CN106423284A - Vinyl acetate catalyst and preparing method thereof - Google Patents
Vinyl acetate catalyst and preparing method thereof Download PDFInfo
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Abstract
The invention relates to a vinyl acetate catalyst, and aims to solve the problem that a current vinyl acetate catalyst has low activity and selectivity. According to the preparing method, the vinyl acetate catalyst is adopted, SiO2, Al2O3 or the mixture of the SiO2 and the Al2O3 is used as a carrier, and a loading activity component comprises metal palladium, metal gold, alkali metal acetate and at least one kind of dendritic macromolecular compound in compound 1 and compound 2 specified in the following formula, wherein the catalyst comprises 1-12g/L of palladium, 0.1-10g/L of gold, 10-100g/L of alkali metal acetate and 0.1-2.0 g/L of dendritic macromolecular compound and E t1-E t 16 are independently chosen from a technical scheme of C1-C3 alkyl group. During the preparing process of the vinyl acetate catalyst, the dendritic macromolecular compound is added after dipping palladium compound and gold compound and before a reduction step during the preparing of the catalyst.
Description
Technical field
The present invention relates to vinyl acetate catalyst and preparation method thereof.
Background technology
Vinyl acetate is important industrial chemicals, be widely used in manufacture polyvinyl alcohol, vinyl copolymer resin, binding agent, coating,
The aspects such as textile processing, paper coating.The production process route of vinyl acetate mainly has ethylene process and two kinds of acetylene method, wherein
Ethylene process due to manufacturability, good economy performance and occupy leading status, total production is accounted for using the vinyl acetate production ability of the method
The 82% of ability.The U.S. completes all conversions using ethylene process route in nineteen eighty-three.At present, most countries increase vinegar
The method of sour ethylene yield is to carry out reorganization and expansion and the update of catalyst, the development trend of ethylene process route to original device, returns
Receive and have several aspects：(1) process units scale tends to maximize.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, also has the above Hoechst company VAC
The expansion energy of device；(2) although ethylene process VAC flow process comparative maturity, but still improve, to reduce unit consumption and energy consumption；At present
Advanced ethylene process technique is the Leap technique of Amoco company and the Vantage technique of Celanese company.Acetylene method technique
Plant investment is higher, and environmental protection difficulty is larger, but high with crude oil price, will keep suitable competition over a period to come
Advantage, and directly facilitate the research and development of C1 chemical method.
The main method producing vinyl acetate in the world today is with ethylene, oxygen and acetic acid as raw material, with palladium-gold-potassium acetate/bis-
Silicon oxide makees catalyst, is produced by gas phase catalytic reaction, generates vinyl acetate, water and by-product carbon dioxide, also generates
Micro ethyl acetate, acetaldehyde and other acetoxylation product.The temperature of the reactor shell-side of this 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 provides one kind to prepare and is loaded with major catalyst noble metal, helps and urge
The preparation method of the catalyst of agent metal and alkali metal or alkaline earth metal compound.Catalyst activity and selection that the method obtains
Property is all than relatively low.
Content of the invention
One of the technical problem to be solved is the low problem of vinyl acetate catalyst activity and selectivity in prior art,
There is provided a kind of vinyl acetate catalyst, this catalyst is active and the high feature of selectivity.
The two of the technical problem to be solved are the preparation methoies providing one of above-mentioned technical problem described catalyst.
The two of the technical problem to be solved, are to provide a kind of synthetic method of the vinyl acetate using above-mentioned catalyst.
For solving one of above-mentioned technical problem, technical scheme is as follows：Vinyl acetate catalyst, with SiO2、Al2O3
Or its mixture is carrier, load active component includes Metal Palladium, Aurum metallicum, alkali metal acetate and the change being shown below
At least one dendrimer compound in compound 1 and compound 2, in catalyst the content of palladium be 1～12g/L, gold
Content 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；
Described dendrimer compound be in the preparation process of catalyst dipping palladium compound and gold compound after and
Add before reduction step.
In technique scheme, Et1～Et16It is preferably ethyl.
In technique scheme, described alkali metal acetate is preferably potassium acetate.
In technique scheme, as preferred technical scheme, described dendritic macromole includes compound 1 and compound 2,
Now two kinds of described macromolecular compounds have synergism in terms of improving selectivity.More preferably compound 1 and compound 2 matter
Amount ratio is 1：(0.05～20).
For solving the two of above-mentioned technical problem, technical scheme is as follows：The system of the described catalyst of one of above-mentioned technical problem
Preparation Method, comprises the following steps：
A (), in being dissolved with the solution of containing palladium compound and gold-containing compound, adds carrier impregnation, prepared catalyst precarsor I；
B () processes catalyged precursor I with alkaline compound solution and obtains catalyst precarsor II；
C (), in the solution containing at least one dendrimer compound in compound 1 and compound 2, adds catalysis
Agent precursor II impregnates, and obtains catalyst precarsor III；
D () catalyst precarsor III is dried after, with reducing agent, the gold of the palladium of compound state and compound state is reduced to simple substance, is urged
Agent precursor I V；
E () uses alkali metal acetate solution impregnation catalyst precursor I V, described catalyst is obtained after being dried.
In technique scheme, described containing palladium compound can be the acid of chlorine palladium or chloropalladate, and gold-containing compound can be gold chloride
Or chloroaurate.
In technique scheme, in the solution of described containing palladium compound and gold-containing compound, palladium content is preferably 0.9g/L～12g/L,
Gold content is preferably 0.1g/L～11g/L.
In technique scheme, in the described solution containing dendrimer compound, the concentration of dendritic macromole is preferably
0.09g/L～2.0g/L, dipping temperature is preferably 20～80 DEG C.
In technique scheme, described reducing agent is preferably hydrogen, and reduction temperature is preferably 100～300 DEG C.
In technique scheme, the solution of described dendrimer compound is not particularly limited to solvent, as long as can be institute
State macromole to dissolve, most economical is water.The solution of the dendrimer compound in the specific embodiment of the invention is all
It is the aqueous solution of dendrimer compound.
For solving the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of vinyl acetate, in above-mentioned technology
In the presence of catalyst any one of the technical scheme of one of problem, oxygen is consisted of with molar ratio computing unstripped gas：Ethylene：Nitrogen
Gas：Acetic acid=1：(5～7)：(4～8)：(1～2), reaction pressure is 0.5～0.9MPa, and reaction temperature is 130～200 DEG C, instead
Vinyl acetate should be obtained.
In technique scheme, described feed gas volume air speed is preferably 1600～3000hr-1.
Catalyst leads to catalyst activity and selectivity not enough in commercial Application because noble metal crystal grain active site position is very few, using this
The vinyl acetate catalyst of bright method, is modified using dendrimer compound in noble metal grain surface, can increase
The active site position of noble metal crystal grain, and after modifying, selectivity of catalyst is also improved.Test result indicate that, reaction
Pressure is 0.7MPa, 140 DEG C of reaction temperature, and reacting gas is with molar ratio computing oxygen：Ethylene：Nitrogen：Acetic acid=1：6.8：7.2：
When 1.7, the contrast prior art catalyst space time yield of the catalyst of the present invention brings up to 465g/L by 315g/L, selectivity by
93.5% brings up to 98.5%, achieves preferable technique effect.
Specific embodiment
【Embodiment 1】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml of the compound 1 for 0.12g/L containing concentration, add catalyst precarsor II dipping,
Obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
For the ease of comparing, the preparation condition of catalyst is listed in table 1.
(2) catalyst characterization
Measure the content of each metallic element in catalyst using inductively coupled plasma spectrum generator (ICP), using X-ray
The content of dendritic macromole in fluorescence spectrum (XRF) analysis of catalyst, income analysis characterize data is listed in table 2.
(3) evaluating catalyst
Use fixed bed reactors evaluation, actual conditions is：
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℃；
Response time：500hr；
With the content of component each in gas chromatography analysis product, then calculate catalysts towards ethylene selectivity, gained is tested
Data is listed in table 2.
【Embodiment 2】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml of the compound 2 for 0.12g/L containing concentration, add catalyst precarsor II dipping,
Obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Embodiment 3】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml containing the compound 1 for 0.12g/L for the concentration and compound 2, wherein compound 1
Mass ratio with compound 2 is 1:1, add catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Embodiment 4】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml containing the compound 1 for 0.12g/L for the concentration and compound 2, wherein compound 1
Mass ratio with compound 2 is 1:0.05, add catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Embodiment 5】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml containing the compound 1 for 0.12g/L for the concentration and compound 2, wherein compound 1
Mass ratio with compound 2 is 1:20, add catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Embodiment 6】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 0.92g/L, golden contains
Measure as 0.105g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml containing the compound 1 for 0.092g/L for the concentration and compound 2, wherein compound 1
Mass ratio with compound 2 is 1:1, add catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Embodiment 7】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 11g/L, golden contains
Measure as 10.5g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml containing the compound 1 for 1.84g/L for the concentration and compound 2, wherein compound 1
Mass ratio with compound 2 is 1:1, add catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Embodiment 8】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium hydroxide is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously, standing
24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml containing the compound 1 for 0.12g/L for the concentration and compound 2, wherein compound 1
Mass ratio with compound 2 is 1:1, add catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Embodiment 9】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml containing the compound 1 for 0.12g/L for the concentration and compound 2, wherein compound 1
Mass ratio with compound 2 is 1:1, add catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 100 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Embodiment 10】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml containing the compound 1 for 0.12g/L for the concentration and compound 2, wherein compound 1
Mass ratio with compound 2 is 1:1, add catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 300 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Embodiment 10】
(1) catalyst preparation
Step (a)：Take the solution 1200ml containing potassium chloropalladate and potassium chloroaurate, wherein in solution, the content of palladium is 2.75g/L,
The content of gold is 0.625g/L, and the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml obtains catalyst
Carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Take the solution 1200ml containing the compound 1 for 0.12g/L for the concentration and compound 2, wherein compound 1
Mass ratio with compound 2 is 1:1, add catalyst precarsor II dipping, obtain catalyst precarsor III；
Step (d)：Catalyst precarsor III is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor IV；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Comparative example 1】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, the preparing spherical SiO 2 carrier adding volume to be a diameter of 4～6mm of 1100ml, obtain catalyst carrier I；
Step (b)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (c)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor III；
Step (d)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
【Comparative example 2】
(1) catalyst preparation
Step (a)：Take chlorine palladium acid gold chloride mixed aqueous solution 1200ml, wherein in solution, the content of palladium is 2.75g/L, golden contains
Measure as 0.625g/L, add quality to be the shown compound 1 of 0.36g and the mixture of compound 2 in above-mentioned solution, wherein change
The mass ratio of compound 1 and compound 2 is 1：1, it is prepared into impregnation liquid；
Step (b) adds the preparing spherical SiO 2 carrier that volume is a diameter of 4～6mm of 1100ml in above-mentioned impregnation liquid, obtains
Catalyst precarsor I；
Step (c)：27.5g sodium silicate nanahydrate is made into 100ml aqueous solution be added in catalyst precarsor I, mix homogeneously,
Standing 24hr, is then dried 8hr at 80 DEG C, prepared catalyst precarsor II；
Step (d)：Catalyst precarsor II is reduced in hydrogen atmosphere, hydrogen flow rate is 0.2ml/min, pressure is 0.5MPa,
Reduction temperature is 200 DEG C, obtains catalyst precarsor III；
Step (e)：Dipping acetic acid aqueous solutions of potassium, makes acetic acid potassium content be 30g/L, finished product catalyst is dried.
Catalyst characterization and appreciation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalyst
Physical data, catalysts towards ethylene selectivity are listed in Tables 1 and 2.
By above-described embodiment and comparative example, find that the mixture process palladium-gold catalyst using compound 1 and compound 2 can
More preferably improve the activity and selectivity of catalyst.And after dipping palladium compound and gold compound and by compound state palladium and change
Better if being processed with the mixture of compound 1 and compound 2 before closing state gold reduction.
Table 1. catalyst preparation conditions
Table 2 catalyst physical property and evaluating data
Claims (10)
1. vinyl acetate catalyst, with SiO2、Al2O3Or its mixture be carrier, load active component include Metal Palladium, Aurum metallicum,
At least one dendrimer compound in alkali metal acetate and the compound 1 and compound 2 that are shown below, urges
In agent the content of palladium be 1～12g/L, gold content be 0.1～10g/L, the content of alkali metal acetate be 10～100g/L, tree
Dendritic macromolecules compounds content is 0.1～2.0g/L；
Wherein Et1～Et16It is independently selected from C1～C3Alkyl；
Described dendrimer compound be in the preparation process of catalyst dipping palladium compound and gold compound after and
Add before reduction step.
2. according to claim 1 vinyl acetate catalyst it is characterised in that Et1～Et16For ethyl.
3. according to claim 1 vinyl acetate catalyst it is characterised in that described alkali metal acetate be potassium acetate.
4. the preparation method of catalyst described in claim 1, the method preparation comprising the following steps：
A (), in being dissolved with the solution of containing palladium compound and gold-containing compound, adds carrier impregnation, prepared catalyst precarsor I；
B () processes catalyged precursor I with alkaline compound solution and obtains catalyst precarsor II；
(c) in the solution containing at least one dendrimer compound in compound 1 and compound 2, add catalyst before
Body II impregnates, and obtains catalyst precarsor III；
D () catalyst precarsor III is dried after, with reducing agent, the gold of the palladium of compound state and compound state is reduced to simple substance, obtains catalyst
Precursor I V；
E () uses alkali metal acetate solution impregnation catalyst precursor I V, described catalyst is obtained after being dried.
5. preparation method according to claim 4 is it is characterised in that described containing palladium compound is the acid of chlorine palladium or chloropalladate, containing gold
Compound is gold chloride or chloroaurate.
6. preparation method according to claim 4 it is characterised in that in the solution of described containing palladium compound and gold-containing compound palladium contain
Measure as 0.9g/L～12g/L, gold content is 0.1g/L～11g/L.
7. preparation method according to claim 4 is it is characterised in that branch in the described solution containing dendrimer compound
The concentration of shape macromole is 0.09g/L～2.0g/L, and dipping temperature is 20～80 DEG C.
8. it is characterised in that described reducing agent is hydrogen, reduction temperature is 100～300 DEG C to preparation method according to claim 4.
9. the synthetic method of vinyl acetate, in the presence of catalyst as any one of claims 1 to 3, with molar ratio computing unstripped gas
Consist of oxygen：Ethylene：Nitrogen：Acetic acid=1：(5～7)：(4～8)：(1～2), reaction pressure is 0.5～0.9MPa, reaction
Temperature is 130～200 DEG C, and reaction obtains vinyl acetate.
10. synthetic method according to claim 9, is characterized in that described feed gas volume air speed is 1600～3000hr-1.
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| US11021383B2 (en) | 2017-08-30 | 2021-06-01 | Ecolab Usa Inc. | Use of di-ionic compounds as corrosion inhibitors in a water system |
| US11058111B2 (en) | 2018-08-29 | 2021-07-13 | Ecolab Usa Inc. | Use of multiple charged cationic compounds derived from primary amines or polyamines for microbial fouling control in a water system |
| 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 |
| US11236040B2 (en) | 2018-08-29 | 2022-02-01 | Ecolab Usa Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and methods of preparation thereof |
| 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 |
| US11359291B2 (en) | 2019-04-16 | 2022-06-14 | Ecolab Usa Inc. | Use of multiple charged cationic compounds derived from polyamines and compositions thereof for corrosion inhibition in a water system |
| 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 |
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| US11261113B2 (en) | 2017-08-30 | 2022-03-01 | Ecolab Usa Inc. | Molecules having one hydrophobic group and two identical hydrophilic ionic groups and compositions thereof and methods of preparation thereof |
| US12103881B2 (en) | 2017-08-30 | 2024-10-01 | Ecolab Usa Inc. | Molecules having one hydrophobic group and two identical hydrophilic ionic groups and compositions thereof and methods of preparation thereof |
| US11021383B2 (en) | 2017-08-30 | 2021-06-01 | Ecolab Usa Inc. | Use of di-ionic compounds as corrosion inhibitors in a water system |
| US11565958B2 (en) | 2017-08-30 | 2023-01-31 | Ecolab Usa Inc. | Use of di-ionic compounds as corrosion inhibitors in a water system |
| 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 |
| 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 |
| US11236040B2 (en) | 2018-08-29 | 2022-02-01 | Ecolab Usa Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and methods of preparation thereof |
| 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 |
| US11702586B2 (en) | 2018-08-29 | 2023-07-18 | Championx Usa Inc. | Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations |
| US11926543B2 (en) | 2018-08-29 | 2024-03-12 | Ecolab Usa Inc. | Use of multiple charged ionic compounds derived from polyamines for waste water clarification |
| US12082580B2 (en) | 2018-08-29 | 2024-09-10 | Ecolab Usa Inc. | Use of multiple charged cationic compounds derived from primary amines or polyamines for microbial fouling control in a water system |
| US11058111B2 (en) | 2018-08-29 | 2021-07-13 | Ecolab Usa Inc. | Use of multiple charged cationic compounds derived from primary amines or polyamines for microbial fouling control in a water system |
| US11359291B2 (en) | 2019-04-16 | 2022-06-14 | Ecolab Usa Inc. | Use of multiple charged cationic compounds derived from polyamines and compositions thereof for corrosion inhibition in a water system |
| US11639553B2 (en) | 2019-04-16 | 2023-05-02 | Ecolab Usa Inc. | Compositions comprising multiple charged cationic compounds derived from polyamines for corrosion inhibition in a water system |
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