CN106423257B - By the catalyst of ethyl acetate and benzene synthesizing ethyl benzene - Google Patents
By the catalyst of ethyl acetate and benzene synthesizing ethyl benzene Download PDFInfo
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Abstract
The present invention relates to the catalyst by ethyl acetate and benzene synthesizing ethyl benzene, it mainly solves the problems, such as hydrogenation catalyst in the prior art and alkylation catalyst to be simply mixed and be used for by ethyl acetate and benzene one-step synthesis ethylbenzene yield low technical, the present invention is by using the catalyst by ethyl acetate and benzene one-step synthesis ethylbenzene, including carrier and active component；The carrier is molecular sieve；The active component includes following components: metallic copper or its oxide；The corresponding simple substance of at least one element or its oxide of II B race in the periodic table of elements；The corresponding simple substance of at least one element or its oxide of VII B race in the periodic table of elements；The corresponding simple substance of at least one element of group of the lanthanides or the technical solution of its oxide preferably solve the technical problem in the periodic table of elements, can be used for by the industrial production of ethyl acetate and benzene one-step synthesis ethylbenzene.
Description
Technical field
The present invention relates to the catalyst by ethyl acetate and benzene synthesizing ethyl benzene, more particularly, to one step of ethyl acetate and benzene
The catalyst of synthesizing ethyl benzene.
Background technique
Ethylbenzene is a kind of important industrial chemicals, is the production indispensable raw material of styrene, about 90% or more second
Benzene is used to produce styrene.And styrene is important basic organic chemical industry raw material, is mainly used for polymeric material field to make
Take polystyrene and its copolymer.With auto industry, insulator industry, packaging industry and daily necessities industry fast-developing band
Come to the growing of styrene monomer demand, the ethylbenzene demand in China is also being continuously increased.
Alkylated reaction is mainly industrially occurred come synthesizing ethyl benzene by benzene and ethylene.Naphtha as ethylene raw comes
Derived from petroleum, and as the increasingly exhausted and oil price of petroleum resources increasingly rises, the production cost of China's ethylene is steeply risen,
It is inherently restricted by the ethylbenzene production of benzene alkylation with ethylene, needs to develop new way and carry out synthesizing ethyl benzene.Ethyl alcohol can be made
For raw material for alkylation, to carry out synthesizing ethyl benzene with benzene reaction, (specific document has Chinese patent CN102276411A, and " ethyl alcohol and benzene are synthesized
The method of ethylbenzene ", CN102276410A).Currently, China's acetic acid esters price will be lower than ethyl alcohol, acetic acid esters hydrogen addition technology system is utilized
Ethyl alcohol (specific document have Chinese patent CN102976892A " method of acetate preparation of ethanol by hydrogenating ", CN102974382A,
It CN101941887A), can be to provide feed ethanol from the production of ethyl alcohol and benzene synthesizing ethyl benzene.First hydrogen is added to obtain using ethyl acetate
The ethyl alcohol arrived again with two step technology paths of benzene alkylation synthesizing ethyl benzene, although can be using ethyl acetate as raw material for alkylation
Synthesizing ethyl benzene, but in this way will after first step ethyl acetate adds hydrogen being separated and being stored to intermediate product ethanol, technique stream
Journey is complicated, and energy consumption and discharge are high.If being able to achieve reacting for ethyl acetate and benzene one-step synthesis ethylbenzene, intermediate product is just eliminated
The links such as the separate transport of ethyl alcohol and storage, can simplify process flow, reduce energy consumption and discharge, develop skill economy.
However the active constituent of existing hydrogenation catalyst or alkylation catalyst has a single function, it is difficult to which a step realizes acetic acid
The reaction process of ethyl ester and benzene synthesizing ethyl benzene；Hydrogenation conditions differ greatly with alkylation reaction condition, by hydrogenation catalyst
It is simply mixed with alkylation catalyst for very low by ethyl acetate and benzene one-step synthesis ethylbenzene yield.
Summary of the invention
The invention solves technical problems first is that hydrogenation catalyst in the prior art and alkylation catalyst is simple
It is mixed for by ethyl acetate and benzene one-step synthesis ethylbenzene yield low technical problem, provides a kind of new by ethyl acetate and benzene one
The catalyst of synthesizing ethyl benzene is walked, which has the advantages that ethylbenzene high income.
The second technical problem to be solved by the present invention is the preparation method of catalyst described in one of above-mentioned technical problem.
The third technical problem to be solved by the present invention is one of above-mentioned technical problem using one of above-mentioned technical problem institute
The method by ethyl acetate and benzene one-step synthesis ethylbenzene for the catalyst stated.
One of to solve above-mentioned technical problem, technical scheme is as follows: by ethyl acetate and benzene one-step synthesis second
The catalyst of benzene, including carrier and active component；The carrier is molecular sieve；The active component includes following components:
Component 1: metallic copper or its oxide；
Component 2: the corresponding simple substance of at least one element or its oxide of II B race in the periodic table of elements；
Component 3: the corresponding simple substance of at least one element or its oxide of VII B race in the periodic table of elements；
Component 4: the corresponding simple substance of at least one element or its oxide of group of the lanthanides in the periodic table of elements；More preferable lanthanum
It is the corresponding simple substance of at least two elements or its oxide；Such as, but not limited to, the lanthanide series includes at least Ce and Pr, this
When described two lanthanide series there is synergistic effect in terms of improving ethylbenzene yield.
In parts by weight, molecular sieve: component 1: component 2: component 3: component 4 is 100:(20~40): (10~20): (2~
10): (2~20).
In above-mentioned technical proposal, the molecular sieve carrier is preferably hydrogen type molecular sieve.
In above-mentioned technical proposal, the molecular sieve carrier is not particularly limited, for example, be chosen as ZSM-5, Beta molecular sieve,
At least one of MCM-22, Y molecular sieve, preferential includes at least one molecular sieve of ZSM-5.
In above-mentioned technical proposal, II B race element preferably includes at least one element of Zn element.
In above-mentioned technical proposal, VII B race element preferably includes at least one element of Mn element.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem
The preparation method of catalyst described in any one of case, the preparation method preferably are selected from any one in coprecipitation or infusion process
Kind.
Coprecipitation described in above-mentioned technical proposal preferably includes following steps: by copper, II B race element, VII B race member
The soluble-salt of element and lanthanide series is made into aqueous solution, using alkaline matter as precipitating reagent, is co-precipitated on molecular sieve carrier,
Then it is filtered, washed, roasts.The alkaline matter can for example be but not limited to sodium carbonate, potassium carbonate, sodium hydroxide etc..
Infusion process described in above-mentioned technical proposal preferably includes following steps: by copper, II B race element, VII B race element
It is made into aqueous solution with the soluble-salt of lanthanide series, then common impregnated zeolite is dried, roasted.
In above-mentioned technical proposal, the method for preparing catalyst, preferably coprecipitation.
Molecular sieve used in the specific embodiment of the invention is hydrogen type molecular sieve.
To solve above-mentioned technical problem three, technical scheme is as follows: the synthetic method of ethylbenzene, with acetic acid second
Ester, benzene and hydrogen are raw material, and the catalyst described in any one of technical solution of one of above-mentioned technical problem in the presence of reacts
To ethylbenzene.
In above-mentioned technical proposal, the temperature of reaction is preferably 300~400 DEG C.
In above-mentioned technical proposal, the pressure of reaction is preferably 1.5~3MPa.Heretofore described pressure refers both to gauge pressure.
In above-mentioned technical proposal, the liquid volume air speed of raw material is preferably 1~5h-1.Institute in the liquid volume air speed of raw material
The liquid stated includes ethyl acetate and benzene.
In above-mentioned technical proposal, the molar ratio of ethyl acetate, benzene and hydrogen is 1:(10~30): (20~50).
The reaction equation by ethyl acetate and benzene one-step synthesis ethylbenzene that catalyst of the present invention is related to is as follows:
Hydrogenation catalyst and alkylation catalyst are simply mixed for by yield when ethyl acetate and benzene one-step synthesis ethylbenzene
It is very low.Using catalyst of the invention, the yield of ethylbenzene is up to 84.3%, achieves preferable technical effect, can be used for by second
In the industrial production of acetoacetic ester and benzene one-step synthesis ethylbenzene.
Wherein, Computer Corp. of ethyl acetate conversion ratio, benzene conversion ratio and ethylbenzene yield is as follows:
Below by embodiment, the present invention is further elaborated, but these embodiments be not to the scope of the present invention into
Row limitation.
Specific embodiment
[embodiment 1]
1, catalyst preparation
Weighing 23.3g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 13.7g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 6.5g mass fraction is 50%3)2) aqueous solution, 3.1g cerous nitrate (molecular formula Ce
(NO3)3·6H2O), (molecular formula is Pr (NO to 3.1g praseodymium nitrate3)3·6H2O), dissolved to form material I with 200mL water；Weigh 50g
Natrium carbonicum calcinatum is dissolved to form material II with 500mL water；It weighs 20g ZSM-5 molecular sieve to be added in 200mL deionized water, stir
1h is mixed, material III is formed；Material I and II is added dropwise under stirring simultaneously at 70 DEG C and quickly and is being co-precipitated in material III, until I
The complete precipitation titration of liquid terminates, and pH is controlled in precipitation process 7.5, precipitating is continued to stir 30min, stands aging at room temperature
2h is filtered, is in neutrality with deionized water to Buchner funnel lower end efflux, 100 DEG C are dried overnight, and 500 DEG C of roasting 3h are finally pressed
Piece crushes, and chooses the particle of 20~40 mesh.The composition of catalyst take weight ratio meter as ZSM-5: copper: Zn-ef ficiency: manganese member
Element: Ce elements: praseodymium element is 100:30:15:5:5:5, is labeled as 30Cu-15Zn-5Mn-5Ce-5Pr-Z5a
2, evaluating catalyst
The reaction of ethyl acetate and benzene synthesizing ethyl benzene carries out on continuous fixed bed reactor, Catalyst packing volume
For 5mL, ethyl acetate and benzene are made into mixture.Before reaction, catalyst is first restored in hydrogen atmosphere, then by temperature of reactor
Reaction temperature is adjusted, is passed through hydrogen, ethyl acetate is reacted with the mixture of benzene.Reaction condition are as follows: reaction temperature 350
DEG C, reaction pressure 2MPa, the liquid volume air speed of raw material is 3h-1, the molar ratio of ethyl acetate, benzene and hydrogen is 1:20:30.
The catalytic performance of catalyst is shown in Table 1.
[embodiment 2]
1, catalyst preparation
Weighing 23.3g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 13.7g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 6.5g mass fraction is 50%3)2) aqueous solution, 4.6g cerous nitrate (molecular formula Ce
(NO3)3·6H2O), (molecular formula is Pr (NO to 1.2g praseodymium nitrate3)3·6H2O), dissolved to form material I with 200mL water；Weigh 50g
Natrium carbonicum calcinatum is dissolved to form material II with 500mL water；It weighs 20g ZSM-5 molecular sieve to be added in 200mL deionized water, stir
1h is mixed, material III is formed；Material I and II is added dropwise under stirring simultaneously at 70 DEG C and quickly and is being co-precipitated in material III, until I
The complete precipitation titration of liquid terminates, and pH is controlled in precipitation process 7.5, precipitating is continued to stir 30min, stands aging at room temperature
2h is filtered, is in neutrality with deionized water to Buchner funnel lower end efflux, 100 DEG C are dried overnight, and 500 DEG C of roasting 3h are finally pressed
Piece crushes, and chooses the particle of 20~40 mesh.The composition of catalyst take weight ratio meter as ZSM-5: copper: Zn-ef ficiency: manganese member
Element: Ce elements: praseodymium element is 100:30:15:5:8:2, is labeled as 30Cu-15Zn-5Mn-8Ce-2Pr-Z5a.
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Catalyst
Catalytic performance be shown in Table 1.
[embodiment 3]
1, catalyst preparation
Weighing 23.3g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 13.7g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 6.5g mass fraction is 50%3)2) aqueous solution, 1.2g cerous nitrate (molecular formula Ce
(NO3)3·6H2O), (molecular formula is Pr (NO to 4.9g praseodymium nitrate3)3·6H2O), dissolved to form material I with 200mL water；Weigh 50g
Natrium carbonicum calcinatum is dissolved to form material II with 500mL water；It weighs 20g ZSM-5 molecular sieve to be added in 200mL deionized water, stir
1h is mixed, material III is formed；Material I and II is added dropwise under stirring simultaneously at 70 DEG C and quickly and is being co-precipitated in material III, until I
The complete precipitation titration of liquid terminates, and pH is controlled in precipitation process 7.5, precipitating is continued to stir 30min, stands aging at room temperature
2h is filtered, is in neutrality with deionized water to Buchner funnel lower end efflux, 100 DEG C are dried overnight, and 500 DEG C of roasting 3h are finally pressed
Piece crushes, and chooses the particle of 20~40 mesh.The composition of catalyst take weight ratio meter as ZSM-5: copper: Zn-ef ficiency: manganese member
Element: Ce elements: praseodymium element is 100:30:15:5:2:8, is labeled as 30Cu-15Zn-5Mn-2Ce-8Pr-Z5a.
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Catalyst
Catalytic performance be shown in Table 1.
[embodiment 4]
1, catalyst preparation
Weighing 23.3g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 13.7g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 6.5g mass fraction is 50%3)2) aqueous solution, 6.2g cerous nitrate (molecular formula Ce
(NO3)3·6H2O), dissolved to form material I with 200mL water；50g natrium carbonicum calcinatum is weighed, dissolves to form material with 500mL water
II；It weighs 20g ZSM-5 molecular sieve to be added in 200mL deionized water, stirs 1h, form material III；By material I and II 70
DEG C and quickly the lower dropwise addition simultaneously of stirring be co-precipitated in material II, until the complete precipitation titration of I liquid terminates, controlled in precipitation process
Precipitating is continued to stir 30min, stands aging 2h at room temperature, filtered, flowed with deionized water to Buchner funnel lower end by pH 7.5
Liquid is in neutrality out, and 100 DEG C are dried overnight, and 500 DEG C of roasting 3h, last tabletting crushes, and chooses the particle of 20~40 mesh.Catalyst
Composition is ZSM-5 with weight ratio meter: copper: Zn-ef ficiency: manganese element: Ce elements 100:30:15:5:10 is labeled as
30Cu-15Zn-5Mn-10Ce-Z5a。
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Catalyst
Catalytic performance be shown in Table 1.
[embodiment 5]
1, catalyst preparation
Weighing 23.3g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 13.7g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 6.5g mass fraction is 50%3)2) aqueous solution, 6.2g praseodymium nitrate (molecular formula Pr
(NO3)3·6H2O), dissolved to form material I with 200mL water；50g natrium carbonicum calcinatum is weighed, dissolves to form material with 500mL water
II；It weighs 20g ZSM-5 molecular sieve to be added in 200mL deionized water, stirs 1h, form material III；By material I and II 70
DEG C and quickly the lower dropwise addition simultaneously of stirring be co-precipitated in material II, until the complete precipitation titration of I liquid terminates, controlled in precipitation process
Precipitating is continued to stir 30min, stands aging 2h at room temperature, filtered, flowed with deionized water to Buchner funnel lower end by pH 7~8
Liquid is in neutrality out, and 100 DEG C are dried overnight, and 500 DEG C of roasting 3h, last tabletting crushes, and chooses the particle of 20~40 mesh.Catalyst
Composition is ZSM-5 with weight ratio meter: copper: Zn-ef ficiency: manganese element: praseodymium element is 100:30:15:5:10, is labeled as
30Cu-15Zn-5Mn-10Pr-Z5a。
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Catalyst
Catalytic performance be shown in Table 1.
[embodiment 6]
1, catalyst preparation
Weighing 31.0g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 18.2g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 13.0g mass fraction is 50%3)2) aqueous solution, (molecular formula is 6.2g cerous nitrate
Ce(NO3)3·6H2O), (molecular formula is Pr (NO to 6.2g praseodymium nitrate3)3·6H2O), dissolved to form material I with 200mL water；It weighs
50g natrium carbonicum calcinatum is dissolved to form material II with 500mL water；20g ZSM-5 molecular sieve is weighed to be added in 200mL deionized water,
1h is stirred, material III is formed；Material I and II is added dropwise under stirring simultaneously at 70 DEG C and quickly and is being co-precipitated in material III,
Terminate to the complete precipitation titration of I liquid, pH is controlled in precipitation process 7~8, precipitating is continued to stir 30min, is stood at room temperature old
Change 2h, filters, be in neutrality with deionized water to Buchner funnel lower end efflux, 100 DEG C are dried overnight, 500 DEG C of roasting 3h, finally
Tabletting crushes, and chooses the particle of 20~40 mesh.The composition of catalyst take weight ratio meter as ZSM-5: copper: Zn-ef ficiency: manganese member
Element: Ce elements: praseodymium element is 100:40:20:10:10:10, is labeled as 40Cu-20Zn-10Mn-10Ce-10Pr-Z5a.
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Catalyst
Catalytic performance be shown in Table 1.
[embodiment 7]
1, catalyst preparation
Weighing 15.5g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 9.1g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 2.6g mass fraction is 50%3)2) aqueous solution, 1.2g cerous nitrate (molecular formula Ce
(NO3)3·6H2O), (molecular formula is Pr (NO to 1.2g praseodymium nitrate3)3·6H2O), dissolved to form material I with 200mL water；Weigh 50g
Natrium carbonicum calcinatum is dissolved to form material II with 500mL water；It weighs 20g ZSM-5 molecular sieve to be added in 200mL deionized water, stir
1h is mixed, material III is formed；Material I and II is added dropwise under stirring simultaneously at 70 DEG C and quickly and is being co-precipitated in material III, until I
The complete precipitation titration of liquid terminates, and pH is controlled in precipitation process 7~8, precipitating is continued to stir 30min, stands aging at room temperature
2h is filtered, is in neutrality with deionized water to Buchner funnel lower end efflux, 100 DEG C are dried overnight, and 500 DEG C of roasting 3h are finally pressed
Piece crushes, and chooses the particle of 20~40 mesh.The composition of catalyst take weight ratio meter as ZSM-5: copper: Zn-ef ficiency: manganese member
Element: Ce elements: praseodymium element is 100:20:10:2:2:2, is labeled as 20Cu-10Zn-2Mn-2Ce-2Pr-Z5a.
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Catalyst
Catalytic performance be shown in Table 1.
[embodiment 8]
1, catalyst preparation
Weighing 15.5g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 9.1g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 2.6g mass fraction is 50%3)2) aqueous solution, 1.2g cerous nitrate (molecular formula Ce
(NO3)3·6H2O), (molecular formula is Pr (NO to 1.2g praseodymium nitrate3)3·6H2O), dissolved to form material I with 200mL water；Weigh 20g
ZSM-5 molecular sieve is added in 200mL deionized water, stirs 1h, forms material II；Material I is added in material II, is impregnated
4h, 100 DEG C are dried overnight, and 500 DEG C of roasting 3h, last tabletting crushes, and choose the particle of 20~40 mesh.The composition of catalyst is with weight
Amount ratio is calculated as, ZSM-5: copper: Zn-ef ficiency: manganese element: Ce elements: praseodymium element is 100:30:15:5:5:5, is labeled as
30Cu-15Zn-5Mn-5Ce-5Pr-Z5b。
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Catalyst
Catalytic performance be shown in Table 1.
With embodiment 1 on year-on-year basis it is found that infusion process effect is good not as good as coprecipitation.
Table 1
[embodiment 9]
1, catalyst preparation
Catalyst is prepared according to the same manner as in Example 1.
2, evaluating catalyst
The reaction of ethyl acetate and benzene synthesizing ethyl benzene carries out on continuous fixed bed reactor, Catalyst packing volume
For 5mL, ethyl acetate and benzene are made into mixture.Before reaction, catalyst is first restored in hydrogen atmosphere, then by temperature of reactor
Reaction temperature is adjusted, is passed through hydrogen, ethyl acetate is reacted with the mixture of benzene.Reaction condition are as follows: reaction temperature 350
DEG C, reaction pressure 3MPa, the liquid volume air speed of raw material is 1h-1, the molar ratio of ethyl acetate, benzene and hydrogen is 1:10:40.
Ethyl acetate conversion ratio is 99.5%, and benzene conversion ratio is 18.1%, and ethylbenzene yield is 81.3%.
[embodiment 10]
1, catalyst preparation
Catalyst is prepared according to the same manner as in Example 1.
2, evaluating catalyst
The reaction of ethyl acetate and benzene synthesizing ethyl benzene carries out on continuous fixed bed reactor, Catalyst packing volume
For 5mL, ethyl acetate and benzene are made into mixture.Before reaction, catalyst is first restored in hydrogen atmosphere, then by temperature of reactor
Reaction temperature is adjusted, is passed through hydrogen, ethyl acetate is reacted with the mixture of benzene.Reaction condition are as follows: reaction temperature 400
DEG C, reaction pressure 2MPa, the liquid volume air speed of raw material is 5h-1, the molar ratio of ethyl acetate, benzene and hydrogen is 1:20:25.
Ethyl acetate conversion ratio is 99.8%, and benzene conversion ratio is 9.7%, and ethylbenzene yield is 73.3%.
[comparative example 1]
1, catalyst preparation
Weighing 23.3g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 13.7g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 6.5g mass fraction is 50%3)2) aqueous solution, 6.2g cerous nitrate (molecular formula Ce
(NO3)3·6H2O), (molecular formula is Pr (NO to 3.1g praseodymium nitrate3)3·6H2O), dissolved to form material I with 200mL water；Weigh 50g
Natrium carbonicum calcinatum is dissolved to form material II with 500mL water；It is added dropwise under material II is stirred at 70 DEG C and quickly in material I
Co-precipitation controls pH 7.5, precipitating is continued to stir 30min, at room temperature until the complete precipitation titration of I liquid terminates in precipitation process
Aging 2h is stood, filters, is in neutrality with deionized water to Buchner funnel lower end efflux, 100 DEG C are dried overnight, 500 DEG C of roastings
3h obtains material III.It weighs 20g ZSM-5 molecular sieve uniformly to mix with material III, last tabletting crushes, and chooses 20~40 mesh
Particle.The composition of catalyst take weight ratio meter as ZSM-5: copper: Zn-ef ficiency: manganese element: Ce elements: praseodymium element is
100:30:15:5:5:5。
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Acetic acid second
Ester conversion rate is 98.2%, and benzene conversion ratio is 4.1%, and ethylbenzene yield is 38.6%.
This comparative example be hydrogenation catalyst (active component be copper, Zn-ef ficiency, manganese element, Ce elements, praseodymium element) with
Catalyst is mixed obtained by alkylation catalyst (ZSM-5 molecular sieve) mechanical mixture tabletting, with embodiment 1 on year-on-year basis it is found that effect
Well below catalyst of the invention.
[comparative example 2]
1, catalyst preparation
Weighing 23.3g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 13.7g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 6.5g mass fraction is 50%3)2) aqueous solution, (molecular formula is 15.1g scandium nitrate
Sc(NO3)3·6H2O), dissolved to form material I with 200mL water；50g natrium carbonicum calcinatum is weighed, dissolves to form material with 500mL water
II；It weighs 20g ZSM-5 molecular sieve to be added in 200mL deionized water, stirs 1h, form material III；By material I and II 70
DEG C and quickly the lower dropwise addition simultaneously of stirring be co-precipitated in material II, until the complete precipitation titration of I liquid terminates, controlled in precipitation process
Precipitating is continued to stir 30min, stands aging 2h at room temperature, filtered, flowed with deionized water to Buchner funnel lower end by pH 7~8
Liquid is in neutrality out, and 100 DEG C are dried overnight, and 500 DEG C of roasting 3h, last tabletting crushes, and chooses the particle of 20~40 mesh.Catalyst
Composition is ZSM-5 with weight ratio meter: copper: Zn-ef ficiency: manganese element: scandium element is 100:30:15:5:10.
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Acetic acid second
Ester conversion rate is 96.9%, and benzene conversion ratio is 5.0%, and ethylbenzene yield is 44.7%.
[comparative example 3]
1, catalyst preparation
Weighing 23.3g copper nitrate, (molecular formula is Cu (NO3)2·3H2O), (molecular formula is Zn (NO to 13.7g zinc nitrate3)2·
6H2O), (molecular formula is Mn (NO to the manganese nitrate that 6.5g mass fraction is 50%3)2) aqueous solution, 8.6g yttrium nitrate (molecular formula Y
(NO3)3·6H2O), dissolved to form material I with 200mL water；50g natrium carbonicum calcinatum is weighed, dissolves to form material with 500mL water
II；It weighs 20g ZSM-5 molecular sieve to be added in 200mL deionized water, stirs 1h, form material III；By material I and II 70
DEG C and quickly the lower dropwise addition simultaneously of stirring be co-precipitated in material II, until the complete precipitation titration of I liquid terminates, controlled in precipitation process
Precipitating is continued to stir 30min, stands aging 2h at room temperature, filtered, flowed with deionized water to Buchner funnel lower end by pH 7~8
Liquid is in neutrality out, and 100 DEG C are dried overnight, and 500 DEG C of roasting 3h, last tabletting crushes, and chooses the particle of 20~40 mesh.Catalyst
Composition is ZSM-5 with weight ratio meter: copper: Zn-ef ficiency: manganese element: yttrium 100:30:15:5:10.
2, evaluating catalyst
The catalyst acetic acid ethyl ester and benzene synthesizing ethyl benzene reactivity worth are evaluated according to the same manner as in Example 1.Acetic acid second
Ester conversion rate is 97.3%, and benzene conversion ratio is 5.1%, and ethylbenzene yield is 45.2%.
By comparative example 2~3 and embodiment 4 or 5 on year-on-year basis it is found that replacing the lanthanide series in the present invention, effect with scandium or yttrium
Equal sharp fall.
Claims (10)
1. by the catalyst of ethyl acetate and benzene one-step synthesis ethylbenzene, including carrier and active component；The carrier is molecular sieve；
The active component includes following components:
Component 1: metallic copper or its oxide；
Component 2: the corresponding simple substance of at least one element or its oxide of II B race in the periodic table of elements；
Component 3: the corresponding simple substance of at least one element or its oxide of VII B race in the periodic table of elements；
Component 4: the corresponding simple substance of at least two elements or its oxide of group of the lanthanides in the periodic table of elements；
In parts by weight, molecular sieve: component 1: component 2: component 3: component 4 is 100:(20 ~ 40): (10 ~ 20): (2 ~ 10): (2 ~
20), at least two elements of the group of the lanthanides in the periodic table of elements include Pr and Ce.
2. catalyst according to claim 1, it is characterized in that: the molecular sieve carrier is hydrogen type molecular sieve.
3. catalyst according to claim 1, it is characterized in that: the molecular sieve carrier be ZSM-5, Beta molecular sieve,
At least one of MCM-22, Y molecular sieve.
4. the preparation method of catalyst described in any one of claims 1 to 3, it is characterized in that the preparation method is selected from coprecipitated
Any one in shallow lake method or infusion process.
5. the preparation method of catalyst according to claim 4, it is characterized in that:
The coprecipitation include the following steps: by copper, II B race element, VII B race element and lanthanide series soluble-salt
It is made into aqueous solution, using alkaline matter as precipitating reagent, is co-precipitated on molecular sieve carrier, is filtered, roasting；
The infusion process includes the following steps: that the soluble-salt by copper, II B race element, VII B race element and lanthanide series is matched
At aqueous solution, impregnated zeolite, roasting.
6. the synthetic method of ethylbenzene is catalyzed described in any one of claim 1 ~ 3 using ethyl acetate, benzene and hydrogen as raw material
Reaction obtains ethylbenzene in the presence of agent.
7. synthetic method according to claim 6, it is characterized in that the temperature of reaction is 300 ~ 400 DEG C.
8. according to the method described in claim 6, it is characterized in that the pressure of reaction is 1.5 ~ 3 MPa.
9. according to the method described in claim 6, it is characterized in that the liquid volume air speed of raw material is 1 ~ 5 h-1。
10. according to the method described in claim 6, it is characterized in that the molar ratio of ethyl acetate, benzene and hydrogen is 1:(10 ~ 30):
(20~50)。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634659A (en) * | 2004-10-15 | 2005-07-06 | 浙江大学 | Low temperature high activity catalyst for directly synthesizing dimethyl ether and its preparation process |
| CN103121909A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for producing ethylbenzene by performing vapor phase alkylation on ethanol and benzene |
| CN104230634A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of ethylbenzene from acetophenone hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634659A (en) * | 2004-10-15 | 2005-07-06 | 浙江大学 | Low temperature high activity catalyst for directly synthesizing dimethyl ether and its preparation process |
| CN103121909A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for producing ethylbenzene by performing vapor phase alkylation on ethanol and benzene |
| CN104230634A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of ethylbenzene from acetophenone hydrogenation |
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