CN107774309A - For synthesizing the catalyst used in acetylene method vinyl acetate - Google Patents
For synthesizing the catalyst used in acetylene method vinyl acetate Download PDFInfo
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- CN107774309A CN107774309A CN201610750379.7A CN201610750379A CN107774309A CN 107774309 A CN107774309 A CN 107774309A CN 201610750379 A CN201610750379 A CN 201610750379A CN 107774309 A CN107774309 A CN 107774309A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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Abstract
The present invention relates to for synthesizing the catalyst used in acetylene method vinyl acetate, mainly solve the problems, such as acetylene in gas phase method poor catalyst stability in the prior art.The present invention is using for synthesizing the catalyst used in acetylene method vinyl acetate, the catalyst uses activated carbon as carrier, active component includes zinc acetate and co-catalyst, the co-catalyst is included selected from least one of metalloid metallic element and the technical scheme selected from least one of platinum group metal metallic element, preferably solves the problem, in the industrial production available for acetylene in gas phase method synthesizing vinyl acetate.
Description
Technical field
The present invention relates to for synthesizing the catalyst used in acetylene method vinyl acetate, the acetylene in gas phase method vinyl acetate is urged
The preparation method of agent and the synthetic method of acetylene in gas phase method vinyl acetate.
Background technology
Vinyl acetate (Vinyl acetate, abbreviation VAC) it is important Organic Chemicals, it is poly- to be widely used in manufacture
Vinyl acetate, polyvinyl alcohol simultaneously are processed further being used for binding agent, coating, vinylon fibre, fabric processing, emulsion, resin and thin
Film etc..At present, the method for industrial production vinyl acetate has acetylene in gas phase method and ethene vapor phase method.
Producing vinyl acetate by acetylene method experienced two developing stage of liquid and gas technique.Before 1940, mainly
Based on liquid phase process, reacted under 30~70 DEG C of normal pressures, catalyst is mercury oxide and sulfuric acid or phosphoric acid；40 years 20th century
After generation, start based on acetylene in gas phase method, catalyst is the activated carbon for having loaded zinc acetate.
Nineteen twenty-two Germany Wacker company Muqaen has found that the zinc acetate of dipping on the activated carbon can be with vapor- phase synthesis acetic acid
Ethene, the method using acetylene in gas phase synthesis VAc is then proposed, input industrial production is improved by Hochst companies.It is catalyzed
Agent is with Zn (OAc)2For active component, using activated carbon as carrier, and use till today always.United States Patent (USP) (US166482,
Production of vinyl acetate) report using catalyst Z n (OAc)2/ C, has synthesized vinyl acetate.It is Chinese special
Sharp CN1903435 is (entitled：A kind of catalyst for vinyl acetate synthesis and preparation method thereof) provide a kind of acetylene method
The preparation method of vinyl acetate catalyst, catalyst activity component uses zinc oxide and acetic acid, and adds a small amount of waltherite, by it
It is immersed in activated carbon and is dried to obtain catalyst.But the catalyst activity that above-mentioned technology provides is not high, stability difference and catalyst
Active reduced rate is too big and the problem of catalyst life is short, so as to limit the application of acetylene method vinyl acetate.
The content of the invention
One of technical problems to be solved by the invention are that acetylene method vinyl acetate catalyst stability is poor in the prior art
With catalyst activity reduced rate it is too big the problem of, there is provided it is a kind of it is new be used to synthesize the catalyst used in acetylene method vinyl acetate,
The catalyst stability is good, and has the characteristics of low catalyst activity reduced rate and long lifespan.
The two of the technical problems to be solved by the invention are the producers using one of the above-mentioned technical problem catalyst
Method.
The three of the technical problems to be solved by the invention are the acetic acid second using one of the above-mentioned technical problem catalyst
The synthetic method of alkene.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：For synthesizing acetylene method acetic acid second
Catalyst used in alkene, the catalyst use activated carbon as carrier, and active component includes zinc acetate and co-catalyst, described to help
Catalyst is included selected from least one of metalloid metallic element and selected from least one of platinum group metal metallic element.
In above-mentioned technical proposal, can with or without alkali metal acetate, more specifically can with or without potassium acetate,
Alkali metal acetate is unfavorable to the stability for improving catalyst, causes catalyst activity reduced rate larger.
When co-catalyst agent includes metalloid element and platinum group, improved between above-mentioned two race metallic element
There is synergy in terms of the space-time yield and reduction catalyst activity reduced rate of vinyl acetate catalyst.
In above-mentioned technical proposal, the activated carbon preferably is selected from ature of coal column charcoal, cocoanut active charcoal, apricot shell activated carbon and bamboo matter
At least one of activated carbon.
In above-mentioned technical proposal, the specific surface area of the activated carbon is preferably 1000~1500cm2/ g, absorption pore volume are preferred
For 0.60~1.00cm3/g。
In above-mentioned technical proposal, the metalloid element preferably is selected from least one of boron, arsenic and tellurium.
In above-mentioned technical proposal, the platinum group preferably is selected from least one of platinum, palladium, osmium, iridium, ruthenium and rhodium.
As one of preferable technical scheme, the metalloid element includes tellurium, the platinum group include platinum or
Palladium, now improving the space-time yield of vinyl acetate catalyst between metalloid element and the race's element of platinum group two and subtracting
There is synergy in terms of small catalyst activity reduced rate.
As another preferable technical scheme, the metalloid element includes tellurium or boron, the platinum group bag
Palladium and platinum are included, now the space-time yield of vinyl acetate catalyst is being improved between palladium and platinum and is reducing catalyst activity reduced rate side
Face has synergy.
As the 3rd preferable technical scheme, the metalloid element includes tellurium and boron, the platinum group bag
Palladium and platinum are included, now the space-time yield of vinyl acetate catalyst is being improved between tellurium and boron and is reducing catalyst activity reduced rate side
Face has synergy.
In above-mentioned technical proposal, the content of zinc acetate is preferably 50~300g/L in the catalyst, more preferably 80~
200g/L。
In above-mentioned technical proposal, cocatalyst content is preferably 0.50~8.00g/L in the catalyst, more preferably
1.00~5.00g/L.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The production method of catalyst described in case, comprises the following steps：
1. the solution of zinc acetate, co-catalyst is mixed with carrier by the composition of catalyst；
2. dry.
In above-mentioned technical proposal, as non-restrictive, the compound of the step 1. metalloid element preferably is selected from boron
At least one of acid, ammonium pentaborate, dimethylamino monoborane, arsenic acid, arsenic trichloride, ammonium tellurate, tellurium dioxide and telluric acid；More
It is preferred that at least one of ammonium pentaborate and ammonium tellurate.
In above-mentioned technical proposal, as non-restrictive, the compound of the step 1. platinum group preferably is selected from
Radium chloride, the part of rhodium acetate two, triphenylphosphine chlorine rhodium, rhodium nitrate, palladium bichloride, the ammonia palladium of dichloro four, palladium, ammonium chloropalladite,
Ruthenic chloride, cross ruthenic acid four in amine, acetic acid ruthenium, platinous chloride, ammonium chloroplatinite, chloroplatinic acid, platinum acetate, osmium trichloride, acetic acid osmium,
At least one of iridous chloride, acetic acid iridium and chloro-iridic acid.
In above-mentioned technical proposal, 2. the drying temperature is preferably 80~120 DEG C to step, more preferably 100~120 DEG C.
To solve the three of above-mentioned technical problem, technical scheme is as follows：Vinyl acetate synthesis method, with acetic acid,
Acetylene is raw material, the reaction generation acetic acid in the presence of catalyst described in any one of technical scheme of one of above-mentioned technical problem
Ethene.
The key of the present invention is the selection of catalyst, and skilled person will know how suitable according to determination is actually needed
Reaction temperature, the reaction time, the proportioning of reaction pressure and material.But the temperature reacted in above-mentioned technical proposal is preferably
150~200 DEG C；The pressure of reaction is preferably 0.1~0.5MPa；Preferably acetylene is formed with molar ratio computing raw material:Acetic acid=(5
~12):1；Raw material volume air speed is preferably 250~350h-1。
The content gas chromatography analysis of each component in reaction product of the present invention, and calculate catalyst space-time yield and
The reduced rate of catalyst activity.
Evaluating catalyst reaction carries out 480h, and the average space-time yield of the catalyst to react initial 10 hours characterizes catalyst
Space-time yield is originated, the average space-time yield of the catalyst to react last 10 hours characterizes the termination space-time yield of catalyst.Urge
The calculation formula of the reduced rate of agent activity is as follows：
The active lifetime of the lower expression catalyst of active reduced rate of catalyst is longer, and catalyst activity stability is higher.
Compared with prior art, key of the invention is that the active component of catalyst includes zinc acetate and selected from metalloid
At least one of metallic element and selected from least one of platinum group metal metallic element, be advantageous to improve the stabilization of catalyst
Property, catalyst activity reduced rate is reduced, so as to reach the catalyst life for improving vinyl acetate.
Test result indicates that during using catalyst of the present invention, after catalyst reaction 480h, the active reduced rate of catalyst is only
Have 3.81%, achieve active component in preferable technique effect, especially catalyst while include zinc acetate, selected from metalloid
At least one of metallic element and during selected from least one of platinum group metal metallic element, achieve more prominent technology
Effect, available in the industrial production of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the ammonium tellurate ((NH of the Te containing 3.38g4)2TeO4) fill
Mixed dissolution is divided maceration extract 350ml to be obtained, by 1L diameters 3mm, long 2cm, pore volume in the aqueous acetic acid that concentration is 10wt%
For 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal cylindrical activated carbon carrier impregnation stands 3h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The acetic acid Zn content for determining or converting the catalyst through ICP is 105g/L, Te contents
3.38g/L。
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 162.43g/Lh, and the termination space-time yield of 480h rear catalysts is
156.24g/Lh, the active reduced rate of catalyst is 3.81%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
【Embodiment 2】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the ammonium chloroplatinite ((NH of the Pt containing 3.38g4)2PtCl4) be sufficiently mixed be dissolved in concentration be 10wt% aqueous acetic acid in, maceration extract 350ml is obtained, by 1L diameters 3mm, length
2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal cylindrical activated carbon carrier impregnation is in above-mentioned maceration extract
In, 3h is stood in 100 DEG C of dryings, obtains the catalyst.It is through ICP measure or the acetic acid Zn content for converting the catalyst
105g/L, Pt content 3.38g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 162.22g/Lh, and the termination space-time yield of 480h rear catalysts is
155.71g/Lh, the active reduced rate of catalyst is 4.01%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2) be completely dissolved in concentration be 10wt% acetic acid it is water-soluble
In liquid, maceration extract 350ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g coal
Matter cylindrical activated carbon carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Surveyed through ICP
Acetic acid Zn content that is fixed or converting the catalyst is 105g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 120.14g/Lh, and the termination space-time yield of 480h rear catalysts is
107.30g/Lh, the active reduced rate of catalyst is 10.69%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing zinc acetate, telluric acid
Ammonium active component while catalyst performance ratio containing zinc acetate, ammonium chloroplatinite active component is urged containing only zinc acetate active component
The performance of agent is more excellent, and the stability of vinyl acetate catalyst will get well, and the reduced rate of catalyst activity is lower, is carried so as to reach
The life-span of high vinyl acetate catalyst.This absolutely proved in catalyst of the present invention active component and meanwhile including zinc acetate, be selected from
At least one of metalloid metallic element and during selected from least one of platinum group metal metallic element, improves vinyl acetate
The stability and reduction catalyst activity reduced rate of catalyst.
【Embodiment 3】
The preparation of catalyst：80g zinc acetates (Zn (OAc) will be contained2), the rhodium acetate (Rh of the Rh containing 1.00g2(OAc)4) fully
Mixed dissolution obtains maceration extract 350ml, is by 1L diameters 3mm, long 2cm, pore volume in the aqueous acetic acid that concentration is 10wt%
0.60cm3/ g, specific surface area 1000cm2/ g cylindrical type cocoanut active charcoal carrier impregnation in above-mentioned maceration extract, stand 3h in
80 DEG C of dryings, obtain the catalyst.The acetic acid Zn content for determining or converting the catalyst through ICP is 80g/L, Rh contents
1.00g/L。
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 102.32g/Lh, and the termination space-time yield of 480h rear catalysts is
98.25g/Lh, the active reduced rate of catalyst is 3.98%.For convenience of description and compare, it is the preparation condition of catalyst, anti-
Condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate is answered to be listed in table 1 and table respectively
2。
【Embodiment 4】
The preparation of catalyst：200g zinc acetates (Zn (OAc) will be contained2), the acetic acid ruthenium (Ru (OAc) of the Ru containing 5.00g3·
3H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, maceration extract 350ml is obtained, by 1L diameters 3mm, length
2cm, pore volume 1.00cm3/ g, specific surface area 1500cm2/ g cylindrical type apricot shell absorbent charcoal carrier is immersed in above-mentioned maceration extract
In, 3h is stood in 120 DEG C of dryings, obtains the catalyst.It is through ICP measure or the acetic acid Zn content for converting the catalyst
200g/L, Ru content 5.00g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 163.36g/Lh, and the termination space-time yield of 480h rear catalysts is
156.87g/Lh, the active reduced rate of catalyst is 3.97%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
【Embodiment 5】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the palladium (Pd (OAc) of the Pd containing 3.38g2) fully
Mixed dissolution obtains maceration extract 350ml, is by 1L diameters 3mm, long 2cm, pore volume in the aqueous acetic acid that concentration is 10wt%
0.80cm3/ g, specific surface area 1200cm2/ g cylindrical type activated carbon from bamboo carrier impregnation in above-mentioned maceration extract, stand 3h in
120 DEG C of dryings, obtain the catalyst.The acetic acid Zn content for determining or converting the catalyst through ICP is 105g/L, Pd contents
3.38g/L。
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 162.27g/Lh, and the termination space-time yield of 480h rear catalysts is
155.84g/Lh, the active reduced rate of catalyst is 3.96%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
【Embodiment 6】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), chlorine osmic acid the ammonium ((NH of the Os containing 3.38g4)2OsCl6·3H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, maceration extract 350ml is obtained, by 1L diameters
3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal cylindrical activated carbon carrier impregnation is above-mentioned
In maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The acetic acid Zn content of the catalyst is determined or converted through ICP
For 105g/L, Os contents 3.38g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System fully purges, and after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, instead
It is 0.25MPa to answer pressure；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 162.25g/Lh, and the termination space-time yield of 480h rear catalysts is
155.74g/Lh, the active reduced rate of catalyst is 4.01%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
【Embodiment 7】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the acetic acid iridium (Ir (OAc) of the Ir containing 3.38g3·
3H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, maceration extract 350ml is obtained, by 1L diameters 3mm, length
2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal cylindrical activated carbon carrier impregnation is in above-mentioned maceration extract
In, 3h is stood in 100 DEG C of dryings, obtains the catalyst.It is through ICP measure or the acetic acid Zn content for converting the catalyst
105g/L, Ir content 3.38g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 150 DEG C, reaction
Pressure is 0.10MPa；Raw material volume air speed：250h-1；Raw material forms：Acetylene/acetic acid mol ratio=5:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 151.88g/Lh, and the termination space-time yield of 480h rear catalysts is
145.77g/Lh, the active reduced rate of catalyst is 4.02%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
【Embodiment 8】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the ammonium pentaborate ((NH of the B containing 3.38g4)B5O8·
8H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, maceration extract 350ml is obtained, by 1L diameters 3mm, length
2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal cylindrical activated carbon carrier impregnation is in above-mentioned maceration extract
In, 3h is stood in 100 DEG C of dryings, obtains the catalyst.It is through ICP measure or the acetic acid Zn content for converting the catalyst
105g/L, B content 3.38g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 200 DEG C, reaction
Pressure is 0.50MPa；Raw material volume air speed：350h-1；Raw material forms：Acetylene/acetic acid mol ratio=12:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 163.01g/Lh, and the termination space-time yield of 480h rear catalysts is
156.69g/Lh, the active reduced rate of catalyst is 3.88%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
【Embodiment 9】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the ammonium tellurate ((NH of the Te containing 1.63g4)2TeO4) and
The ammonium chloroplatinite ((NH of the Pt containing 1.75g4)2PtCl4) be sufficiently mixed be dissolved in concentration be 10wt% aqueous acetic acid in, obtain
To maceration extract 350ml, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal cylinder
Shaped activated carbon carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Determine or roll over through ICP
The acetic acid Zn content for calculating the catalyst is 105g/L, Te contents 1.63g/L, Pt content 1.75g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 164.44g/Lh, and the termination space-time yield of 480h rear catalysts is
159.31g/Lh, the active reduced rate of catalyst is 3.12%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
Found out on year-on-year basis by embodiment 9 and embodiment 1 and embodiment 2, improve vinyl acetate catalyst stability and
In terms of reducing catalyst activity reduced rate, in the catalyst that the present invention uses, in metalloid in metallic element Te and platinum group metal
Metallic element Pt has preferable synergy, illustrates improving catalyst between zinc acetate, ammonium tellurate and ammonium chloroplatinite
There is preferable cooperative effect in terms of stability and reduction catalyst activity reduced rate.
【Embodiment 10】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the ammonium tellurate ((NH of the Te containing 1.63g4)2TeO4) and
Palladium (the Pd (OAc) of the Pd containing 1.75g2) be sufficiently mixed be dissolved in concentration be 10wt% aqueous acetic acid in, impregnated
Liquid 350ml, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal is cylindrical activated
High-area carbon is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.Determine through ICP or convert this and urge
The acetic acid Zn content of agent is 105g/L, Te contents 1.63g/L, Pd content 1.75g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 164.35g/Lh, and the termination space-time yield of 480h rear catalysts is
159.14g/Lh, the active reduced rate of catalyst is 3.17%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
【Embodiment 11】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the ammonium tellurate ((NH of the Te containing 1.63g4)2TeO4)、
The ammonium chloroplatinite ((NH of the Pt containing 1.13g4)2PtCl4) and the Pd containing 0.62g palladium (Pd (OAc)2) it is sufficiently mixed dissolving
In the aqueous acetic acid that concentration is 10wt%, maceration extract 350ml is obtained, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/
G, specific surface area is 1200cm2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for/g ature of coal cylindrical activated carbon carrier impregnation
It is dry, obtain the catalyst.The acetic acid Zn content for determining or converting the catalyst through ICP is 105g/L, Te content 1.63g/L,
Pt contents 1.13g/L, Pd content 0.62g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 167.29g/Lh, and the termination space-time yield of 480h rear catalysts is
163.17g/Lh, the active reduced rate of catalyst is 2.46%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
Found out on year-on-year basis by embodiment 11 and embodiment 9 and embodiment 10, improving the stability of vinyl acetate catalyst
In terms of catalyst activity reduced rate is reduced, in the catalyst that the present invention uses, metallic element Te and platinum group metal in metalloid
Middle metallic element Pt, Pd and between have synergy.Illustrate between zinc acetate, ammonium tellurate, ammonium chloroplatinite and palladium
There is preferable cooperative effect in terms of improving the stability of catalyst and reducing catalyst activity reduced rate.
【Embodiment 12】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the ammonium pentaborate ((NH of the B containing 1.63g4)B5O8·
8H2O), the ammonium chloroplatinite ((NH of the Pt containing 1.13g4)2PtCl4) and the Pd containing 0.62g palladium (Pd (OAc)2) be sufficiently mixed
It is dissolved in the aqueous acetic acid that concentration is 10wt%, obtains maceration extract 350ml, be by 1L diameters 3mm, long 2cm, pore volume
0.80cm3/ g, specific surface area 1200cm2/ g ature of coal cylindrical activated carbon carrier impregnation in above-mentioned maceration extract, stand 3h in
100 DEG C of dryings, obtain the catalyst.The acetic acid Zn content for determining or converting the catalyst through ICP is 105g/L, B content
1.63g/L, Pt content 1.13g/L, Pd content 0.62g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 167.42g/Lh, and the termination space-time yield of 480h rear catalysts is
163.17g/Lh, the active reduced rate of catalyst is 2.54%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
【Embodiment 13】
The preparation of catalyst：105g zinc acetates (Zn (OAc) will be contained2), the ammonium tellurate ((NH of the Te containing 1.18g4)2TeO4)、
The ammonium pentaborate ((NH of the B containing 0.45g4)B5O8·8H2O), the ammonium chloroplatinite ((NH of the Pt containing 1.13g4)2PtCl4) and contain
0.62g Pd palladium (Pd (OAc)2) be sufficiently mixed be dissolved in concentration be 10wt% aqueous acetic acid in, obtain maceration extract
350ml, by 1L diameters 3mm, long 2cm, pore volume 0.80cm3/ g, specific surface area 1200cm2/ g ature of coal cylindrical activated carbon
Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalysis is determined or converted through ICP
The acetic acid Zn content of agent is 105g/L, Te content 1.18g/L, B content 0.45g/L, Pt content 1.13g/L, Pd content 0.62g/
L。
The synthesis of vinyl acetate：By 30ml Catalyst packings in micro fixed-bed reactor, N2After leak test, N is used2To being
System fully purging, after system heating, closes N2, acetylene is cut successively, opens acetic acid pump, and controlling reaction temperature is 175 DEG C, reaction
Pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=6:1, sustained response 480h
Afterwards, reaction is stopped.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The starting space-time yield for being computed catalyst is 168.90g/Lh, and the termination space-time yield of 480h rear catalysts is
165.99g/Lh, the active reduced rate of catalyst is 1.72%.For convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the starting of catalyst, termination space-time yield and catalyst activity reduced rate are listed in the and of table 1 respectively
Table 2.
Found out on year-on-year basis by embodiment 13 and embodiment 11 and embodiment 12, improving the stability of vinyl acetate catalyst
In terms of catalyst activity reduced rate is reduced, in the catalyst that the present invention uses, metallic element Te, B and platinum family gold in metalloid
There is synergy in category between metallic element Pt, Pd.Illustrate zinc acetate, ammonium tellurate, ammonium pentaborate, ammonium chloroplatinite and vinegar
There is preferable cooperative effect in terms of improving the stability of catalyst and reducing catalyst activity reduced rate between sour palladium.
Table 1
Table 2
Claims (10)
1. for synthesizing the catalyst used in acetylene method vinyl acetate, the catalyst uses activated carbon as carrier, active component
Including zinc acetate and co-catalyst, the co-catalyst is included selected from least one of metalloid metallic element and selected from platinum family
At least one of metal metallic element.
2. catalyst according to claim 1, it is characterised in that the activated carbon be ature of coal column charcoal, cocoanut active charcoal,
At least one of apricot shell activated carbon and activated carbon from bamboo.
3. catalyst according to claim 1, it is characterised in that the specific surface area of the activated carbon is 1000~1500cm2/
G, absorption pore volume are 0.60~1.00cm3/g。
4. catalyst according to claim 1, it is characterised in that the metalloid element in boron, arsenic and tellurium at least one
Kind.
5. catalyst according to claim 1, it is characterised in that the platinum group be selected from platinum, palladium, osmium, iridium, ruthenium and
At least one of rhodium.
6. catalyst according to claim 1, it is characterised in that the content of zinc acetate is in catalyst：50~300g/L.
7. catalyst according to claim 1, it is characterised in that cocatalyst content described in catalyst be 0.50~
8.00g/L。
8. as the production method of the catalyst described in claim 1, comprise the following steps：
1. the solution of zinc acetate, co-catalyst is mixed with carrier by the composition of catalyst；
2. dry.
9. vinyl acetate synthesis method, using acetic acid, acetylene as raw material, closed under catalyst any one of claim 1~7
Into vinyl acetate.
10. synthetic method according to claim 9, it is characterized in that being formed with molar ratio computing raw material as acetylene:Acetic acid=(5
~12):1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056563A (en) * | 1975-01-31 | 1977-11-01 | Boyadzhian Varazdat Karapetovi | Method of producing allylacetate |
| CN104549497A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for vinyl acetate synthesis by acetylene method and preparation method thereof |
| CN105498778A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Acetylene process vinyl acetate catalyst |
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2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056563A (en) * | 1975-01-31 | 1977-11-01 | Boyadzhian Varazdat Karapetovi | Method of producing allylacetate |
| CN104549497A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for vinyl acetate synthesis by acetylene method and preparation method thereof |
| CN105498778A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Acetylene process vinyl acetate catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 兰州化工学校基本有机合成专业教研组: "《基本有机合成工艺学-下册》", 30 June 1964, 中国工业出版社 * |
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