When temperature in the beds reaches 120 ℃, drop into acetic acid, the acetic acid flow is 9.30mol/h.After half an hour, progressively drop into oxygen, throw sufficient oxygen amount after 2 hours, flow reaches 3.87mol/h, and the control raw material ratio is: ethene/acetic acid/oxygen=83.0/12.0/5.0 (mol ratio).
Control bed hot(test)-spot temperature is 142 ℃ in the course of reaction, reactor inlet pressure 0.8MPa.Ethene, acetic acid and oxygen are chargings after mixing in preheater.Regulate the acetic acid pump to control its flow, ethene and oxygen flow all adopt the control of mass velocity controller, reaction gas discharges after condenser condenses, product vinyl acetate in the analytical reactions liquid and unreacted acetic acid amount, and side reaction product carbon dioxide in the tail gas, uncooled vinyl acetate and unreacted oxygen.
The evaluation result of each embodiment and comparative example catalyst sees Table 2, and activity of such catalysts and selectivity definition are:
Table 1.
| Sintering temperature (℃) | Roasting time (hour) | Calcination atmosphere is formed | |
| Embodiment 1 | 500 | 2 | Hydrogen |
| Embodiment 2 | 1000 | 10 | Nitrogen |
| Embodiment 3 | 650 | 5 | Hydrogen/nitrogen |
| Embodiment 4 | 600 | 3.5 | Hydrogen/nitrogen |
Table 2.
| Active (g/lhr) | Selectivity (%) | |
| Embodiment 1 | 369 | 94.3 |
| Embodiment 2 | 377 | 94.8 |
| Embodiment 3 | 372 | 94.4 |
| Embodiment 4 | 374 | 94.5 |
| Comparative example | 346 | 92.1 |
Claims (5)
1, a kind of preparation method who is used for by the loaded catalyst of ethene, acetic acid and oxygen-containing gas gas-phase reaction synthesizing vinyl acetate ester, catalyst carrier is SiO
2Or Al
2O
3In a kind of, or both mixtures, the catalyst activity component comprises Metal Palladium, metallic gold, metallic copper and alkali metal acetate, the content of each active constituent is: Metal Palladium 1～12g/l; Metallic gold 0.5～10g/l; Metallic copper 0.5～5g/l, alkali metal acetate 10～80g/l, the preparation method may further comprise the steps successively:
1) carrier places the aqueous solution that contains water-soluble copper-containing compound to flood;
2) carrier contacts ageing with alkaline solution;
3) carrier floods in containing the liquid phase material of reducing agent and makes the copper-containing compound in the carrier be converted into metallic copper;
4) carrier is washed and is made catalyst precarsor after the drying in addition;
5) catalyst precarsor roasting under the mixture atmosphere of inert gas, reducibility gas or inert gas and reducibility gas, sintering temperature is 500～1000 ℃, roasting time is 2～10 hours;
6) catalyst precarsor places the solution that contains palladium compound and gold-containing compound to flood;
7) catalyst precarsor contacts ageing with alkaline solution;
8) catalyst precarsor in containing the liquid phase material of reducing agent, flood make in the catalyst precarsor contain palladium compound and gold-containing compound is converted into Metal Palladium and gold;
9) with alkali metal acetate solution immersion catalyst precarsor;
10) catalyst precarsor makes finished catalyst after the drying in addition.
2, the preparation method of loaded catalyst according to claim 1 is characterized in that the described sintering temperature of step 5 is 600～800 ℃.
3, the preparation method of loaded catalyst according to claim 1 is characterized in that the described roasting time of step 5 is 3～6 hours.
4, the preparation method of loaded catalyst according to claim 1 is characterized in that the described reducibility gas of step 5 is hydrogen or carbon monoxide.
5, the preparation method of loaded catalyst according to claim 1 is characterized in that the described inert gas of step 5 is nitrogen, carbon dioxide or helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100164351A CN100336593C (en) | 2004-02-19 | 2004-02-19 | Preparation method of supported catalyst for synthesizing vinyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100164351A CN100336593C (en) | 2004-02-19 | 2004-02-19 | Preparation method of supported catalyst for synthesizing vinyl acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1657169A CN1657169A (en) | 2005-08-24 |
| CN100336593C true CN100336593C (en) | 2007-09-12 |
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|---|---|---|---|
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102371182B (en) * | 2010-08-23 | 2013-04-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing acetate propylene ester and preparation method thereof |
| CN102463139B (en) * | 2010-11-17 | 2013-12-18 | 中国石油化工股份有限公司 | Catalyst for synthesizing isopropenyl acetate and preparation method thereof |
| CN103055941B (en) * | 2011-10-24 | 2014-11-26 | 中国石油化工股份有限公司 | Allyl acetate catalyst and preparation method thereof |
| CN104107722B (en) * | 2013-04-16 | 2016-05-18 | 中国石油化工股份有限公司 | For the synthetic catalyst of allyl acetate |
| CN106582826B (en) * | 2015-10-19 | 2019-11-08 | 中国石油化工股份有限公司 | Produce catalyst used in ethylene process vinyl acetate |
| CN114425445B (en) * | 2020-10-14 | 2023-09-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN114425454B (en) * | 2020-10-14 | 2024-02-02 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and vinyl acetate synthesis method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194417A (en) * | 1991-12-05 | 1993-03-16 | Quantum Chemical Corporation | Pretreatment of palladium-gold catalysts useful in vinyl acetate synthesis |
| CN1259060A (en) * | 1997-06-03 | 2000-07-05 | 国际人造丝公司 | Vinyl acetate catalyst comprising palladium and gold deposited on a copper containing carrier |
-
2004
- 2004-02-19 CN CNB2004100164351A patent/CN100336593C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194417A (en) * | 1991-12-05 | 1993-03-16 | Quantum Chemical Corporation | Pretreatment of palladium-gold catalysts useful in vinyl acetate synthesis |
| CN1259060A (en) * | 1997-06-03 | 2000-07-05 | 国际人造丝公司 | Vinyl acetate catalyst comprising palladium and gold deposited on a copper containing carrier |
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| CN1657169A (en) | 2005-08-24 |
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