CN100586567C - Catalyst for preparing vinyl acetate - Google Patents
Catalyst for preparing vinyl acetate Download PDFInfo
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- CN100586567C CN100586567C CN200610116230A CN200610116230A CN100586567C CN 100586567 C CN100586567 C CN 100586567C CN 200610116230 A CN200610116230 A CN 200610116230A CN 200610116230 A CN200610116230 A CN 200610116230A CN 100586567 C CN100586567 C CN 100586567C
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Abstract
The present invention relates to a catalyst for preparing ethylene acetate. Said invention uses SiOz or Al2O3 or their mixture as carrier, on the carrier Pd, Au, KAc and in-situ formed aluminium compound are loaded. Said catalyst can be used in industrial production of ethylene acetate.
Description
Technical field
The present invention relates to a kind of catalyst that is used to prepare vinyl acetate, relate in particular to that to be used for ethene, acetic acid and oxygen or oxygen-containing gas be raw material, the catalyst of Fixed Bed Gas Phase prepared in reaction vinyl acetate.
Background technology
Be raw material with ethene, acetic acid and oxygen or oxygen-containing gas, in the reaction of Fixed Bed Gas Phase prepared in reaction vinyl acetate, with SiO
2, Al
2O
3Perhaps SiO
2With Al
2O
3The mixture of forming is a carrier, and load has Pd, Au and KAc (potassium acetate), and Pd and Au be catalyst that eggshell type distributes for well known to those of ordinary skill in the art on carrier, and this catalyst is by USP4, and 048,096 is disclosed.But this catalyst in preparation process since noble metal especially the adhesion of Au and carrier cause noble metal inadequately especially the loss of Au be serious, make the cost of catalyst higher.ZL97193880.6 adopted for two steps added the holdup that carries that the Au method has significantly improved Au, but this method step is many, compares with traditional catalyst, and the complexity of preparation increases.
Year holdup of noble metal is defined as follows and provides:
Summary of the invention
Technical problem to be solved by this invention is to overcome in the vinyl acetate catalyst of the prior art noble metal to carry holdup on the low side or carry and hold the process complicated problems, and a kind of new catalyst that is used to prepare vinyl acetate is provided.This catalyst has year holdup height of noble metal, the advantage that preparation process is simple, the preparation process cost is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used to prepare vinyl acetate comprises following component by weight percentage:
(A) 60～95% be selected from SiO
2, Al
2O
3Or the carrier of its mixture;
(B) 0.3～3.0% Pd;
(C) 0.01～3.0% Au;
(D) 3.0～15.0% KAc;
(E) 0.02～1.0% generated in-situ Al compound in aluminium;
SiO wherein
2, Al
2O
3Or the specific surface of its mixture carrier is 50～300 meters
2/ gram; Generated in-situ Al compound is at least a in aluminium oxide or the aluminium hydroxide.
In the technique scheme, the consumption preferable range of Pd is 0.6～2.5% by weight percentage; The consumption preferable range of Au is 0.06～1.5% by weight percentage.The consumption preferable range of KAc is 5.0～10.0% by weight percentage.The preferred version of carrier is SiO
2Another preferred version of carrier is the rule or the irregular spheroid of 4～8 mm dias.
The Preparation of catalysts method concrete steps that the present invention is used to prepare vinyl acetate are as follows:
(1) carrier is in the water miscible Pd of containing compound with contain in the solution of Au compound and flood; The volume of maceration extract is about 95-100% of catalyst carrier hygroscopicity value, and preferable range is 98～99%.
(2) the dipping back contacts with alkaline ageing liquid.Described alkaline ageing liquid is sodium metasilicate (potassium) solution, NaOH (potassium) solution that contains sodium aluminate (or potassium aluminate) that contains sodium aluminate (or potassium aluminate), sodium carbonate (potassium) solution that contains sodium aluminate (or potassium aluminate).Sodium aluminate (or potassium aluminate) in the described alkaline ageing liquid can obtain by directly add sodium aluminate (or potassium aluminate) mode in alkali lye, can be by obtaining to the reaction of alkali lye and aluminium hydroxide, also can obtain by aluminium reactant salts such as alkali lye and aluminum nitrate, aluminium chloride, aluminum sulfate.
(3) in containing the liquid phase material of hydrazine hydrate or containing to contain the Pd compound in the nitrogen of ethene and contain the Au compound and be converted into simple substance Pd and simple substance Au.When adopting hydrazine hydrate reduction, the weight ratio of hydrazine hydrate and noble metal is 10: 1～15: 1, and preferable range is 12: 1, and reduction reaction is carried out at normal temperatures.
(4) pure water washing.
(5) with liquor kalii acetici dipping and the dry finished catalyst that gets.
Owing to adopted the ageing liquid that contains aluminium compound in the Preparation of Catalyst of the present invention, make the catalyst finished product contain generated in-situ aluminium compound, increased the adhesion between noble metal and the carrier, year holdup that makes Pd is up to 98.9%, Au's carries holdup up to 97.3%, and do not increase preparation process, reduce catalyst production cost, thereby obtained better technical effect.
Above-mentioned catalyst that makes and comparative catalyst be with the content of aas determination Pd, Au, K and Al well known to those of ordinary skill in the art, through the holdup that carries of noble metal in the content that calculates potassium acetate in the catalyst and the catalyst.
Said method makes catalyst and the comparative catalyst estimates and calculate activity of such catalysts and selectivity with 900 milliliters of fixed bed reactors respectively.Evaluation method is the 900 milliliters of catalyst of packing in reactor, earlier with ethene pressure testing leak test, after confirming not have leakage, the ethene flow is transferred to 82.8 moles/hour, heat up simultaneously, when temperature in the beds reaches 120 ℃, can drop into acetic acid, the acetic acid flow is 12.1 moles/hour, drops into oxygen after half an hour gradually, throw sufficient amount of oxygen after 2 hours and reach 5.63 moles/hour, air speed is 2500 hours
-1Control bed hot(test)-spot temperature is 145 ℃ in the course of reaction, reactor inlet pressure 0.67MPa.
Each components contents in the gc analysis product, and press following formula and calculate space-time yield and selectivity:
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Getting particle diameter and be 4～6 millimeters, specific surface is 120 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 3.78 gram Pd and 1.97 gram Au
2PdCl
4, HAuCl
4448 milliliters of the aqueous solution, dipping rotate 60 milliliters of thread shape addings down and contain 19.3 gram Na for a moment
2SiO
39H
2The ageing liquid of O and 0.66 gram sodium aluminate, under the room temperature static 12 hours then, rotate that to add 74 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the 439 milliliters of dippings of the potassium acetate aqueous solution that contain 29 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 0.72% of this catalyst (3.36 grams per liter), Pd carries holdup 98.0%, Au weight content 0.35% (1.62 grams per liter), and Au carries holdup 91.5%, potassium acetate weight content 5.3% (24.7 grams per liter), aluminium anchoring agent weight content 0.032% (0.15 grams per liter).The space-time yield of this catalyst is 285 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 95.0%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[comparative example 1]
Comparative example for [embodiment 1].
Getting particle diameter and be 4～6 millimeters, specific surface is 120 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 3.77 gram Pd and 1.92 gram Au
2PdCl
4, HAuCl
4448 milliliters of the aqueous solution, rotate thread shape down and add contain identical with [embodiment 1] total alkalinity of 66.0 grams (60 milliliters) and 20.1 restrain Na at dipping a moment
2SiO
39H
2The ageing liquid of O, under the room temperature static 12 hours then, rotate that to add 74 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 28 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 0.71% of this catalyst (3.31 grams per liter), Pd carries holdup 96.5%, Au weight content 0.32% (1.51 grams per liter), Au carries holdup 85.3%, potassium acetate weight content 5.3% (24.5 grams per liter).The space-time yield of this catalyst is 280 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.5%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[embodiment 2]
Getting particle diameter and be 4～6 millimeters, specific surface is 150 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 4.46 gram Pd and 2.12 gram Au
2PdCl
4, HAuCl
4440 milliliters of the aqueous solution, rotate down the thread shape and add 67.2 grams (60 milliliters) and contain 19.0 gram Na at dipping a moment
2SiO
39H
2The ageing liquid of O and 4.84 gram sodium aluminates, under the room temperature static 12 hours then, rotate that to add 93 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 33 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 0.85% of this catalyst (3.97 grams per liter), Pd carries holdup 98.3%, Au weight content 0.38% (1.79 grams per liter), and Au carries holdup 92.3%, potassium acetate weight content 6.2% (29.3 grams per liter), aluminium anchoring agent content 0.22% (1.08 grams per liter).The space-time yield of this catalyst is 342 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.8%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[comparative example 2]
Comparative example for [embodiment 2].
Getting particle diameter and be 4～6 millimeters, specific surface is 150 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 4.38 gram Pd and 2.12 gram Au
2PdCl
4, HAuCl
4440 milliliters of the aqueous solution, rotate thread shape down and add contain identical with [embodiment 2] total alkalinity of 67.5 grams (60 milliliters) and 25.3 restrain Na at dipping a moment
2SiO
39H
2The ageing liquid of O, under the room temperature static 12 hours then, rotate that to add 93 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 33 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
Pd weight content 0.84 gram (3.91 grams per liter) of this catalyst, Pd carries holdup 96.8%, Au weight content 0.36% (1.70 grams per liter), Au carries holdup 87.6%, potassium acetate weight content 6.3% (29.4 grams per liter).The space-time yield of this catalyst is 335 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.3%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[embodiment 3]
Getting particle diameter and be 4～6 millimeters, specific surface is 180 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 4.38 gram Pd and 2.12 gram Au
2PdCl
4, HAuCl
4440 milliliters of the aqueous solution, rotate down the thread shape and add 71.5 grams (65 milliliters) and contain 11.7 gram Na at dipping a moment
2SiO
39H
2The ageing liquid of O and 8.25 gram sodium aluminates, under the room temperature static 12 hours then, rotate that to add 92 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 35 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 0.84% of this catalyst (3.91 grams per liter), Pd carries holdup 98.7%, Au weight content 0.39% (1.84 grams per liter), and Au carries holdup 94.5%, potassium acetate weight content 6.5% (30.2 grams per liter), aluminium anchoring agent content 0.39% (1.82 grams per liter).The space-time yield of this catalyst is 330 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.6%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[comparative example 3]
Comparative example for [embodiment 3].
Getting particle diameter and be 4～6 millimeters, specific surface is 180 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 4.37 gram Pd and 2.13 gram Au
2PdCl
4, HAuCl
4440 milliliters of the aqueous solution, rotate thread shape down and add contain identical with [embodiment 3] total alkalinity of 73.5 grams (65 milliliters) and 26.0 restrain Na at dipping a moment
2SiO
39H
2The ageing liquid of O, under the room temperature static 12 hours then, rotate that to add 92 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 35 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 0.82% of this catalyst (3.80 grams per liter), Pd carries holdup 96.0%, Au weight content 0.36% (1.68 grams per liter), Au carries holdup 86.6%, potassium acetate weight content 6.5% (30.1 grams per liter).The space-time yield of this catalyst is 323 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.2%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[embodiment 4]
Getting particle diameter and be 4～6 millimeters, specific surface is 190 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 6.88 gram Pd and 3.48 gram Au
2PdCl
4, HAuCl
4440 milliliters of the aqueous solution, rotate down the thread shape and add 81.6 grams (70 milliliters) and contain 21.2 gram Na at dipping a moment
2SiO
39H
2The ageing liquid of O and 12.21 gram sodium aluminates, under the room temperature static 12 hours then, rotate that to add 146 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 45 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 1.29% of this catalyst (6.71 grams per liter), Pd carries holdup 98.9%, Au weight content 0.62% (2.97 grams per liter), and Au carries holdup 94.3%, potassium acetate weight content 8.3% (39.6 grams per liter), aluminium anchoring agent weight content 0.56% (2.65 grams per liter).The space-time yield of this catalyst is 526 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 93.9%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[comparative example 4]
Comparative example for [embodiment 4].
Getting particle diameter and be 4～6 millimeters, specific surface is 190 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 6.88 gram Pd and 3.48 gram Au
2PdCl
4, HAuCl
4440 milliliters of the aqueous solution, rotate thread shape down and add contain identical with [embodiment 4] total alkalinity of 84.7 grams (70 milliliters) and 42.4 restrain Na at dipping a moment
2SiO
39H
2The ageing liquid of O, under the room temperature static 12 hours then, rotate that to add 146 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 45 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 1.27% of this catalyst (6.01 grams per liter), Pd carries holdup 96.3%, Au weight content 0.55% (2.60 grams per liter), Au carries holdup 82.5%, potassium acetate weight content 8.3% (39.5 grams per liter).The space-time yield of this catalyst is 513 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 93.5%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[embodiment 5]
Getting particle diameter and be 7～8 millimeters, specific surface is 120 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 3.70 gram Pd and 1.88 gram Au
2PdCl
4, HAuCl
4430 milliliters of the aqueous solution, dipping for a moment, rotating down, the thread shape adds the ageing liquid that 66.2 grams (60 milliliters) contain 12.0 gram sodium aluminates, under the room temperature static 12 hours then, rotate that to add 79 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 29 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 0.73% of this catalyst (3.30 grams per liter), Pd carries holdup 98.5%, Au weight content 0.36% (1.65 grams per liter), and Au carries holdup 95.4%, potassium acetate weight content 5.5% (24.9 grams per liter), aluminium anchoring agent weight content 0.56% (2.56 grams per liter).The space-time yield of this catalyst is 276 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 95.6%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[comparative example 5]
Comparative example for [embodiment 5].
Getting particle diameter and be 7～8 millimeters, specific surface is 120 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 3.70 gram Pd and 1.89 gram Au
2PdCl
4, HAuCl
4430 milliliters of the aqueous solution, rotate thread shape down and add contain identical with [embodiment 5] total alkalinity of 66.2 grams (60 milliliters) and 20.7 restrain Na at dipping a moment
2SiO
39H
2The ageing liquid of O, under the room temperature static 12 hours then, rotate that to add 79 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 29 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 0.73% of this catalyst (3.29 grams per liter), Pd carries holdup 98.2%, Au weight content 0.33% (1.50 grams per liter), Au carries holdup 86.7%, potassium acetate weight content 5.5% (25.0 grams per liter).The space-time yield of this catalyst is 278 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.5%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[embodiment 6]
Getting particle diameter and be 7～8 millimeters, specific surface is 150 meters
2The carrier (containing the silica of 50% weight, hundred umbers and the aluminium oxide of 50% weight, hundred umbers) of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 6.69 gram Pd and 3.31 gram Au
2PdCl
4, HAuCl
4435 milliliters of the aqueous solution, dipping for a moment, rotating down, the thread shape adds the ageing liquid that 71.2 grams (65 milliliters) contain 4.0 gram NaOH and 15.0 gram sodium aluminates, under the room temperature static 12 hours then, rotate that to add 153 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 45 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 1.24% of this catalyst (5.95 grams per liter), Pd carries holdup 98.0%, Au weight content 0.60% (2.90 grams per liter), and Au carries holdup 96.0%, potassium acetate weight content 8.2% (39.4 grams per liter), the anchoring agent weight content is expressed as 0.75% (3.61 grams per liter) with aluminium.The space-time yield of this catalyst is 499 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.3%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[comparative example 6]
Comparative example for [embodiment 6].
Getting particle diameter and be 7～8 millimeters, specific surface is 150 meters
2The carrier (containing the silica of 50% weight, hundred umbers and the aluminium oxide of 50% weight, hundred umbers) of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 6.67 gram Pd and 3.33 gram Au
2PdCl
4, HAuCl
4435 milliliters of the aqueous solution, rotate thread shape down and add contain identical with [embodiment 6] total alkalinity of 74.8 grams (65 milliliters) and 26.0 restrain Na at dipping a moment
2SiO
39H
2The ageing liquid of O, 4.0 gram NaOH, under the room temperature static 12 hours then, rotate that to add 153 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 45 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 1.24% of this catalyst (5.90 grams per liter), Pd carries holdup 97.2%, Au weight content 0.55% (2.61 grams per liter), Au carries holdup 86.4%, potassium acetate weight content 8.3% (39.5 grams per liter).The space-time yield of this catalyst is 495 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 93.3%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[embodiment 7]
Getting particle diameter and be 7～8 millimeters, specific surface is 190 meters
2The alumina support of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 11.50 gram Pd and 5.43 gram Au
2PdCl
4, HAuCl
4450 milliliters of the aqueous solution, rotate down the thread shape and add 151.6 grams (140 milliliters) and contain 15.3 gram Na at dipping a moment
2SiO
39H
2The ageing liquid of O, 8.7 gram NaOH and 8.8 gram sodium aluminates, under the room temperature static 12 hours then, rotate that to add 279 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 48 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 2.08% of this catalyst (10.3 grams per liter), Pd carries holdup 98.9%, Au weight content 0.95% (4.70 grams per liter), and Au carries holdup 95.7%, potassium acetate weight content 8.4% (41.8 grams per liter), the anchoring agent weight content is counted 0.38% (1.90 grams per liter) with aluminium.The space-time yield of this catalyst is 839 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 93.8%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[comparative example 7]
Comparative example for [embodiment 7].
Getting particle diameter and be 7～8 millimeters, specific surface is 190 meters
2The alumina support of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 11.49 gram Pd and 5.40 gram Au
2PdCl
4, HAuCl
4450 milliliters of the aqueous solution, rotate thread shape down and add contain identical with [embodiment 7] total alkalinity of 157.9 grams (140 milliliters) and 42.4 restrain Na at dipping a moment
2SiO
39H
2The ageing liquid of O and 8.7 gram NaOH, under the room temperature static 12 hours then, rotate that to add 279 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 48 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 2.03% of this catalyst (9.97 grams per liter), Pd carries holdup 95.4%, Au weight content 0.88% (4.32 grams per liter), Au carries holdup 88.0%, potassium acetate weight content 8.6% (42.0 grams per liter).The space-time yield of this catalyst is 821 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 93.0%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[embodiment 8]
Getting particle diameter and be 7～8 millimeters, specific surface is 190 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 16.67 gram Pd and 10.16 gram Au
2PdCl
4, HAuCl
4448 milliliters of the aqueous solution, rotate down the thread shape and add 155.3 grams (140 milliliters) and contain 20.3 gram Na at dipping a moment
2SiO
39H
2The ageing liquid of O, 11.6 gram NaOH and 11.7 gram sodium aluminates, under the room temperature static 12 hours then, rotate that to add 442 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 72 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 3.01% of this catalyst (14.95 grams per liter), Pd carries holdup 98.7%, Au weight content 1.78% (8.84 grams per liter), and Au carries holdup 95.8%, potassium acetate weight content 12.8% (63.6 grams per liter), aluminium anchoring agent weight content 0.57% (2.83 grams per liter).The space-time yield of this catalyst is 1210 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.5%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[comparative example 8]
Comparative example for [embodiment 8].
Getting particle diameter and be 7～8 millimeters, specific surface is 190 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 16.69 gram Pd and 10.98 gram Au
2PdCl
4, HAuCl
4448 milliliters of the aqueous solution, rotate thread shape down and add contain identical with [embodiment 1] total alkalinity of 163.8 grams (140 milliliters) and 56.4 restrain Na at dipping a moment
2SiO
39H
2The ageing liquid of O and 11.6 gram NaOH, under the room temperature static 12 hours then, rotate that to add 442 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 72 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 2.90% of this catalyst (14.40 grams per liter), Pd carries holdup 95.0%, Au weight content 1.76% (9.24 grams per liter), Au carries holdup 87.6%, potassium acetate weight content 12.72% (63.2 grams per liter).The space-time yield of this catalyst is 1165 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.3%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[embodiment 9]
Getting particle diameter and be 4～6 millimeters, specific surface is 120 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 2.68 gram Pd and 0.95 gram Au
2PdCl
4, HAuCl
4448 milliliters of the aqueous solution, rotate down the thread shape and add 63.9 grams (60 milliliters) and contain 12.2 gram Na at dipping a moment
2SiO
39H
2The ageing liquid of O and 0.41 gram sodium aluminate, under the room temperature static 12 hours then, rotate that to add 48 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the 439 milliliters of dippings of the potassium acetate aqueous solution that contain 21 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 0.51% of this catalyst (2.38 grams per liter), Pd carries holdup 98.0%, Au weight content 0.18% (0.84 grams per liter), and Au carries holdup 97.3%, potassium acetate weight content 3.81% (17.8 grams per liter), aluminium anchoring agent weight content 0.022% (0.103 grams per liter).The space-time yield of this catalyst is 195 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 95.3%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
[comparative example 9]
Comparative example for [embodiment 9].
Getting particle diameter and be 4～6 millimeters, specific surface is 120 meters
2The silica supports of/gram is put 5 liters for 1.1 liters to be changeed in the pot, opens and changes pot, and rotating speed is 10 rev/mins, adds the Na that contains 2.67 gram Pd and 1.05 gram Au
2PdCl
4, HAuCl
4448 milliliters of the aqueous solution, rotate thread shape down and add contain identical with [embodiment 9] total alkalinity of 63.9 grams (60 milliliters) and 12.7 restrain Na at dipping a moment
2SiO
39H
2The ageing liquid of O, under the room temperature static 12 hours then, rotate that to add 48 gram concentration down be that the hydrazine hydrate of 85% (weight) leaves standstill reduction 4 hours, use deionized water rinsing negative to the reaction of 0.1 mol silver nitrate then until eluate.100 ℃ dry 4 hours down, be cooled to after the room temperature with the potassium acetate aqueous solution incipient impregnation that contains 21 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture content and obtain catalyst prod less than 2%.
The Pd weight content 0.50% of this catalyst (2.34 grams per liter), Pd carries holdup 96.5%, Au weight content 0.18% (0.84 grams per liter), Au carries holdup 88.2%, potassium acetate weight content 3.86% (18.1 grams per liter).The space-time yield of this catalyst is 191 grams per liters hour, and the Dichlorodiphenyl Acetate selectivity of ethylene is 94.8%.
For ease of relatively, rerum natura, Preparation of catalysts condition, the rerum natura of catalyst and the detailed data of catalytic performance of carrier are listed in table 1, table 2 and the table 3 respectively.
The physical data of table 1 carrier
| Carrier is formed | Particle diameter (millimeter) | Specific surface (rice 2/ gram) | Bulk density (grams per liter) | Hygroscopicity value (weight %) | |
| Embodiment 1 | Silica | 4～6 | 120 | 436 | 93.5 |
| Comparative example 1 | Silica | 4～6 | 120 | 436 | 93.5 |
| Embodiment 2 | Silica | 4～6 | 150 | 432 | 92.8 |
| Comparative example 2 | Silica | 4～6 | 150 | 432 | 92.8 |
| Embodiment 3 | Silica | 4～6 | 180 | 428 | 94.1 |
| Comparative example 3 | Silica | 4～6 | 180 | 428 | 94.1 |
| Embodiment 4 | Silica | 4～6 | 190 | 425 | 94.8 |
| Comparative example 4 | Silica | 4～6 | 190 | 425 | 94.8 |
| Embodiment 5 | Silica | 7～8 | 120 | 421 | 93.5 |
| Comparative example 5 | Silica | 7～8 | 120 | 421 | 93.5 |
| Embodiment 6 | 50% silica+50% aluminium oxide | 7～8 | 150 | 429 | 92.8 |
| Comparative example 6 | 50% silica+50% aluminium oxide | 7～8 | 150 | 429 | 92.8 |
| Embodiment 7 | Aluminium oxide | 7～8 | 190 | 434 | 94.8 |
| Comparative example 7 | Aluminium oxide | 7～8 | 190 | 434 | 94.8 |
| Embodiment 8 | Silica | 7～8 | 190 | 434 | 94.8 |
| Comparative example 8 | Silica | 7～8 | 190 | 434 | 94.8 |
| Embodiment 9 | Silica | 4～6 | 120 | 436 | 93.5 |
| Comparative example 9 | Silica | 4～6 | 120 | 436 | 93.5 |
Claims (6)
1, a kind of catalyst that is used to prepare vinyl acetate comprises following component by weight percentage:
(A) 60～95% be selected from SiO
2, Al
2O
3Or the carrier of its mixture;
(B) 0.3～3.0% Pd;
(C) 0.01～3.0% Au;
(D) 3.0～15.0% KAc;
(E) 0.02～1.0% generated in-situ Al compound in aluminium;
SiO wherein
2, Al
2O
3Or the specific surface of its mixture carrier is 50～300 meters
2/ gram; Generated in-situ Al compound is at least a in aluminium oxide or the aluminium hydroxide.
2, the catalyst that is used to prepare vinyl acetate according to claim 1 is characterized in that the consumption of Pd is 0.6～2.5% by weight percentage.
3, the catalyst that is used to prepare vinyl acetate according to claim 1 is characterized in that the consumption of Au is 0.06～1.5% by weight percentage.
4, the catalyst that is used to prepare vinyl acetate according to claim 1 is characterized in that the consumption of KAc is 5.0～10.0% by weight percentage.
5, the catalyst that is used to prepare vinyl acetate according to claim 1 is characterized in that carrier is SiO
2
6, the catalyst that is used to prepare vinyl acetate according to claim 1 is characterized in that carrier is the rule or the irregular spheroid of 4～8 mm dias.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610116230A CN100586567C (en) | 2006-09-20 | 2006-09-20 | Catalyst for preparing vinyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610116230A CN100586567C (en) | 2006-09-20 | 2006-09-20 | Catalyst for preparing vinyl acetate |
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|---|---|
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| CN100586567C true CN100586567C (en) | 2010-02-03 |
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| CN104437624B (en) * | 2013-09-24 | 2016-09-07 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof and vinyl acetate synthesis method |
| JP6366841B2 (en) * | 2015-06-29 | 2018-08-01 | 昭和電工株式会社 | Method for producing allyl acetate |
| WO2018093915A1 (en) * | 2016-11-17 | 2018-05-24 | Lyondellbasell Acetyls, Llc | High pore volume alumina supported catalyst for vinyl acetate monomer (vam) process |
| CN114425444B (en) * | 2020-10-14 | 2024-01-26 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
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