CN106607073A - Catalyst for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation and use thereof - Google Patents
Catalyst for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation and use thereof Download PDFInfo
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- CN106607073A CN106607073A CN201510690501.1A CN201510690501A CN106607073A CN 106607073 A CN106607073 A CN 106607073A CN 201510690501 A CN201510690501 A CN 201510690501A CN 106607073 A CN106607073 A CN 106607073A
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- C07C2529/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention relates a catalyst for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation. The catalyst solves the problem that the existing catalyst for toluene and methanol side chain alkylation has a low methanol use rate and low ethylbenzene and styrene selectivity. Under toluene and methanol side chain alkylation conditions, raw materials contacts with the catalyst and undergoes a reaction to produce ethylbenzene and styrene. The catalyst is an X molecular sieve having a molar ratio of SiO2/Al2O3 of 2 to 3. Before use, an X molecular sieve is subjected to ion exchange with at least two of potassium ions, rubidium ions and cesium ions, and then the molecular sieve catalyst is loaded with one or more of iron, cobalt, chromium, zirconium and bismuth by an impregnation method. The catalyst well solves the existing problem and can be used for the industrial production of ethylbenzene and styrene through toluene and methanol side chain alkylation.
Description
Technical field
The present invention relates to a kind of be used to prepare ethylbenzene and cinnamic molecular sieve catalyst and application thereof, particularly methylbenzene methanol side
Alkyl group prepares cinnamic molecular sieve catalyst of ethylbenzene and application thereof.
Background technology
Styrene monomer is a kind of important Organic Chemicals, be mainly used in polystyrene, (ABS) resin, butadiene-styrene rubber,
The production of the products such as unsaturated-resin.In addition, it may also be used for pharmacy, dyestuff produce farm chemical emulgent and dressing agent etc.,
Purposes is quite varied.The yield of styrene series resin is only second to PE, PVC and comes in third in synthetic resin.At present
Most of industry styrene is to generate ethylbenzene by benzene and ethylene Jing Friedel-Craft reactions, then Jing catalytic dehydrogenations get.The method
Flow process is more compared with long, side reaction, high energy consumption, and cost of material accounts for the 85% of production variable cost, and production cost is higher.Toluene and
Methanol alkylation is the cinnamic route for having a potential application foreground of production, and Sidorenko in 1967 etc. is first with alkali gold
The X-type and y-type zeolite of category ion exchange successfully uses toluene and methanol-fueled CLC ethylbenzene and styrene for catalyst.With biography
System technique is compared, and the method has the advantages that raw material sources wide, low cost, energy consumption be low, pollution is few.Thus this react once
Report is just subject to the people's attention, and the research about this respect also begins to increase.
The catalyst of methylbenzene methanol side chain alkylation preparation of styrene belongs to solid base catalyst, but catalytic process is soda acid collaboration
Catalytic reaction, and be leading with the catalysis of basic active position.The acid potential energy of catalyst plays a part of stable toluene phenyl ring, and
The methyl group of alkaline potential energy activation Toluene and methanol.First methanol is decomposed in the heart formaldehyde in alkali, and toluene adsorbs in acid site
On, its pendant methyl is activated by alkali center, then formaldehyde and activated methyl reaction production styrene, part styrene with
The hydrogen reaction of generation generates ethylbenzene.If catalyst alkalescence is too strong, formaldehyde can be made further to decompose, while producing more hydrogen
Gas and ethylbenzene；If acidity of catalyst is too strong, alkylation and the toluene disproportionation of phenyl ring can occur, generate benzene and dimethylbenzene,
It requires that there is catalyst suitable soda acid to match, while the presence of phenyl ring requires that catalyst has certain space pore structure.
The reaction of methylbenzene methanol side chain alkylation was once conducted extensive research on multiple catalysts.Many molecular sieves such as X, Y,
L, β, ZSM-5, and some basic anhydride such as MgO, MgO-TiO2And CaO-TiO2All be reported research application
In the reaction of catalysis methylbenzene methanol side chain alkylation, such as JOURNAL OF CATALYSIS 173,490-500 (1998)
With CN101623649A, CN101623650A.Result of study finds, wants to reach preferable side chain alkylation catalysis effect
Really, catalyst must is fulfilled for following 4 points requirement：Catalyst is it is necessary to have enough basic center activation methanol conversions are methyl
Change reagent formaldehyde；There are weak Lewis acid sites to stablize toluene with its methyl that polarizes；Toluene and methanol on a catalyst will
There is a good stoichiometric adsorption equilibrium；Catalyst must have micropore canals structure.Therefore, to some zeolite catalysises
The result of study of activity shows that the X-type zeolite of alkali metal cation-exchanged is the catalyst of relative efficiency.Y-type zeolite it is anti-
Active should be inferior to X-type zeolite.And the reactivity of other such as L, β, ZSM-5 type zeolites is all undesirable, and some do not have
There are the basic anhydride of microcellular structure, such as MgO, MgO-TiO2And CaO-TiO2Deng only very low activity.But from mesh
From the point of view of front prior art, methylbenzene methanol side chain alkylation catalyst also exist activity it is low, ethylbenzene selectivity of styrene is not high
Shortcoming.Therefore, how to improve the activity and selectivity of this kind of catalyst and become methylbenzene methanol and prepare the cinnamic crucial institute of ethylbenzene
.
The content of the invention
To be solved by this invention is that methanol side chain alkylation catalyst activity is low in prior art, and ethylbenzene selectivity of styrene is not
High problem, there is provided a kind of new for toluene and methanol side chain alkylation synthesizing ethyl benzene and cinnamic catalyst, and by this
Catalyst is used to be catalyzed in the cinnamic reaction of methylbenzene methanol side chain alkylation generation ethylbenzene.The catalyst has use ratio of methanol
The characteristics of high and ethylbenzene selectivity of styrene is high.
To solve above-mentioned technical problem, the technical scheme that the present invention takes is as follows：One kind is for toluene and methanol side chain alkylation
Ethylbenzene processed and cinnamic catalyst, by weight percentage, including following components：
A) X molecular sieve that 95～99.9% alkali metal ion is exchanged；
B) element such as 0.1～5% ferrum, cobalt, chromium, zirconium or bismuth.
In above-mentioned technical proposal, it is preferable that the silica alumina ratio SiO of the X molecular sieve2/Al2O3For 2～3.
In above-mentioned technical proposal, it is highly preferred that the silica alumina ratio SiO of the X molecular sieve2/Al2O3For 2～2.5.
In above-mentioned technical proposal, it is preferable that the one kind of component b) in metallic elements of ferrum, cobalt, chromium, zirconium, bismuth.
In above-mentioned technical proposal, it is preferable that the one kind and bismuth of component b) in metallic element cobalt, chromium and zirconium.
In above-mentioned technical proposal, it is highly preferred that the constituent content such as ferrum, cobalt, chromium, zirconium or bismuth is 0.5～2.0%.
In above-mentioned technical proposal, it is preferable that the X molecular sieve that the alkali metal ion is exchanged is to make X molecular sieve and alkali metal
Ion source is contacted and carried out obtained from the method for ion exchange, methods described include making X molecular sieve and potassium ion source, rubidium from
The step of at least one in component or Ces Ium Ion Sources at least contacts one time.It is highly preferred that methods described includes making X molecular sieve
The step of one time at least being contacted with least two in potassium ion source, rubidium ion source or Ces Ium Ion Sources respectively.Most preferably, institute
Stating method includes the step of making X molecular sieve at least contact one time respectively with potassium ion source, rubidium ion source and Ces Ium Ion Sources.Especially
Preferably, methods described includes making X molecular sieve at least contact one respectively with potassium ion source, rubidium ion source and Ces Ium Ion Sources successively
Secondary step.
In above-mentioned technical proposal, it is preferable that toluene is 2～7 with methanol molar ratio, reaction temperature is 350～500 DEG C, instead
Pressure is answered to be 0～0.2MPa, raw material weight air speed is 1～8 hour-1。
In the inventive method, as the ion source, such as these alkali-metal hydroxide, inorganic acid salt (ratio can be enumerated
Such as halide salts, nitrate) and acylate (such as acetate etc.) etc., it is not particularly limited.To described point
Son sieve contacts with the alkali metal ion source and carries out the mode of ion exchange there is no particular limitation, can be normal according to this area
The mode of rule is carried out.For example, temperature is 50～90 DEG C, and each time of contact is 1～3 hour, and solvent and solute weight ratio is 5～10.
In the inventive method, it is in the art to make the elements such as ferrum, cobalt, chromium, zirconium or bismuth be carried on the mode on X molecular sieve
Known infusion process, is loaded the elements such as ferrum, cobalt, chromium, zirconium or bismuth using the saline solution of ferrum, cobalt, chromium, zirconium or bismuth etc.
To on X molecular sieve.Dipping temperature is that between 40～80 DEG C, dip time is 3～8 hours.
The using method of above-mentioned catalyst is as follows：It is 200～600 DEG C in reaction temperature with toluene and methanol as raw material, reaction
Pressure is 0～0.5MPa, and raw material weight air speed is 0.5～10 hour-1Under conditions of, raw material is contacted with catalyst, reaction
Generate ethylbenzene and styrene；Toluene and methanol molar ratio are 0.1～10 in raw material.
In above-mentioned technical proposal, it is preferable that toluene is 2～7 with methanol molar ratio.
In above-mentioned technical proposal, it is preferable that reaction temperature is 350～500 DEG C.
In above-mentioned technical proposal, it is preferable that reaction pressure is 0～0.2MPa.
In above-mentioned technical proposal, it is preferable that raw material weight air speed is 1～8 hour-1。
The inventive method can be carried out in continuous flow reactor of fixed bed, and its process is summarized as follows：Take the desired amount of catalysis
Agent is put into the flat-temperature zone of reactor, and catalyst bottom is filled with quartz sand.Under temperature, the pressure of setting, by toluene and first
Alcohol mixes, and with micro being pumped into after preheater and nitrogen mixture reactor upper end is entered, and flows through beds and is urged
Change reaction, product is directly analyzed with valve injection into gas chromatogram.
The activity and selectivity of catalyst is calculated according to below equation：
In the evaluation result of the present invention, in industrial applications, use ratio of methanol is more crucial.
The inventive method effectively increases toluene first from the method for adding rare earth element and alkaline earth element auxiliary agent in X molecular sieve
Alcohol catalysis activity, so as to effectively increase use ratio of methanol.It is 6: 1 in toluene and methanol molar ratio using the inventive method,
Reaction temperature is 425 DEG C, and reaction pressure is normal pressure, and raw material weight air speed is 2.0 hours-1Under conditions of, use ratio of methanol can
To be up to 43%, ethylbenzene styrene overall selectivity achieves preferable technique effect up to 97%.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by ferric nitrate wiring solution-forming, ferrum is impregnated into into above-mentioned modified molecules
On sieve material.The content of load rear catalyst ferrum is 0.8%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.As a result it is as shown in table 1.
【Embodiment 2】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by cobalt nitrate wiring solution-forming, cobalt is impregnated into into above-mentioned modified molecules
On sieve material.The content of load rear catalyst cobalt is 0.9%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Embodiment 3】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by chromic nitrate wiring solution-forming, chromium is impregnated into into above-mentioned modified molecules
On sieve material.The content of load rear catalyst chromium is 1%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Embodiment 4】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by zirconium nitrate wiring solution-forming, zirconium is impregnated into into above-mentioned modified molecules
On sieve material.The content of load rear catalyst zirconium is 0.9%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Embodiment 5】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by bismuth nitrate wiring solution-forming, bismuth is impregnated into into above-mentioned modified molecules
On sieve material.The content of load rear catalyst bismuth is 1%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Embodiment 6】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by zirconium nitrate and bismuth nitrate wiring solution-forming, zirconium and bismuth are impregnated into
On above-mentioned modified molecular screen material.The content of load rear catalyst zirconium is 0.1%, and the content of bismuth is 0.9%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Embodiment 7】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by zirconium nitrate and bismuth nitrate wiring solution-forming, zirconium and bismuth are impregnated into
On above-mentioned modified molecular screen material.The content of load rear catalyst zirconium is 0.9%, and the content of bismuth is 0.1%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Embodiment 8】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by chromic nitrate and bismuth nitrate wiring solution-forming, chromium and bismuth are impregnated into
On above-mentioned modified molecular screen material.The content of load rear catalyst chromium is 0.5%, and the content of bismuth is 0.5%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Embodiment 9】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by cobalt nitrate and bismuth nitrate wiring solution-forming, cobalt and bismuth are impregnated into
On above-mentioned modified molecular screen material.The content of load rear catalyst cobalt is 0.5%, and the content of bismuth is 0.5%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Embodiment 10】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.Then by ferric nitrate and bismuth nitrate wiring solution-forming, ferrum and bismuth are impregnated into
On above-mentioned modified molecular screen material.The content of load rear catalyst ferrum is 0.5%, and the content of bismuth is 0.5%.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Comparative example 1】
Take silica alumina ratio SiO2/Al2O3=2.19 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
【Comparative example 2】
Take silica alumina ratio SiO2/Al2O3=2.80 NaX molecular sieves, use KNO3Solution, RbNO3Solution and CsNO3It is molten
Liquid carries out successively ion exchange, 100 DEG C of dryings 10 hours after filtration.After exchange, alkali metal ion exchanges molecule in catalyst
The ion-exchange degree of sodium ion is more than 85% in sieve.
By the beaded catalyst of the mesh of catalyst tablet forming obtained above 40～60, load reactor, in normal pressure, toluene
Methanol molar ratio was 6, at 2.0 hours-1Liquid air speed, 425 DEG C, N2Flow velocity is to carry out under conditions of 10 ml/mins
Activity rating.
As a result it is as shown in table 1.
Table 1
Claims (10)
1. it is a kind of to be used for toluene and methanol side chain alkylation ethylbenzene and cinnamic catalyst, by weight percentage, bag
Include following components：
A) X molecular sieve that 95～99.9% alkali metal ion is exchanged；
B) at least one in 0.1～5% ferrum, cobalt, chromium, zirconium or bismuth element.
2. toluene and methanol side chain alkylation synthesizing ethyl benzene and cinnamic catalyst are used for according to claim 1, its
It is characterised by that the molecular sieve is SiO2/Al2O3For 2～3 modified X molecular sieve.
3. toluene and methanol side chain alkylation synthesizing ethyl benzene and cinnamic catalyst are used for according to claim 2, its
It is characterised by that the molecular sieve is SiO2/Al2O3For the modified X molecular sieve of 2-2.5.
4. toluene and methanol side chain alkylation synthesizing ethyl benzene and cinnamic catalyst are used for according to claim 1, its
It is characterised by the one kind of component b) in metallic elements of ferrum, cobalt, chromium, zirconium, bismuth.
5. toluene and methanol side chain alkylation synthesizing ethyl benzene and cinnamic catalyst are used for according to claim 1, its
It is characterised by the one kind and bismuth of component b) in metallic element cobalt, chromium and zirconium.
6. toluene and methanol side chain alkylation synthesizing ethyl benzene and cinnamic catalyst are used for according to claim 1, its
It is characterised by by weight percentage, the content of component b) is 0.5～2%.
7. toluene is used for described in any one of claim 1～6 with methanol side chain alkylation synthesizing ethyl benzene and cinnamic catalyst
Preparation method, comprise the following steps：X molecular sieve using it is front with the alkali metal containing that concentration is 0.5～2.5 mol/L from
The solution of son carries out the X molecular sieve that ion exchange obtains alkali metals modified, and exchange temperature is 50～90 DEG C, when exchanging every time
Between 1～3 hour, solid-liquid weight ratio be 1: (5～10)；Then by least in metallic elements of ferrum, cobalt, chromium, zirconium, bismuth
Plant or several loading to obtain on modified molecular screen catalyst.
8. toluene is used for according to claim 7 with methanol side chain alkylation synthesizing ethyl benzene and the system of cinnamic catalyst
Preparation Method, it is characterised in that at least swapped with two kinds of alkali metal, exchange rear catalyst in potassium ion, rubidium ion or caesium from
It is 10～90% that at least two alkali metal ions in son exchange the ion-exchange degree of sodium ion in molecular sieve.
9. toluene is used for according to claim 7 with methanol side chain alkylation synthesizing ethyl benzene and the system of cinnamic catalyst
Preparation Method, it is characterised in that infusion process is adopted when in metallic elements of ferrum, cobalt, chromium, zirconium, bismuth even load to modified molecular screen,
Dipping temperature is 40～80 DEG C, and dip time is 3～8 hours.
10. a kind of Side chain alkylation method of toluene with methanol, with toluene and methanol as raw material, toluene and methanol molar ratio in raw material
It is 200～600 DEG C in reaction temperature for 0.1～10, reaction pressure is 0～0.5MPa, raw material weight air speed is 0.5～
Under conditions of 10 hours -1, raw material generates ethylbenzene and styrene with catalyst haptoreaction described in any one of claim 1～6.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529910A (en) * | 2018-11-29 | 2019-03-29 | 中国科学院大连化学物理研究所 | Catalyst, styrene preparation method for the reaction of methylbenzene methanol side chain alkylation |
| CN110152715A (en) * | 2019-05-28 | 2019-08-23 | 内江师范学院 | Fe-X type core-shell structure molecular sieve catalyst and its preparation method and application |
| CN110624600A (en) * | 2019-10-12 | 2019-12-31 | 厦门大学 | Catalyst for preparing ethylbenzene and xylene by alkylating toluene and methanol, preparation and application thereof |
| CN111072488A (en) * | 2019-12-16 | 2020-04-28 | 中国科学院大连化学物理研究所 | Preparation process of hexamethylene diamine based on cyclohexene |
| CN111085247A (en) * | 2019-12-16 | 2020-05-01 | 中国科学院大连化学物理研究所 | Alkaline molecular sieve supported catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110270006A1 (en) * | 2010-04-20 | 2011-11-03 | Fina Technology, Inc. | Use of an Additive in the Coupling of Toluene with a Carbon Source |
| CN103539601A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene and styrene through methylbenzene and methanol side chain alkylation |
| US8697593B2 (en) * | 2012-03-12 | 2014-04-15 | King Fahd University Of Petroleum And Minerals | Zeolite catalyst for the alkylation of toluene with methanol |
| CN104557374A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Toluene/methanol side chain alkylation method |
-
2015
- 2015-10-22 CN CN201510690501.1A patent/CN106607073B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110270006A1 (en) * | 2010-04-20 | 2011-11-03 | Fina Technology, Inc. | Use of an Additive in the Coupling of Toluene with a Carbon Source |
| US8697593B2 (en) * | 2012-03-12 | 2014-04-15 | King Fahd University Of Petroleum And Minerals | Zeolite catalyst for the alkylation of toluene with methanol |
| CN103539601A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene and styrene through methylbenzene and methanol side chain alkylation |
| CN104557374A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Toluene/methanol side chain alkylation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529910A (en) * | 2018-11-29 | 2019-03-29 | 中国科学院大连化学物理研究所 | Catalyst, styrene preparation method for the reaction of methylbenzene methanol side chain alkylation |
| CN109529910B (en) * | 2018-11-29 | 2020-08-07 | 中国科学院大连化学物理研究所 | Catalyst for toluene methanol side-chain alkylation reaction and styrene preparation method |
| CN110152715A (en) * | 2019-05-28 | 2019-08-23 | 内江师范学院 | Fe-X type core-shell structure molecular sieve catalyst and its preparation method and application |
| CN110624600A (en) * | 2019-10-12 | 2019-12-31 | 厦门大学 | Catalyst for preparing ethylbenzene and xylene by alkylating toluene and methanol, preparation and application thereof |
| CN111072488A (en) * | 2019-12-16 | 2020-04-28 | 中国科学院大连化学物理研究所 | Preparation process of hexamethylene diamine based on cyclohexene |
| CN111085247A (en) * | 2019-12-16 | 2020-05-01 | 中国科学院大连化学物理研究所 | Alkaline molecular sieve supported catalyst and preparation method and application thereof |
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