CN107774333B - The catalyst of vinyl acetate synthesis - Google Patents
The catalyst of vinyl acetate synthesis Download PDFInfo
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- CN107774333B CN107774333B CN201610750873.3A CN201610750873A CN107774333B CN 107774333 B CN107774333 B CN 107774333B CN 201610750873 A CN201610750873 A CN 201610750873A CN 107774333 B CN107774333 B CN 107774333B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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- 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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- 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
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
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Abstract
The present invention relates to the catalyst of vinyl acetate synthesis, mainly solve the problems, such as that by-product benzene content existing in the prior art is high.The present invention uses the catalyst of vinyl acetate synthesis, the catalyst uses active carbon for carrier, active component includes zinc acetate and co-catalyst, the co-catalyst includes the technical solution selected from least one of metalloid element, it preferably solves the problems, such as this, can be used in the industrial production of acetylene method vinyl acetate synthesis.
Description
Technical field
The present invention relates to acetylene in gas phase method vinyl acetate catalyst, the preparation method of the catalyst and vinyl acetates
Synthetic method.
Background technique
Vinylacetate, abbreviation vinyl acetate (VAM) are a kind of important Organic Chemicals, mainly for the production of poly-
Vinyl acetate (PVAc), polyvinyl alcohol (PVOH), vinyl acetate-ethylene copolymerization emulsions (VAE) or copolymer resins (EVA), acetic acid
The derivatives such as ethylene-vinyl chloride copolymer (EVC), polyacrylonitrile comonomer and acetal resin, in coating, slurry, bonding
Agent, polyvinyl, film, leather processing, synthetic fibers, soil improvement etc. have extensive value of exploiting and utilizing.With production
Technology is constantly progressive, and application field is also constantly extending.
Global vinyl acetate production capacity is concentrated mainly on Asia, North America and West Europe up to 743.4 ten thousand tons/year within 2011.By area
Production capacity statistics, Asia-Pacific are 398.8 ten thousand tons/year, account for 53.6%；North America is 206.3 ten thousand tons/year, accounts for 27.8%；West Europe is 117.1
Ten thousand tons/year, account for 15.8%；Other areas account for 2.9%.Wherein, the production capacity of Chinese vinyl acetate is 216.5 ten thousand tons/year.
Currently, vinyl acetate main production route is ethylene process and acetylene method.Wherein, acetylene method includes natural gas again
Acetylene method and two kinds of carbide acetylene method.Gas acetylene method uses fixed-bed process, selects graininess zinc acetate/activated carbon catalysis
Agent；And carbide acetylene method uses fluidized-bed process, the Zinc Acetate/activated Carbon Catalyst of choice of powder shape.Not due to resource structures
Together, North America, West Europe, the countries and regions such as Singapore, Japan and Korea S use ethylene process technique substantially, and Korea, and India is then all using second
Alkynes method technique, China, Russia, the countries and regions such as Eastern Europe then two kinds of techniques and are deposited.With China new natural gas and shale
The discovery of gas resource and the maturation of its production technique and perfect, Devoting Major Efforts To Developing and popularization gas acetylene method acetic acid second in China
Alkene production technology has very good prospect.
The method that nineteen twenty-two Germany Wacker company uses acetylene in gas phase synthesis VAM first, is improved by Hochst company
Put into industrial production.Its catalyst using zinc acetate as active component, using active carbon as carrier, and use till today always.The catalysis
Agent disadvantage includes that activity decline is fast, and production capacity is not high, is increased as reaction temperature increases by-product, catalyst service life is not
It is long.Meanwhile acetylene method has technically simple, catalyst is inexpensive, is easy to get, and activity is fair, and selectivity is high, and it is excellent that expense of founding the factory is low etc.
Point.Therefore, the activity and service life for how effectively improving the catalyst become one important scientific issues of the catalytic field, respectively
State researcher starts with from active component, co-catalyst, the selection of carrier and modification, catalyst preparation process etc. asks this
Topic has carried out system research, achieves certain phasic results.
Acetylene method synthetic route used catalyst active component is mainly zinc acetate, but researcher attempts using other more
Kind composite oxides replace zinc acetate as active component.As Japanese scholars are proposed with bi component oxide (V2O5-ZnO、
Fe2O3- ZnO) or three component oxide (16ZnO32Fe2O3·V2O5And 24ZnO8Cr2O3·V2O5) it is used as catalyst
Active component, although above-mentioned catalyst 250 urge it is lower have be higher than Zn (OAc)2The activity of/C catalyst, but because of reaction temperature
The disadvantages of high, at high cost, active decline is fast is not able to achieve industrialization.Soviet Union scholar once studied the silicate and aluminic acid of Cd and Zn
The catalyst such as zinc.A kind of Chinese patent (CN 86107833A, catalyst and preparation method thereof for vinyl acetate synthesis) report
Road ZnO-ZnCl2Its space time yield of/C catalyst is higher than Zn (OAc)2/ C catalyst about 30%, but in the catalyst preparation process
Because having used nitrate, when decomposition, generates a large amount of NOxAnd environment is polluted, and joined ZnCl in catalyst2, Cl-Equipment is generated
Corrosivity limits the popularization of the catalyst.The research of acetylene method vinyl acetate catalyst active component substitution is not taken
Substantial progress is obtained, up to the present, acetylene method vinyl acetate catalyst is still using zinc acetate as active component.
Meanwhile researcher attempts at Zn (OAc)2Co-catalyst is added in/C catalyst and reaches improvement catalyst performance
Purpose.As Chinese patent (CN 1903435A, a kind of catalyst and preparation method thereof for vinyl acetate synthesis) selects alkali formula
Waltherite is as co-catalyst, so that the vinyl acetate space-time yield of the catalyst is by 2.02t/m3D is increased to 2.67t/m3·
D, catalyst activity improve 32.2%.Master's thesis (University of Fuzhou, 2006, acetylene method vapor- phase synthesis vinyl acetate catalyst
Research) point out that Zn (OAc) can be improved in co-catalyst potassium, barium and lanthanum2The activity of/C catalyst.The addition of co-catalyst is obvious
The activity of the catalyst is improved, basic bismuth carbonate has been applied to the life of industrial acetic acid catalyst for ethylene as co-catalyst at present
In production.
For a long time, many scholars at home and abroad attempt to replace carried by active carbon with silica gel, aluminium oxide, alumina silicate and molecular sieve etc.
The experiment of body is simultaneously failed.Document (chemical workshop, 1962,85 (16): 1；Petrochemical industry, 1979, (8) 7:49) research hair
Existing, when silica gel, aluminium oxide, alumina silicate and molecular sieve etc. are as carrier, catalyst activity specific activity high-area carbon catalyst activity is low
Very much.It was verified that up to the present active carbon can not be substituted as acetylene method vinyl acetate catalyst carrier.Meanwhile
Researcher considers to modify absorbent charcoal carrier, to achieve the purpose that improve carrier property.As document (petrochemical industry,
2004,33 (11): 1024) the study found that the active carbon crossed through 15% nitric acid treatment of mass fraction is catalyst made from carrier
5.36% is improved than the activity that untreated active carbon is catalyst made from carrier.Chinese patent (CN 102029193A,
A kind of active carbon that making catalyst carrier and its processing method and application) select hydrogen peroxide to carry out pre-treatment to absorbent charcoal carrier,
The result shows that its catalytic activity of catalyst made from the active carbon handled using the invention the method improves 2~15%.
Chinese patent (CN 102284304A, a kind of preparation method of high-efficiency catalyst for vinyl acetate synthesis by acetylene method) removes hydrogen peroxide
Outside, it is used to synthesize vinegar after also selecting a series of oxidants such as sulfuric acid, potassium permanganate and ammonium persulfate to carry out pre-treatment to active carbon
The preparation of sour catalyst for ethylene, the patent only report the percentage composition of vinyl acetate in product, do not specify the work of the catalyst
Property data.Though the activity of catalyst can be improved to a certain extent by selecting oxidant to carry out pre-treatment to absorbent charcoal carrier, through acid
Or the active carbon after other oxidizer treatments needs through a long time washing, extraction to be in neutrality active carbon mostly, and drying time
It is long, increase production time and the cost of catalyst.
As newly-built and enlarging vinyl acetate device domestic in recent years is constantly driven, domestic vinyl acetate market has become
Nearly saturation, or even there is superfluous sign.Therefore, vinyl acetate Downstream Market how is opened up, developing has high added value
Vinyl acetate downstream product is the task of top priority.And improving vinyl acetate product quality is to develop its high added value downstream product
One of important prerequisite factor.
Vinyl acetate one purposes with high added value is synthesizing vinyl acetate-ethylene copolymer (VAE) lotion, is used for
Cigarette glue in cigarette production process, but domestic only ethylene process vinyl acetate product index reaches for cigarette industry cigarette at present
Glue quality requirement.And the vinyl acetate product of acetylene method production constrains it and is used for because containing a small amount of by-product benzene (< 5ppmw)
The problem of producing cigarette glue raw material VAE lotion, how reducing by-product benzene in acetylene method vinyl acetate product becomes restriction, and it is answered
Key problem for cigarette glue raw material.And academia and industry are for the research work master of acetylene method vinyl acetate catalyst
It concentrates on the problems such as improving catalyst activity and catalyst life, for improving the selectivity of catalyst, especially reduces
The problem of by-product benzene content, has not been reported.
Summary of the invention
The first technical problem to be solved by the present invention is the high problem of by-product benzene content existing in the prior art, is mentioned
For a kind of new vinyl acetate catalyst, which has the characteristics that the by-product benzene content generated is low.
The second technical problem to be solved by the present invention is to provide a kind of catalysis corresponding with one of above-mentioned technical problem
The preparation method of agent.
The third technical problem to be solved by the present invention is to provide a kind of using catalyst described in one of above-mentioned technical problem
Vinyl acetate synthetic method.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: the catalyst of vinyl acetate synthesis,
The catalyst uses active carbon for carrier, and active component includes zinc acetate and co-catalyst, and the co-catalyst includes being selected from
At least one of metalloid element.
The addition of metalloid element reduces the content of impurity benzene in product.
In above-mentioned technical proposal, alkali metal acetate can be free of in catalyst composition, such as potassium acetate, alkali can be free of
Metal acetate salt causes the content of objectionable impurities benzene in product to increase.
In above-mentioned technical proposal, the active carbon preferably is selected from coaly activated carbon, cocoanut active charcoal, apricot shell active carbon and bamboo matter
At least one of active carbon.
In above-mentioned technical proposal, the specific surface area of the active carbon is preferably 1000~1500m2/ g, adsorption hole hold preferred
For 0.50~1.00cm3/g。
In above-mentioned technical proposal, the metalloid element preferably is selected from least one of boron, silicon, germanium, arsenic, antimony and tellurium.
In above-mentioned technical proposal, the co-catalyst in addition to include selected from least one of metalloid element element with
It outside, further comprise at least one of VIIB race element metallic element.
In above-mentioned technical proposal, VIIB race element is selected from least one of manganese, technetium and rhenium.
When the co-catalyst includes simultaneously metalloid element and VIIB race element, and metalloid element include at least Ge or
When Sb, VIIB race element include at least Mn, above-mentioned two race element has synergistic effect in reducing product in terms of impurity benzene content.
It should be pointed out that without discovery, there are this synergistic effects between tellurium and rhenium between tellurium and manganese.
When the co-catalyst includes simultaneously metalloid element and VIIB race element, and metalloid element include at least Ge and
When Sb, VIIB race element include at least Mn or Re, above-mentioned element has synergistic effect in reducing product in terms of impurity benzene content.
When the co-catalyst includes simultaneously metalloid element and VIIB race element, and metalloid element include at least Ge and
When Sb, VIIB race element include at least Mn and Re, above-mentioned element has synergistic effect in reducing product in terms of impurity benzene content.
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 0.10~10.0g/L in the catalyst, more preferably
1.00~5.00g/L.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem
The production method of catalyst described in case, includes the following steps:
1. the solution of zinc acetate, co-catalyst is mixed with carrier by the composition of catalyst.
2. drying.
In above-mentioned technical proposal, as non-restrictive, the correspondence compound form of the co-catalyst be may is that
The compound preferred boric acid of the metalloid element, ammonium pentaborate, germanium tetrachloride, nitric acid germanium, antimony trifluoride, three oxygen
Change at least one of antimony, ammonium tellurate, tellurium dioxide and telluric acid, more preferably from least one of nitric acid germanium, antimony trifluoride；It is described
The compound of VIIB race preferably is selected from least one of manganese acetate, manganese chloride, manganese sulfate, methyl rhenium trioxide and ammonium perrhenate,
More preferably from least one of manganese acetate and ammonium perrhenate.
To solve above-mentioned technical problem three, technical scheme is as follows: vinyl acetate synthesis method, with acetic acid,
Acetylene is raw material, and reaction generates acetic acid in the presence of the catalyst described in any one of technical solution of one of above-mentioned technical problem
Ethylene.
Key of the invention is the selection of catalyst, and skilled person will know how suitable determine according to actual needs
Reaction temperature, the reaction time, reaction pressure and material proportion.But the temperature reacted in above-mentioned technical proposal is preferably
160~200 DEG C；The pressure of reaction is preferably 0.1~0.5atm；Preferably acetylene: acetic acid=(5 is formed with molar ratio computing raw material
~12): 1；Raw material volume air speed is preferably 250~350h-1。
The content of each component is analyzed with gas chromatography mass spectrometer (GC-MS) in reaction product of the present invention, and is calculated
The vinyl acetate space-time yield of catalyst.
Compared with prior art, key of the invention is in the active component of catalyst including zinc acetate and selected from quasi- gold
Belong to the compound at least one of VIIB race element, is conducive to improve catalyst choice, reduces by-product benzene in product
Content.
The experimental results showed that the vinyl acetate space-time yield of catalyst reaches 75.9g/ when using catalyst of the present invention
(Lh), benzene content is reduced to 2520ppbw in reaction mixture, achieves living in preferable technical effect, especially catalyst
Property component simultaneously include zinc acetate, selected from least one of metalloid element compound and selected from least one of VIIB race
When metallic element compound, technical effect more outstanding is achieved, can be used in the industrial production of vinyl acetate.Below by
The present invention is further elaborated for embodiment.
Specific embodiment
[embodiment 1]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the nitric acid germanium (GeNO of the Ge containing 2.90g4) sufficiently mixed
Conjunction is dissolved in aqueous acetic acid, the maceration extract 350ml that pH is 4.8 is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei
0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon carrier impregnation of/g in above-mentioned maceration extract, stand 3h in
110 stains are dry, obtain the catalyst.The acetic acid Zn content for measuring the catalyst through ICP is 100g/L, Ge content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 75.9g/ (Lh), benzene content in reaction mixture
2520ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 2]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the manganese acetate (Mn of the Mn containing 2.90g
(CH3COO)2·4H2O it) is sufficiently mixed and is dissolved in aqueous acetic acid, the maceration extract 350ml that pH is 4.8 is obtained, by 1L diameter
3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon carrier impregnation of/g is in above-mentioned leaching
In stain liquid, 3h drying on 110 is stood, the catalyst is obtained.The Zn content for measuring the catalyst through ICP is 100g/L, Mn
Content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MS) analysis.
The vinyl acetate space-time yield for being computed catalyst is 74.6g/ (Lh), benzene content in reaction mixture
3100ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2) be dissolved in aqueous acetic acid, obtaining pH is 4.8
Maceration extract, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon of/g
Carrier impregnation stands 3h drying on 110, obtains the catalyst in above-mentioned maceration extract.The vinegar of the catalyst is measured through ICP
Sour Zn content is 100g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 64.1g/ (Lh), benzene content in reaction mixture
5530ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[comparative example 2]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), 6.30g potassium acetate (CH3COOK), Mn containing 2.90g
Manganese acetate (Mn (CH3COO)2·4H2O it) is sufficiently mixed and is dissolved in aqueous acetic acid, obtain the maceration extract that pH is 4.8
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon of/g carries
Body is immersed in above-mentioned maceration extract, is stood 3h drying on 110, is obtained the catalyst.The acetic acid of the catalyst is measured through ICP
Zn content is 100g/L, and acetic acid potassium content is 6.30g/L, Mn content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 81.4g/ (Lh), benzene content in reaction mixture
5620ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 3]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the antimony trifluoride (SbF of the Sb containing 2.90g3) sufficiently
Mixed dissolution obtains the maceration extract 350ml that pH is 4.8, by 1L diameter 3mm, long 2cm, Kong Rongwei in aqueous acetic acid
0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon rhodium chloride carrier impregnation of/g in above-mentioned maceration extract,
It is dry on 110 to stand 3h, obtains the catalyst.The acetic acid Zn content for measuring the catalyst through ICP is 100g/L, Sb content
2.90g/L。
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 76.7g/ (Lh), benzene content in reaction mixture
2630ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 4]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the ammonium tellurate ((NH of the Te containing 2.90g4)2TeO4) fill
Divide mixed dissolution in aqueous acetic acid, the maceration extract 350ml that pH is 4.8 is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei
0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon carrier impregnation of/g in above-mentioned maceration extract, stand 3h in
It is dry on 110, obtain the catalyst.The acetic acid Zn content for measuring the catalyst through ICP is 100g/L, Te content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 75.7g/ (Lh), benzene content in reaction mixture
2700ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 5]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the ammonium perrhenate (NH of the Re containing 2.90g4ReO4) fill
Divide mixed dissolution in aqueous acetic acid, the maceration extract 350ml that pH is 4.8 is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei
0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon carrier impregnation of/g in above-mentioned maceration extract, stand 3h in
It is dry on 110, obtain the catalyst.The acetic acid Zn content for measuring the catalyst through ICP is 100g/L, Re content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 74.3g/ (Lh), benzene content in reaction mixture
3250ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[comparative example 3]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), 6.30g potassium acetate (CH3COOK), Re containing 2.90g
Ammonium perrhenate (NH4ReO4) be sufficiently mixed and be dissolved in aqueous acetic acid, the maceration extract 350ml for obtaining that pH is 4.8 is straight by 1L
Diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon carrier impregnation of/g is above-mentioned
In maceration extract, 3h is stood in the drying of 110 types, obtains the catalyst.The acetic acid Zn content for measuring the catalyst through ICP is
100g/L, acetic acid potassium content are 6.30g/L, Re content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 81.1g/ (Lh), benzene content in reaction mixture
6210ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 6]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the ammonium pentaborate (NH of the B containing 2.90g4B5O8) sufficiently
Mixed dissolution obtains the maceration extract 350ml that pH is 4.8, by 1L diameter 3mm, long 2cm, Kong Rongwei in aqueous acetic acid
0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon carrier impregnation of/g in above-mentioned maceration extract, stand 3h in
It is dry on 110, obtain the catalyst.The acetic acid Zn content for measuring the catalyst through ICP is 100g/L, B content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 75.9g/ (Lh), benzene content in reaction mixture
2680ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[comparative example 4]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), 6.30g potassium acetate (CH3COOK), B containing 2.90g
Ammonium pentaborate (NH4B5O8) be sufficiently mixed and be dissolved in aqueous acetic acid, the maceration extract 350ml for obtaining that pH is 4.8 is straight by 1L
Diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon carrier impregnation of/g is above-mentioned
In maceration extract, 3h drying on 110 is stood, the catalyst is obtained.The acetic acid Zn content for measuring the catalyst through ICP is
100g/L, acetic acid potassium content are 6.30g/L, B content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 81.7g/ (Lh), benzene content in reaction mixture
5890ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 7]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the manganese acetate (Mn of the Mn containing 1.50g
(CH3COO)2·4H2) and the nitric acid germanium (GeNO of the Ge containing 1.40g O4) be sufficiently mixed and be dissolved in aqueous acetic acid, obtaining pH is
4.8 maceration extract 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The cylindrical type of/g
Coaly activated carbon carrier impregnation stands 3h drying on 110, obtains the catalyst in above-mentioned maceration extract.It should through ICP measurement
The acetic acid Zn content of catalyst is 100g/L, Mn content 1.50g/L, Ge content 1.40g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 75.4g/ (Lh), benzene content in reaction mixture
2050ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 8]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the manganese acetate (Mn of the Mn containing 1.50g
(CH3COO)2·4H2) and the antimony trifluoride (SbF of the Sb containing 1.40g O3) be sufficiently mixed and be dissolved in aqueous acetic acid, obtain pH
For 4.8 maceration extract 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The cylinder of/g
Moulded coal activated carbon carrier impregnation stands 3h drying on 110, obtains the catalyst in above-mentioned maceration extract.It is measured through ICP
The acetic acid Zn content of the catalyst is 100g/L, Mn content 1.50g/L, Sb content 1.40g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 75.2g/ (Lh), benzene content in reaction mixture
2140ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[comparative example 5]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the manganese acetate (Mn of the Mn containing 1.50g
(CH3COO)2·4H2) and the ammonium tellurate ((NH of the Te containing 1.40g O4)2TeO4) be sufficiently mixed and be dissolved in aqueous acetic acid, it obtains
The maceration extract 350ml that pH is 4.8, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The circle of/g
Column type coaly activated carbon carrier impregnation stands 3h in 110 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.It is surveyed through ICP
The acetic acid Zn content of the fixed catalyst is 100g/L, Mn content 1.50g/L, Te content 1.40g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 75.1g/ (Lh), benzene content in reaction mixture
2950ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[comparative example 6]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the ammonium perrhenate (NH of the Re containing 1.50g4ReO4) and
The ammonium tellurate ((NH of the Te containing 1.40g4)2TeO4) be sufficiently mixed and be dissolved in aqueous acetic acid, obtain the maceration extract that pH is 4.8
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon of/g carries
Body is immersed in above-mentioned maceration extract, is stood 3h in 110 DEG C of dryings, is obtained the catalyst.The acetic acid of the catalyst is measured through ICP
Zn content is 100g/L, Re content 1.50g/L, Te content 1.40g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 74.7g/ (Lh), benzene content in reaction mixture
2980ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 9]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the manganese acetate (Mn of the Mn containing 1.50g
(CH3COO)2·4H2O), the nitric acid germanium (GeNO of the Ge containing 1.00g4) and the Sb containing 0.40g antimony trifluoride (SbF3) be sufficiently mixed
It is dissolved in aqueous acetic acid, the maceration extract 350ml that pH is 4.8 is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/
G, specific surface area is 1200m2The cylindrical type coaly activated carbon carrier impregnation of/g stands 3h and does on 110 in above-mentioned maceration extract
It is dry, obtain the catalyst.The acetic acid Zn content for measuring the catalyst through ICP is 100g/L, Mn content 1.50g/L, Ge content
1.00g/L, Sb content 0.40g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 75.6g/ (Lh), benzene content in reaction mixture
1560ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 10]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the ammonium perrhenate (NH of the Re containing 1.50g4ReO4)、
Nitric acid germanium (the GeNO of the Ge containing 1.00g4) and the Sb containing 0.40g antimony trifluoride (SbF3) be sufficiently mixed and be dissolved in aqueous acetic acid
In, the maceration extract 350ml that pH is 4.8 is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area are
1200m2The cylindrical type coaly activated carbon carrier impregnation of/g stands 3h in the drying of 110 types, obtains described urge in above-mentioned maceration extract
Agent.The acetic acid Zn content for measuring the catalyst through ICP is 100g/L, Re content 1.50g/L, Ge content 1.00g/L, Sb content
0.40g/L。。
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 75.3g/ (Lh), benzene content in reaction mixture
1680ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
[embodiment 11]
The preparation of catalyst: by 100g zinc acetate (Zn (CH3COO)2), the manganese acetate (Mn of the Mn containing 0.90g
(CH3COO)2·4H2O), the ammonium perrhenate (NH of the Re containing 0.60g4ReO4), the nitric acid germanium (GeNO of the Ge containing 1.00g4) and contain
Antimony trifluoride (the SbF of 0.40g Sb3) be sufficiently mixed and be dissolved in aqueous acetic acid, the maceration extract 350ml that pH is 4.8 is obtained,
By 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The cylindrical type coaly activated carbon carrier impregnation of/g
In above-mentioned maceration extract, 3h is stood in the drying of 110 types, obtains the catalyst.The acetic acid Zn content of the catalyst is measured through ICP
For 100g/L, Mn content 0.90g/L, Re content 0.60g/L, Ge content 1.00g/L, Sb content 0.40g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 178 DEG C, instead
Answering pressure is 0.25atm；Raw material volume air speed: 300h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop reaction.
Reaction mixture analysis: the reaction mixture that above-mentioned reaction is obtained uses gas chromatograph-mass spectrometer (GC-MS) (GC-
MS it) analyzes.
The vinyl acetate space-time yield for being computed catalyst is 76.1g/ (Lh), benzene content in reaction mixture
590ppbw.For ease of description and compare, the composition of catalyst, the vinyl acetate space-time yield of catalyst and reaction are mixed
Benzene content is listed in table 1 in object.
By comparing example 1 with embodiment 1~11 on year-on-year basis as can be seen that there is reduction to react mixed for metalloid or VIIB race element
Close the effect of impurity benzene content in object.
By implementing 7 with embodiment 1 and embodiment 2 on year-on-year basis as can be seen that Mn and Ge impurity in reducing reaction mixture
There is synergistic effect in terms of the content of benzene.By implementing 8 with embodiment 2 and embodiment 3 on year-on-year basis as can be seen that Mn and Sb is being reduced
There is in terms of the content of impurity benzene synergistic effect in reaction mixture.But comparative example 5 and embodiment 2 and embodiment 4 are on year-on-year basis, or
Comparative example 6 but finds out on year-on-year basis with embodiment 4 and embodiment 5, Mn and Te or Re and Te, the impurity in reducing reaction mixture
There is no synergistic effects in terms of the content of benzene.
Embodiment 9 and embodiment 7 and 8 are on year-on-year basis as can be seen that the content of Ge and Sb impurity benzene in reducing reaction mixture
Aspect has synergistic effect.
Embodiment 11 and embodiment 9 and 10 are on year-on-year basis as can be seen that Mn and Re impurity benzene in reduce reaction mixture contains
Amount aspect has synergistic effect.
Table 1
Claims (4)
1. the catalyst of vinyl acetate synthesis, the catalyst uses active carbon for carrier, and active component includes zinc acetate and helps
Catalyst, the co-catalyst are made of at least one of germanium, two kinds of metallic elements of antimony and VIIB race metallic element element, and
VIIB race metallic element includes at least manganese；Wherein, in the catalyst zinc acetate content are as follows: 50~300g/L, co-catalyst
Content are as follows: 0.10~10.0g/L.
2. catalyst according to claim 1, it is characterised in that the active carbon be coaly activated carbon, cocoanut active charcoal,
At least one of apricot shell active carbon and activated carbon from bamboo.
3. catalyst according to claim 1, it is characterised in that the specific surface area of the active carbon is 1000~1500m2/
G, it is 0.50~1.00cm that adsorption hole, which holds,3/g。
4. being included the following steps: by the production method of catalyst described in claim 1
1. the solution of zinc acetate, co-catalyst is mixed with carrier by the composition of catalyst；
2. drying.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1550700A1 (en) * | 1987-10-13 | 1996-03-27 | В.А. Мамян | Catalyst for vinyl acetate synthesis |
| CN104437627A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Acetylene method vinyl acetate catalyst and preparation method thereof |
| 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 |
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2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1550700A1 (en) * | 1987-10-13 | 1996-03-27 | В.А. Мамян | Catalyst for vinyl acetate synthesis |
| CN104437627A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Acetylene method vinyl acetate catalyst and preparation method thereof |
| 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 |
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