CN1114917A - Catalyzer and carrier for synthetic unsaturated acid ester - Google Patents
Catalyzer and carrier for synthetic unsaturated acid ester Download PDFInfo
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- CN1114917A CN1114917A CN 94112224 CN94112224A CN1114917A CN 1114917 A CN1114917 A CN 1114917A CN 94112224 CN94112224 CN 94112224 CN 94112224 A CN94112224 A CN 94112224A CN 1114917 A CN1114917 A CN 1114917A
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- catalyst
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- per liters
- hollow ring
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Abstract
The catalyst for production of unsaturated acid ester contains such active components as Pb (2.5-4.9 g/l), Au (1-4g/l) and potassium acetate (22-40 g/l) and is used to impregnate on surface of its carrier with specific surface area of 100-250 m square/g. Said catalyst features high space-time output and selectivity and low bed pressure.
Description
The present invention relates to be used for the catalyst and the carrier of synthetic unsaturated acid ester, particularly about the hollow ring catalyst and the carrier of synthesizing vinyl acetate.
Vinyl acetate is important Organic Chemicals, is widely used in to make polyvinyl alcohol, vinyl copolymer resins, aspects such as binding agent, coating, textile processing, paper coating.The main method of producing vinyl acetate in the world today is to be raw material with ethene, oxygen and acetic acid, makes catalyst with palladium-Jin-potassium acetate/silica, and is synthetic by gas phase catalytic reaction.Be to obtain the catalyst that high activity, high selectivity and catalyst bed stressor layer reduce, update at aspects such as the shape of catalyst, preparation technologies.Before and after the sixties, that the shape of fixed bde catalyst mostly is greatly is natural shaped, spherical, strip and cylinder, after the eighties, often catalyst shape is changed into annular or abnormity, but solid often.Document EP 0464633 has proposed catalyst is made the notion of hollow ring, and when using this catalyst, the space time yield of device has had raising than in the past.But the actual demand of industry is that selection of catalysts, space time yield are high more good more, and the catalyst bed stressor layer falls low more good more, and withstand voltage, the scuff resistance of catalyst then should have certain requirement.In order to have under the possible prerequisite of commercial Application in the compressive resistance and the scuff resistance that keep catalyst, obtain the catalyst that higher space time yield and lower bed layer pressure are fallen, we have invented a kind of better catalyst and carrier thereof.
Design of the present invention is to realize by following technical scheme.At first in the silica gel powder, add releasing agent and binding agent, they are fully mixed, be shaped to make and contain at least one duct, be shaped as annular, be of a size of external diameter: 3～10 millimeters, internal diameter is at least 1 millimeter, thickness is not more than 3 millimeters, the hollow ring precursor carrier that height is 3～10 millimeters.Then this hollow ring precursor carrier is dried, drying temperature is 10～40 ℃, and the time is 20～500 hours, carries out drying after drying, and baking temperature is 70～105 ℃, and the time is 4～48 hours, places roasting in the muffle furnace then.Sintering temperature is 350～800 ℃, and roasting time is 1～10 hour, promptly gets the hollow ring carrier after the cooling.If need to regulate its aperture, then further carry out pressurized heat and handle.The pressurization heat-treating methods is that the hollow ring carrier that said method makes is placed in the autoclave, one or more compounds in the salt-mixture that adding acetic acid, ammonium acetate, ammonium hydroxide, ammonium chloride, sodium acid carbonate, sodium sulphate or lithium chloride, sodium chloride, potash, potassium acetate are formed, the solution that is mixed with, heat up, be pressurized to 0.1～10MPa, constant voltage was taken out silica-gel carrier after 2～30 hours, be washed till neutrality with distilled water, and then place in the muffle furnace in 200～500 ℃ of roasting temperatures 1～10 hour, promptly getting specific area after the cooling is 100～250 meters
2The hollow ring carrier of/gram.During the preparation catalyst, the better scope of the specific area of carrier is 140～195 meters
2/ gram.
With the above-mentioned hollow ring carrier impregnation catalyst activity component palladium-Jin-potassium acetate that makes, its consumption is a palladium content: 2.5～4.9 grams per liters, gold content: 1.0～4 grams per liters, potassium acetate content are 22～40 grams per liters, so just obtain can be used for producing unsaturated acid ester, particularly produced the hollow ring catalyst of vinyl acetate.
Get 900 milliliters of above-mentioned catalyst, be positioned in the reaction tube of 30 * 25 * 2450 millimeters of φ, reaction tube is outer to be made up of the chuck that fills conduction oil.Carry out activity of such catalysts and selective evaluation on these 900 milliliters of evaluating apparatus, respond well, space time yield has had significant raising, and obvious reduction falls in bed layer pressure, produces a desired effect.
Embodiment 1
At first in silica white, add releasing agent and binding agent, they are fully mixed, the annular hollow precursor carrier of 5.5 millimeters * 1.8 millimeters * 5.5 millimeters (external diameter * internal diameters * length) is made in shaping, then this annular hollow precursor carrier is dried, drying temperature is 25 ℃, and flash-off time is 48 hours, carry out drying after drying, baking temperature is 100 ℃, and the time is 24 hours, places roasting in the muffle furnace then.Its sintering temperature is 650 ℃, roasting time is 3 hours, put into autoclave after the cooling, the solution that adding acetic acid, ammonium acetate are made into, the solution amount of every liter of hollow ring silica-gel carrier adding is 4 liters, heats up, is forced into 1MPa, constant voltage was taken out carrier after 16 hours, be washed till neutrality with distilled water, place then in the muffle furnace in 450 ℃ of roasting temperatures 3 hours, promptly getting specific area after the cooling is 120 meters
2The hollow ring carrier of/gram.
With the above-mentioned hollow ring carrier impregnation catalyst activity component palladium-Jin-potassium acetate that makes, its consumption is a palladium content: 4.8 grams per liters, gold content are: 3.5 grams per liters, potassium acetate content are 40 grams per liters, have so just made the hollow ring catalyst that can be used for producing vinyl acetate.
With the above-mentioned catalyst that makes, through 900 milliliters of evaluating apparatus evaluations, its result is as follows:
Reactant ratio: ethene: oxygen: acetic acid (mol ratio)=74.8: 5.2: 20
Reaction pressure: 0.8MPa
Reaction temperature: 155 ℃
Air speed: 2000 hours
-1
Selectivity: 92.50%
Space time yield: during 410.0 grams per liters
Bed layer pressure is fallen: 83 millimetress of mercury
Embodiment 2
According to each step of embodiment 1, the specific area of control hollow ring carrier is 150 meters
2/ gram.With the hollow ring carrier impregnation catalyst activity component palladium-Jin-potassium acetate that makes, its consumption is a palladium content: 4.2 grams per liters, gold content are: 1.6 grams per liters, potassium acetate content are 35 grams per liters, have so just made the hollow ring catalyst that can be used for producing vinyl acetate.
With the above-mentioned catalyst that makes, 900 milliliters of evaluating apparatus evaluations, its result is as follows:
Reactant ratio: ethene: oxygen: acetic acid (mol ratio)=74.8: 5.2: 20
Reaction pressure: 0.8MPa
Reaction temperature: 155 ℃
Air speed: 2000 hours
-1
Selectivity: 92.60%
Space time yield: during 440.0 grams per liters
Bed layer pressure is fallen: 84 millimetress of mercury
Embodiment 3
According to each step of embodiment 1, the specific area of control hollow ring carrier is 170 meters
2/ gram.With the hollow ring carrier impregnation catalyst activity component palladium-Jin-potassium acetate that makes, its consumption is a palladium content: 4.0 grams per liters, gold content are: 1.5 grams per liters, potassium acetate content are 30 grams per liters, have so just made the hollow ring catalyst that can be used for producing vinyl acetate.
With the above-mentioned catalyst that makes, 900 milliliters of evaluating apparatus evaluations, its result is as follows:
Reactant ratio: ethene: oxygen: acetic acid (mol ratio)=74.8: 5.2: 20
Reaction pressure: 0.8MPa
Reaction temperature: 155 ℃
Air speed: 2000 hours
-1
Selectivity: 92.90%
Space time yield: during 460.0 grams per liters
Bed layer pressure is fallen: 82 millimetress of mercury
Embodiment 4
According to each step of embodiment 1, the specific area of control hollow ring carrier is 190 meters
2/ gram.With the hollow ring carrier impregnation catalyst activity component palladium-Jin-potassium acetate that makes, its consumption is a palladium content: 3.8 grams per liters, gold content are: 1.7 grams per liters, potassium acetate content are 35 grams per liters, have so just made the hollow ring catalyst that can be used for producing vinyl acetate.
With the above-mentioned catalyst that makes, 900 milliliters of evaluating apparatus evaluations, its result is as follows:
Reactant ratio: ethene: oxygen: acetic acid (mol ratio)=74.8: 5.2: 20
Reaction pressure: 0.8MPa
Reaction temperature: 153 ℃
Air speed: 2500 hours
-1
Selectivity: 92.50%
Space time yield: during 530.0 grams per liters
Bed layer pressure is fallen: 90 millimetress of mercury
Embodiment 5
According to each step of embodiment 1, the specific area of control hollow ring carrier is 240 meters
2/ gram.With the hollow ring carrier impregnation catalyst activity component palladium-Jin-potassium acetate that makes, its consumption is a palladium content: 2.8 grams per liters, gold content are: 1.3 grams per liters, potassium acetate content are 25 grams per liters, have so just made the hollow ring catalyst that can be used for producing vinyl acetate.
With the above-mentioned catalyst that makes, 900 milliliters of evaluating apparatus evaluations, its result is as follows:
Reactant ratio: ethene: oxygen: acetic acid (mol ratio)=74.8: 5.2: 20
Reaction pressure: 0.8MPa
Reaction temperature: 153 ℃
Air speed: 2500 hours
-1
Selectivity: 91.70%
Space time yield: during 500.0 grams per liters
Bed layer pressure is fallen: 90 millimetress of mercury
Claims (3)
1. carrier that is used for synthetic unsaturated acids ester catalyst, it contains at least one duct, be shaped as annular, it is of a size of external diameter: 3～10 millimeters, internal diameter be at least 1 millimeter, thickness be not more than 3 millimeters, highly: 3～10 millimeters, the specific area that it is characterized in that carrier is 100～250 meters
2/ gram.
2. carrier according to claim 1, the specific area that it is characterized in that carrier is 140～195 meters
2/ gram.
3. the catalyst that carrier according to claim 1 is made, the catalyst activity component that impregnated in carrier surface is palladium-Jin-potassium acetate, it is characterized in that palladium content is 2.5～4.9 grams per liters in the catalyst, gold content is that 1.0～4 grams per liters, potassium acetate content are 22～40 grams per liters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94112224 CN1114917A (en) | 1994-07-13 | 1994-07-13 | Catalyzer and carrier for synthetic unsaturated acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94112224 CN1114917A (en) | 1994-07-13 | 1994-07-13 | Catalyzer and carrier for synthetic unsaturated acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1114917A true CN1114917A (en) | 1996-01-17 |
Family
ID=5036016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94112224 Pending CN1114917A (en) | 1994-07-13 | 1994-07-13 | Catalyzer and carrier for synthetic unsaturated acid ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1114917A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657734A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Regeneration method of deactivated catalyst of vinyl acetate industrial device |
-
1994
- 1994-07-13 CN CN 94112224 patent/CN1114917A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657734A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Regeneration method of deactivated catalyst of vinyl acetate industrial device |
| CN103657734B (en) * | 2012-09-05 | 2015-12-09 | 中国石油化工股份有限公司 | The renovation process of vinyl acetate commercial plant decaying catalyst |
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| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |