CN106423284B - Vinyl acetate catalyst and preparation method thereof - Google Patents
Vinyl acetate catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN106423284B CN106423284B CN201510493370.8A CN201510493370A CN106423284B CN 106423284 B CN106423284 B CN 106423284B CN 201510493370 A CN201510493370 A CN 201510493370A CN 106423284 B CN106423284 B CN 106423284B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- compound
- gold
- palladium
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to vinyl acetate catalysts, mainly solve the problems, such as that the activity and selectivity of existing vinyl acetate catalyst is low.The present invention is by using vinyl acetate catalyst, with SiO2、Al2O3Or mixtures thereof be carrier, load active component includes Metal Palladium, metallic gold, alkali metal acetate and at least one of the compound 1 being shown below and compound 2 dendrimer compound, and the content of palladium is 1~12g/L in catalyst, the content of gold is 0.1~10g/L, the content of alkali metal acetate is 10~100g/L, dendrimer compound content is 0.1~2.0g/L；Wherein Et1~Et16It is independently selected from C1~C3Alkyl；The dendrimer compound is to be added after impregnating palladium compound and gold compound in the preparation process of catalyst and before the reduction step.
Description
Technical field
The present invention relates to vinyl acetate catalysts and preparation method thereof.
Background technique
Vinyl acetate is important industrial chemicals, be widely used in manufacture polyvinyl alcohol, vinyl copolymer resin, binder,
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 craftsmanship, 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. completes all in nineteen eighty-three using the conversion of ethylene process route.Currently, most of states
The method that family increases 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 has been summed up several aspects: (1) process units scale tends to enlargement.Such as USI company of U.S. the seventies initial stage
Process units scale is ten thousand tons/year of 13.6-15.9, and nineteen ninety unit scale reaches 360,000 tons/year, and there are also described above
The expansion energy of Hoechst company VAC device；(2) although ethylene process VAC process comparative maturity, but still improving, with reduce unit consumption with
Energy consumption；Current state-of-the-art ethylene process technique is the Leap technique of Amoco company and the Vantage technique of Celanese company.
Acetylene method process unit high investment, environmentally friendly difficulty is larger, but high with crude oil price, will keep over a period to come
Comparable competitive advantage, and directly facilitate the research and development of C1 chemical method.
It is using ethylene, oxygen and acetic acid as raw material, with palladium-gold-vinegar that the main method of vinyl acetate is produced in the world today
Sour potassium/silica makees catalyst, is produced by gas phase catalytic reaction, generates vinyl acetate, water and by-product 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 it is a kind of prepare load have major catalyst noble metal,
The preparation method of the catalyst of promoter metal and alkali or alkaline earth metal compound.The catalyst activity that this method obtains
It is all relatively low with selectivity.
Summary of the invention
The first technical problem to be solved by the present invention is that vinyl acetate catalyst activity and selectivity is low in the prior art
The problem of, a kind of vinyl acetate catalyst is provided, the feature that the catalyst is active and selectivity is high.
The second technical problem to be solved by the present invention is to provide the preparation side of catalyst described in one of above-mentioned technical problem
Method.
The second technical problem to be solved by the present invention is to provide a kind of synthesis of vinyl acetate using above-mentioned catalyst
Method.
One of to solve above-mentioned technical problem, technical scheme is as follows: vinyl acetate catalyst, with SiO2、
Al2O3Or mixtures thereof be carrier, load active component includes Metal Palladium, metallic gold, alkali metal acetate and is shown below
Compound 1 and at least one of compound 2 dendrimer compound, in catalyst the content of palladium be 1~12g/L,
The content of gold is 0.1~10g/L, the content of alkali metal acetate is 10~100g/L, dendrimer compound content is
0.1~2.0g/L；
Wherein Et1~Et16It is independently selected from C1~C3Alkyl；
The dendrimer compound be impregnated in the preparation process of catalyst palladium compound and gold compound it
It is added afterwards and before the reduction step.
In above-mentioned technical proposal, Et1~Et16Preferably ethyl.
In above-mentioned technical proposal, the alkali metal acetate is preferably potassium acetate.
In above-mentioned technical proposal, the dendritic macromole includes compound 1 and compound as a preferred technical solution,
2, two kinds of macromolecular compounds have synergistic effect in terms of improving selectivity at this time.More preferable compound 1 and compound 2
Mass ratio is 1:(0.05~20).
To solve above-mentioned technical problem two, technical scheme is as follows: being catalyzed described in one of above-mentioned technical problem
The preparation method of agent, comprising the following steps:
(a) in the solution dissolved with containing palladium compound and gold-containing compound, carrier impregnation is added, catalyst precarsor is made
I；
(b) catalyst precarsor II is obtained with alkaline compound solution processing catalytic precursor I；
(c) it in the solution containing at least one of compound 1 and compound 2 dendrimer compound, is added
Catalyst precarsor II dipping, obtains catalyst precarsor III；
(d) after catalyst precarsor III is dry, the gold of the palladium of compound state and compound state is reduced to simple substance with reducing agent, is obtained
To catalyst precarsor IV；
(e) alkali metal acetate solution impregnation catalyst precursor I V is used, the catalyst is made after dry.
In above-mentioned technical proposal, the containing palladium compound can be able to be for chlorine palladium acid or chloropalladate, gold-containing compound
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, the concentration of dendritic macromole is excellent in the solution containing dendrimer compound
It is selected as 0.09g/L~2.0g/L, dipping temperature is preferably 20~80 DEG C.
In above-mentioned technical proposal, the reducing agent is preferably hydrogen, and reduction temperature is preferably 100~300 DEG C.
In above-mentioned technical proposal, solvent is not particularly limited in the solution of the dendrimer compound, as long as energy
Enough that the macromolecular is dissolved, most economical is water.Dendrimer compound in the specific embodiment of the invention
Solution be all dendrimer compound aqueous solution.
To solve above-mentioned technical problem three, technical scheme is as follows: the synthetic method of vinyl acetate, above-mentioned
In the presence of catalyst described in any one of technical solution of one of technical problem, oxygen: second is become with molar ratio computing unstripped gas group
Alkene: 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, reaction obtains vinyl acetate.
In above-mentioned technical proposal, the feed gas volume air speed is preferably 1600~3000hr-1。
Catalyst causes catalyst activity and selectivity insufficient in industrial application because noble metal crystal grain activity point is very few, adopts
With the vinyl acetate catalyst of the method for the present invention, modified in noble metal grain surface using dendrimer compound,
Can increase the active point of noble metal crystal grain, and by modification after, the selectivity of catalyst is also improved.Experimental result table
Bright, reaction pressure 0.7MPa, 140 DEG C of reaction temperature, reaction gas is with molar ratio computing oxygen: ethylene: nitrogen: acetic acid=1:
When 6.8:7.2:1.7, the comparison prior art catalyst space time yield of catalyst of the invention is increased to 465g/L by 315g/L,
Selectivity is increased to 98.5% by 93.5%, achieves preferable technical effect.
Specific embodiment
[embodiment 1]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): taking the solution 1200ml containing the compound 1 that concentration is 0.12g/L, and catalyst precarsor II leaching is added
Stain obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
For the ease of comparing, the preparation condition of catalyst is listed in table 1.
(2) catalyst characterization
Using the content of each metallic element in inductively coupled plasma spectrum generator (ICP) measurement catalyst, penetrated using X
The content of dendritic macromole, income analysis characterize data are listed in table 2 in line fluorescence spectrum (XRF) analysis of catalyst.
(3) evaluating catalyst
It is evaluated with fixed bed reactors, actual conditions are as follows:
Catalyst packing volume: 400ml；
Reaction raw materials form (with molar ratio computing): oxygen: ethylene: 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 DEG C；
Reaction time: 500hr；
With the content of each component in gas chromatography analysis reaction product, catalysts towards ethylene selectivity, institute are then calculated
It obtains test data and is listed in table 2.
[embodiment 2]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): taking the solution 1200ml containing the compound 2 that concentration is 0.12g/L, and catalyst precarsor II leaching is added
Stain obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 3]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): the solution 1200ml containing compound 1 and compound 2 that concentration is 0.12g/L is taken, wherein compound 1
Mass ratio with compound 2 is 1:1, and catalyst precarsor II dipping is added, obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 4]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): the solution 1200ml containing compound 1 and compound 2 that concentration is 0.12g/L is taken, wherein compound 1
Mass ratio with compound 2 is 1:0.05, and catalyst precarsor II dipping is added, obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 5]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): the solution 1200ml containing compound 1 and compound 2 that concentration is 0.12g/L is taken, wherein compound 1
Mass ratio with compound 2 is 1:20, and catalyst precarsor II dipping is added, obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 6]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 0.92g/L, gold in solution
Content be 0.105g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): the solution 1200ml containing compound 1 and compound 2 that concentration is 0.092g/L is taken, wherein compound
1 and compound 2 mass ratio be 1:1, be added catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 7]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 11g/L in solution, golden
Content is 10.5g/L, and it is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst carrier I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): the solution 1200ml containing compound 1 and compound 2 that concentration is 1.84g/L is taken, wherein compound 1
Mass ratio with compound 2 is 1:1, and catalyst precarsor II dipping is added, obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 8]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium hydroxide and be added in catalyst precarsor I, is uniformly mixed, and stands
Catalyst precarsor II is made then in 80 DEG C of dry 8hr in r for 24 hours；
Step (c): the solution 1200ml containing compound 1 and compound 2 that concentration is 0.12g/L is taken, wherein compound 1
Mass ratio with compound 2 is 1:1, and catalyst precarsor II dipping is added, obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 9]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): the solution 1200ml containing compound 1 and compound 2 that concentration is 0.12g/L is taken, wherein compound 1
Mass ratio with compound 2 is 1:1, and catalyst precarsor II dipping is added, obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 100 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 10]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): the solution 1200ml containing compound 1 and compound 2 that concentration is 0.12g/L is taken, wherein compound 1
Mass ratio with compound 2 is 1:1, and catalyst precarsor II dipping is added, obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 300 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 10]
(1) catalyst preparation
Step (a): the solution 1200ml containing potassium chloropalladate and potassium chloroaurate is taken, wherein the content of palladium is in solution
2.75g/L, golden content are 0.625g/L, and it is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, is obtained
To catalyst carrier I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): the solution 1200ml containing compound 1 and compound 2 that concentration is 0.12g/L is taken, wherein compound 1
Mass ratio with compound 2 is 1:1, and catalyst precarsor II dipping is added, obtains catalyst precarsor III；
Step (d): catalyst precarsor III is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor IV；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[comparative example 1]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, it is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, obtains catalyst load
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (d): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[comparative example 2]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, in the above solution be added quality be 0.36g shown compound 1 and compound 2 mixture,
The mass ratio of middle compound 1 and compound 2 is 1:1, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
Through the foregoing embodiment and comparative example, discovery handle palladium-gold catalyst using the mixture of compound 1 and compound 2
The activity and selectivity of catalyst can more preferably be improved.And after dipping palladium compound and gold compound and by compound state
Better effect if being handled before palladium and the reduction of compound state gold with the mixture of compound 1 and compound 2.
1. catalyst preparation conditions of table
2 catalyst physical property of table and evaluation data
Claims (10)
1. vinyl acetate catalyst, with SiO2、Al2O3Or mixtures thereof be carrier, load active component includes Metal Palladium, metal
Gold, alkali metal acetate and at least one of the compound 1 being shown below and compound 2 dendritic macromole chemical combination
Object, the content of palladium is 1~12g/L in catalyst, the content of gold is 0.1~10g/L, the content of alkali metal acetate be 10~
100g/L, dendrimer compound content are 0.1~2.0g/L；
Wherein Et1~Et16It is independently selected from C1~C3Alkyl；
The dendrimer compound be after impregnating palladium compound and gold compound in the preparation process of catalyst simultaneously
And it is added before the reduction step.
2. vinyl acetate catalyst according to claim 1, it is characterised in that Et1~Et16For ethyl.
3. vinyl acetate catalyst according to claim 1, it is characterised in that the alkali metal acetate is potassium acetate.
4. the preparation method of catalyst described in claim 1, method comprising the following steps preparation:
(a) in the solution dissolved with containing palladium compound and gold-containing compound, carrier impregnation is added, catalyst precarsor I is made；
(b) catalyst precarsor II is obtained with alkaline compound solution processing catalyst precarsor I；
(c) in the solution containing at least one of compound 1 and compound 2 dendrimer compound, catalysis is added
Agent precursor II dipping, obtains catalyst precarsor III；
(d) after catalyst precarsor III is dry, the gold of the palladium of compound state and compound state is reduced to simple substance with reducing agent, is urged
Agent precursor I V；
(e) alkali metal acetate solution impregnation catalyst precursor I V is used, the catalyst is made after dry.
5. the preparation method according to claim 4, it is characterised in that the containing palladium compound be chlorine palladium acid or chloropalladate,
Gold-containing compound is gold chloride or chloroaurate.
6. the preparation method according to claim 4, it is characterised in that the solution of the containing palladium compound and gold-containing compound
Middle palladium content is 0.9g/L~12g/L, and gold content is 0.1g/L~11g/L.
7. the preparation method according to claim 4, it is characterised in that the solution containing dendrimer compound
The concentration of middle dendritic macromole is 0.09g/L~2.0g/L, and dipping temperature is 20~80 DEG C.
8. the preparation method according to claim 4, it is characterised in that the reducing agent be hydrogen, reduction temperature be 100~
300℃。
9. the synthetic method of vinyl acetate, in the presence of the catalyst as described in any one of claims 1 to 3, with molar ratio computing
Unstripped gas group become oxygen: ethylene: nitrogen: acetic acid=1:(5~7): (4~8): (1~2), reaction pressure be 0.5~
0.9MPa, reaction temperature are 130~200 DEG C, and reaction obtains vinyl acetate.
10. synthetic method according to claim 9, it is characterized in that the feed gas volume air speed is 1600~3000hr-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493370.8A CN106423284B (en) | 2015-08-12 | 2015-08-12 | Vinyl acetate catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493370.8A CN106423284B (en) | 2015-08-12 | 2015-08-12 | Vinyl acetate catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106423284A CN106423284A (en) | 2017-02-22 |
| CN106423284B true CN106423284B (en) | 2019-01-25 |
Family
ID=58092446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510493370.8A Active CN106423284B (en) | 2015-08-12 | 2015-08-12 | Vinyl acetate catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423284B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111315718B (en) | 2017-08-30 | 2024-02-20 | 埃科莱布美国股份有限公司 | Molecules having one hydrophobic group and two identical hydrophilic ionic groups and compositions thereof |
| US11685709B2 (en) | 2018-08-29 | 2023-06-27 | Ecolab Usa Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and use thereof as reverse emulsion breakers in oil and gas operations |
| US11084974B2 (en) | 2018-08-29 | 2021-08-10 | Championx Usa Inc. | Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations |
| US11292734B2 (en) | 2018-08-29 | 2022-04-05 | Ecolab Usa Inc. | Use of multiple charged ionic compounds derived from poly amines for waste water clarification |
| WO2020047015A1 (en) | 2018-08-29 | 2020-03-05 | Ecolab Usa Inc. | Use of multiple charged cationic compounds derived from primary amines or polyamines for microbial fouling control in a water system |
| EP3843870A1 (en) | 2018-08-29 | 2021-07-07 | Ecolab USA Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and methods of preparation thereof |
| WO2020214196A1 (en) | 2019-04-16 | 2020-10-22 | Ecolab Usa Inc. | Use of multiple charged cationic compounds derived from polyamines and compositions thereof for corrosion inhibition in a water system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693586A (en) * | 1996-06-28 | 1997-12-02 | Hoechst Celanese Corporation | Palladium-gold catalyst for vinyl acetate production |
| 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 |
-
2015
- 2015-08-12 CN CN201510493370.8A patent/CN106423284B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693586A (en) * | 1996-06-28 | 1997-12-02 | Hoechst Celanese Corporation | Palladium-gold catalyst for vinyl acetate production |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106423284A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106423284B (en) | Vinyl acetate catalyst and preparation method thereof | |
| CN106423269B (en) | Unsaturated acetic acid ester catalyst and preparation method thereof | |
| CN104437648B (en) | Vinyl acetate catalyst, preparation method and vinyl acetate synthesis method | |
| CN104437654B (en) | Vinyl acetate catalyst and its preparation method | |
| CN103121952B (en) | Vinyl acetate preparation method | |
| CN105435779B (en) | Carbon monoxide vapor- phase synthesis oxalate catalyst | |
| CN103878023A (en) | Preparation method of catalyst for synthesizing vinyl acetate | |
| CN105727992A (en) | Palladium-nickel series supported hydrogenation catalyst | |
| CN107866277A (en) | The preparation method of vinyl acetate catalyst | |
| CN104119205A (en) | Method for high-selectivity synthesis of ethanol | |
| CN103934037A (en) | Regeneration method of catalyst for vinyl acetate | |
| CN103204835B (en) | A kind of preparation method of butyrolactone | |
| CN103934021B (en) | Acetylene method vinyl acetate catalyst and the synthetic method of vinyl acetate | |
| CN103657735B (en) | The renovation process of allyl acetate commercial plant decaying catalyst | |
| CN112517063B (en) | Preparation method of vinyl acetate catalyst | |
| CN107282105A (en) | Unsaturated acetic acid ester catalyst and preparation method thereof | |
| CN105732267A (en) | Process for the selective hydrogenation of a carbon-containing fraction | |
| CN105732271A (en) | Front hydrogenation method of trace acetylene in methanol-to-olefin device | |
| CN105396584B (en) | CO couplings catalyst for synthesizing oxalic ester, preparation method and its usage | |
| CN107774317B (en) | Catalyst for vinyl acetate synthesis | |
| CN107282137A (en) | The method for preparing catalyst of vinyl acetate | |
| CN103657734B (en) | The renovation process of vinyl acetate commercial plant decaying catalyst | |
| CN107774319B (en) | Catalyst for acetylene method vinyl acetate and preparation method thereof | |
| CN107282136A (en) | The preparation method and vinyl acetate synthesis method of vinyl acetate catalyst | |
| CN108250023A (en) | Method for removing alkyne by hydrogenation in pre-deethanization and pre-hydrogenation process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |