CN107866277A - The preparation method of vinyl acetate catalyst - Google Patents
The preparation method of vinyl acetate catalyst Download PDFInfo
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- CN107866277A CN107866277A CN201610852842.9A CN201610852842A CN107866277A CN 107866277 A CN107866277 A CN 107866277A CN 201610852842 A CN201610852842 A CN 201610852842A CN 107866277 A CN107866277 A CN 107866277A
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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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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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Abstract
The present invention relates to the preparation method of vinyl acetate catalyst, mainly solves the problems, such as that the activity and selectivity of existing vinyl acetate catalyst is low.The invention provides a kind of method for preparing vinyl acetate catalyst, comprise the following steps：(a) silica mixes with thionyl chloride liquid, is added after drying in the chloroform soln dissolved with cyclodextrin and diethylamine, handles and catalyst carrier is made；(b) catalyst carrier mixes with the solution dissolved with containing palladium compound and gold-containing compound, and catalyst precarsor I is made；(c) containing palladium compound and gold-containing compound is converted into sedimentation type with alkaline solution treatment catalyzed precursor I, obtain catalyst precarsor II；(d) after catalyst precarsor II is dried, handled with reducing agent, obtain catalyst precarsor III；(e) alkali metal acetate solution impregnation catalyst precursor II I is used, the catalyst is made after drying, preferably solves the problem, in the production available for vinyl acetate commercial plant.
Description
Technical field
The present invention relates to the preparation method of vinyl acetate catalyst and its synthetic method.
Background technology
Vinyl acetate is important industrial chemicals, be widely used in manufacture polyvinyl alcohol, vinyl copolymer resin, binding agent,
Coating, textile processing, paper coating etc..The production process route of vinyl acetate mainly has ethylene process and acetylene method two
Kind, wherein ethylene process due to manufacturability, good economy performance and occupy leading status, using the vinyl acetate production ability of this method
Account for the 82% of total productive capacity.The U.S. has completed all in nineteen eighty-three using the conversion of ethylene process route.At present, most of states
The method of family's increase vinyl acetate yield is to carry out reorganization and expansion and the update of catalyst, the hair of ethylene process route to original device
Exhibition trend, several aspects have been summed up it：(1) process units scale tends to maximization.Such as USI companies of U.S. the seventies initial stages
Process units scale is ten thousand tons/year of 13.6-15.9, and nineteen ninety unit scale reaches 360,000 tons/year, also described above
The expansion energy of Hoechst companies VAC devices；(2) although ethylene process VAC flow comparative maturities, but still improving, with reduce unit consumption with
Energy consumption；Current state-of-the-art ethylene process technique is the Leap techniques of Amoco companies and the Vantage techniques of Celanese companies.
The investment of acetylene method process unit is higher, and environmentally friendly difficulty is larger, but high with crude oil price, will keep over a period to come
Suitable competitive advantage, and directly facilitate the research and development of C1 chemical methods.
The main method that vinyl acetate is produced in the world today is using ethene, oxygen and acetic acid as raw material, with palladium-gold-vinegar
Sour potassium/silica makees catalyst, is produced by gas phase catalytic reaction, generation vinyl acetate, water and accessory substance carbon dioxide,
Also generate micro ethyl acetate, acetaldehyde and other acetoxylation product.The temperature of the reactor shell-side of the reaction can be
About 100 to about 180 DEG C, and reaction pressure is about 0.5-1.0MPa, gas volume air speed is about 500 to about 3000hr-1。
The patent (CN1226188A) of Hanchester rayon Co., Ltd provide one kind prepare be loaded with major catalyst noble metal,
The preparation method of the catalyst of promoter metal and alkali metal or alkaline earth metal compound.The catalyst activity that this method obtains
With selectivity all than relatively low, and using hydrogen or hydrazine hydrate reduction energy consumption and pollute higher.
The content of the invention
One of technical problems to be solved by the invention are to provide a kind of and method that is preparing vinyl acetate catalyst, use
Vinyl acetate catalyst prepared by this method can solve the problems, such as that catalyst activity and selectivity is low in the prior art, have and live
Property and selectivity it is high the characteristics of.
The two of the technical problems to be solved by the invention, it is to provide a kind of using one of the above-mentioned technical problem catalyst
Vinyl acetate synthetic method.
It is as follows to solve one of above-mentioned technical problem technical scheme：The method for preparing catalyst of vinyl acetate,
Comprise the following steps：
(a) silica is mixed with thionyl chloride liquid, and three chloromethanes dissolved with cyclodextrin and acid-acceptor are added after drying
In alkane solution, handle and catalyst carrier is made；
(b) catalyst carrier mixes with the solution dissolved with containing palladium compound and gold-containing compound, and catalyst precarsor is made
I；
(c) containing palladium compound and gold-containing compound is converted into sedimentation type with alkaline solution treatment catalyzed precursor I, obtain
Catalyst precarsor II；
(d) after catalyst precarsor II is dried, reduced with reducing agent, obtain catalyst precarsor III；
(e) alkali metal acetate solution impregnation catalyst precursor II I is used, the catalyst is made after drying.
In above-mentioned technical proposal, the cyclodextrin is alpha-cyclodextrin or beta-schardinger dextrin or the mixture of the two.
In above-mentioned technical proposal, the preferred organic amine of acid-acceptor described in step (a), commonly used in the art that can be selected
A bit, this is not particularly limited.For example can be C1~C6 primary amine, secondary amine or tertiary amine as non limiting example.The most this
The non-limiting particular compound of a little amines, such as can be diethylamine, triethylamine, pyridine etc..
In above-mentioned technical proposal, as a result of step (a), silicone hydroxyl and the thionyl chloride reaction of silica surface are given birth to
Into silicon chlorine key, then in the case where organic amine is as acid-acceptor, silicon chlorine key and the hydroxyl reaction generation Si-O-C in cyclodextrin
Key will connect silica and cyclodextrin, so as to improve the activity and selectivity of catalyst.
Only as an example, in the specific embodiment of the invention, with volume basis, silica in step (a):Dichloro is sub-
Sulfone:The volume ratio of chloroform soln can be 1:(0.9~2):(2~4).
In above-mentioned technical proposal, the containing palladium compound is preferably that chlorine palladium is sour or chloropalladate, gold-containing compound are preferably
Gold chloride or chloroaurate.
In above-mentioned technical proposal, in the solution of the containing palladium compound and gold-containing compound palladium content be preferably 0.9g/L~
12g/L, gold content are preferably 0.1g/L~11g/L.
In above-mentioned technical proposal, step (c) aqueous slkali is preferably alkali silicate or alkali metal hydroxide, is made
For non limiting example, sodium silicate nanahydrate solution is used in the present embodiment.
In above-mentioned technical proposal, step (a) the chloroform soln cyclodextrin class concentration is preferably 1~20mmol/
L。
In above-mentioned technical proposal, in step (a) chloroform soln concentration of acid-acceptor be preferably 80~
200mmol/L。
In above-mentioned technical proposal, the temperature of step (a) processing is preferably 40~60 DEG C.
In above-mentioned technical proposal, the time of step (a) processing is preferably 10~30hr.
In above-mentioned technical proposal, the cyclodextrin is preferably alpha-cyclodextrin or beta-schardinger dextrin, more preferably alpha-cyclodextrin and β-
The mixture of both cyclodextrin, when the cyclodextrin is the mixture of both alpha-cyclodextrin and beta-schardinger dextrin, it is catalyzed improving
There is synergy in terms of agent space-time and catalyst choice between alpha-cyclodextrin and beta-schardinger dextrin.
In above-mentioned technical proposal, when the cyclodextrin is both alpha-cyclodextrin and beta-schardinger dextrin blend mixture, preferably
The mol ratio of alpha-cyclodextrin and beta-schardinger dextrin is preferably 1：(0.5~2).
In above-mentioned technical proposal, step (d) reducing agent is preferably hydrogen, and reduction temperature is preferably 100~200 DEG C.
In above-mentioned technical proposal, step (e) alkali metal acetate is preferably potassium acetate.
It is as follows to solve two technical solution of the present invention of above-mentioned technical problem：The synthetic method of vinyl acetate, in such as right
It is required that in the presence of catalyst any one of 1~9, formed with molar ratio computing unstripped gas as oxygen：Ethene：Nitrogen：Acetic acid=
1：(5~7)：(4~8)：(1~2), reaction pressure are 0.5~0.9MPa, and reaction temperature is 130~200 DEG C, feed gas volume
Air speed is 1600~3000hr-1, react and obtain vinyl acetate.
Catalyst is in commercial Application because noble metal crystal grain active site position is very few and alloy forms deficiency and causes catalyst activity
With selective deficiency, using the vinyl acetate catalyst of the inventive method, catalyst carrier, energy are handled with cyclodextrin compounds
Enough strengthen the combination of noble metal crystal grain and carrier, increase the active site position of noble metal crystal grain, so that the activity of catalyst and choosing
Selecting property is also improved.Test result indicates that reaction pressure 0.7MPa, 140 DEG C of reaction temperature, reacting gas is with molar ratio computing oxygen
Gas：Ethene：Nitrogen：Acetic acid=1：6.8：7.2：When 1.7, the contrast prior art catalyst space time yield of catalyst of the invention
495g/Lhr is brought up to by 325g/Lhr, selectivity brings up to 98.6% by 93.8%, achieves preferable technique effect.
Embodiment
【Embodiment 1】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, add volume and contain alpha-cyclodextrin and diethyl for 3000ml
The content of alpha-cyclodextrin is 10mmol/L in the chloroform soln of amine, wherein chloroform soln, and the content of diethylamine is
130mmol/L, 12hr is handled at being 50 DEG C in temperature, catalyst carrier is obtained after drying.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
For the ease of comparing, the preparation condition of catalyst is listed in table 1.
(2) catalyst characterization
The content of each element in catalyst, income analysis table are measured using inductively coupled plasma spectrum generator (ICP)
Sign data are listed in table 2.
(3) evaluating catalyst
Evaluated with fixed bed reactors, actual conditions is：
Catalyst packing volume：400ml；
Reaction raw materials are formed (with molar ratio computing)：Oxygen：Ethene：Nitrogen：Acetic acid=1：6.8：7.2：1.7；
Reaction raw materials Feed space velocities：2000hr-1；
Reaction pressure：0.7MPa；
Reaction temperature：140℃；
Reaction time：500hr；
With the content of each component in gas chromatography analysis reaction product, catalysts towards ethylene selectivity, institute are then calculated
Obtain test data and be listed in table 2.
【Embodiment 2】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, add volume and contain beta-schardinger dextrin and diethyl for 3000ml
The content of beta-schardinger dextrin is 10mmol/L in the chloroform soln of amine, wherein chloroform soln, and the content of diethylamine is
130mmol/L, 12hr is handled at being 50 DEG C in temperature, catalyst carrier is obtained after drying.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Embodiment 3】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, it is being pasted containing alpha-cyclodextrin, β-ring for 3000ml to add volume
The chloroform soln of essence and diethylamine, the content of alpha-cyclodextrin is 5mmol/L wherein in chloroform soln, beta-schardinger dextrin
Content is 5mmol/L, and the content of diethylamine is 130mmol/L, and 12hr is handled at being 50 DEG C in temperature, and obtaining catalyst after drying carries
Body.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Embodiment 4】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, it is being pasted containing alpha-cyclodextrin, β-ring for 3000ml to add volume
The chloroform soln of essence and diethylamine, the content of alpha-cyclodextrin is 3.3mmol/L wherein in chloroform soln, beta-schardinger dextrin
Content be 6.7mmol/L, the content of diethylamine is 130mmol/L, handles 12hr at being 50 DEG C in temperature, must be catalyzed after drying
Agent carrier.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Embodiment 5】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, it is being pasted containing alpha-cyclodextrin, β-ring for 3000ml to add volume
The chloroform soln of essence and diethylamine, the content of alpha-cyclodextrin is 6.7mmol/L wherein in chloroform soln, beta-schardinger dextrin
Content be 3.3mmol/L, the content of diethylamine is 130mmol/L, handles 12hr at being 50 DEG C in temperature, must be catalyzed after drying
Agent carrier.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Embodiment 6】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, it is being pasted containing alpha-cyclodextrin, β-ring for 3000ml to add volume
The chloroform soln of essence and diethylamine, the content of alpha-cyclodextrin is 1.0mmol/L wherein in chloroform soln, diethylamine
Content is 130mmol/L, handles 12hr at being 50 DEG C in temperature, catalyst carrier is obtained after drying.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Embodiment 7】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, add volume and contain alpha-cyclodextrin and diethyl for 3000ml
The content of alpha-cyclodextrin is 20mmol/L in the chloroform soln of amine, wherein chloroform soln, and the content of diethylamine is
130mmol/L, 12hr is handled at being 50 DEG C in temperature, catalyst carrier is obtained after drying.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Embodiment 8】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, add volume and contain beta-schardinger dextrin and diethyl for 3000ml
The content of beta-schardinger dextrin is 1.0mmol/L in the chloroform soln of amine, wherein chloroform soln, and the content of diethylamine is
130mmol/L, 12hr is handled at being 50 DEG C in temperature, catalyst carrier is obtained after drying.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Embodiment 9】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, add volume and contain beta-schardinger dextrin and diethyl for 3000ml
The content of beta-schardinger dextrin is 20mmol/L in the chloroform soln of amine, wherein chloroform soln, and the content of diethylamine is
130mmol/L, 12hr is handled at being 50 DEG C in temperature, catalyst carrier is obtained after drying.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Embodiment 10】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, add volume and contain alpha-cyclodextrin and diethyl for 3000ml
The content of alpha-cyclodextrin is 10mmol/L in the chloroform soln of amine, wherein chloroform soln, and the content of diethylamine is
130mmol/L, 12hr is handled at being 40 DEG C in temperature, catalyst carrier is obtained after drying.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 0.85g/L wherein in solution,
The content of gold is 0.1g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 100 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Embodiment 11】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, add volume and contain beta-schardinger dextrin and diethyl for 3000ml
The content of beta-schardinger dextrin is 10mmol/L in the chloroform soln of amine, wherein chloroform soln, and the content of diethylamine is
130mmol/L, 12hr is handled at being 50 DEG C in temperature, catalyst carrier is obtained after drying.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Comparative example 1】
(1) catalyst preparation
Step (a)：The solution 1200ml containing chlorine palladium acid and gold chloride is taken, the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 1100ml, obtains catalyst load
Body I；
Step (b)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 150 DEG C, obtain catalyst precarsor III；
Step (d)：Acetic acid aqueous solutions of potassium is impregnated, it is 30g/L to make acetic acid potassium content, dries finished product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
【Comparative example 2】
(1) catalyst preparation
Step (a)：The preparing spherical SiO 2 carrier that volume is a diameter of 5.0mm of 2000ml is taken to add 2500ml thionyl chlorides
In solution, under temperature 60 C after processing 20hr after filtration drying, three chloromethanes containing diethylamine that volume is 3000ml are added
The content of diethylamine is 130mmol/L in alkane solution, wherein chloroform soln, handles 12hr at being 50 DEG C in temperature, dries
Catalyst carrier is obtained afterwards.
Step (b) takes the solution 1200ml containing chlorine palladium acid and gold chloride, and the content of palladium is 2.75g/L wherein in solution,
The content of gold is 0.625g/L, adds the catalyst carrier that above-mentioned volume is 1100ml, obtains catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrates are made into the 100ml aqueous solution to be added in catalyst precarsor I, are well mixed,
24hr is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e)：Catalyst precarsor III impregnates acetic acid aqueous solutions of potassium, and it is 30g/L to make acetic acid potassium content, and drying is made into
Product catalyst.
Other steps are identical in embodiment 1, for the ease of comparing the physical property number of the preparation condition of catalyst, catalyst
Tables 1 and 2 is selectively listed according to, catalysts towards ethylene.
By above-described embodiment and comparative example, find to urge using the blend mixture processing of both alpha-cyclodextrin and beta-schardinger dextrin
The palladium-gold catalyst prepared after agent carrier can more preferably improve the activity and selectivity of catalyst.
The catalyst preparation conditions of table 1.
The catalyst physical property of table 2 and evaluating data
Claims (9)
1. the preparation method of vinyl acetate catalyst, it is characterised in that comprise the following steps：
(a) silica is mixed with thionyl chloride liquid, and the chloroform dissolved with cyclodextrin and acid-acceptor is added after drying
In solution, handle and catalyst carrier is made；
(b) catalyst carrier mixes with the solution dissolved with containing palladium compound and gold-containing compound, and catalyst precarsor I is made；
(c) containing palladium compound and gold-containing compound is converted into sedimentation type with alkaline solution treatment catalyzed precursor I, be catalyzed
Agent precursor II；
(d) after catalyst precarsor II is dried, reduced with reducing agent, obtain catalyst precarsor III；
(e) alkali metal acetate solution impregnation catalyst precursor II I is used, the catalyst is made after drying.
2. according to the method for claim 1, it is characterised in that the containing palladium compound is chlorine palladium acid or chloropalladate, containing gold
Compound is gold chloride or chloroaurate.
3. according to the method for claim 1, it is characterised in that palladium in the solution of the containing palladium compound and gold-containing compound
Content is 0.9g/L~12g/L, and gold content is 0.1g/L~11g/L.
4. according to the method for claim 1, it is characterised in that the aqueous slkali is alkali silicate or alkali metal hydrogen-oxygen
Compound.
5. according to the method for claim 1, it is characterised in that the chloroform soln cyclodextrin class concentration be 1~
20mmol/L。
6. according to the method for claim 1, it is characterised in that the reducing agent is hydrogen, and reduction temperature is 100~200
℃。
7. according to the method for claim 1, it is characterised in that the alkali metal acetate is potassium acetate.
8. the catalyst obtained using method any one of claim 1~7.
9. the synthetic method of vinyl acetate, in the presence of the catalyst as any one of claim 8, with molar ratio computing raw material
Gas composition is oxygen：Ethene：Nitrogen：Acetic acid=1：(5~7)：(4~8)：(1~2), reaction pressure are 0.5~0.9MPa, instead
It is 130~200 DEG C to answer temperature, and feed gas volume air speed is 1600~3000hr-1, react and obtain vinyl acetate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113877630A (en) * | 2021-10-11 | 2022-01-04 | 万华化学集团股份有限公司 | Catalyst for preparing bis [ (3-dimethylamino) propyl ] amine and application thereof |
| CN114177938A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0539243A2 (en) * | 1991-10-25 | 1993-04-28 | Hidefumi Hirai | Process for introducing a carboxyl group to an aromatic carboxylic acid or a derivative thereof |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN103878023A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing vinyl acetate |
| CN104437654A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN104437648A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method and vinyl acetate synthesis method |
-
2016
- 2016-09-26 CN CN201610852842.9A patent/CN107866277B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0539243A2 (en) * | 1991-10-25 | 1993-04-28 | Hidefumi Hirai | Process for introducing a carboxyl group to an aromatic carboxylic acid or a derivative thereof |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN103878023A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing vinyl acetate |
| CN104437654A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN104437648A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method and vinyl acetate synthesis method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114177938A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
| CN113877630A (en) * | 2021-10-11 | 2022-01-04 | 万华化学集团股份有限公司 | Catalyst for preparing bis [ (3-dimethylamino) propyl ] amine and application thereof |
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