CN104276924B - Toluene and ethylbenzene selective disproportionation method - Google Patents
Toluene and ethylbenzene selective disproportionation method Download PDFInfo
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Abstract
The present invention relates to a kind of toluene and ethylbenzene selective disproportionation method, catalyst modification is all modified using zeolite crystal outer surface in mainly solving existing disproportionation process, cause benzene to align aromatic hydrocarbons to be easily diffused into outside molecular sieve, contraposition aromatics yield is low, product benzene yield technical problem higher.The present invention by with toluene and ethylbenzene as raw material, 300~500 DEG C of reaction condition temperature, pressure 0.1MPa~10MPa, hydrogen-hydrocarbon ratio 0~10,0.1~10h of weight space velocity- 1Lower operation, raw material is contacted with catalyst, used catalyst by weight percentage, including following component：a）40~95% SiO2/Al2O3Molecular proportion is 12~100 molecular sieves of ZSM 5；b）4.9~59.9% binding agent selected from silica, aluminum oxide or the combination of the two composition；c）Technical scheme containing 0.1%~15% boron element or its oxide, preferably solves the problem, can be used in toluene and ethylbenzene shape-selective disproportionation reaction.
Description
Technical field
The present invention relates to a kind of toluene and ethylbenzene selective disproportionation method.
Background technology
Methylbenzene shape-selective disproportionation reaction is typical selective reaction in commercial Application, it by toluene conversion into benzene and highly concentrated
The paraxylene of degree, wherein xylene products are the equilibrium composition mixtures of its three isomers, have the call to diformazan
Benzene accounts for more than 80%.P-methyl-ethylbenzene downstream product p-methylstyrene can improve the performance of polymer, and reducing density has weight
The performance wanted.Conventional industrial catalyst uses ZSM-5 zeolite molecular sieve, the molecular sieve to constitute 3 D pore canal body by 10 membered oxygen rings
System, with the aperture and aperture close with molecular size, the diameter of straight hole road and sinusoidal duct connecting place reaches 1 in 3 D pore canal
Nanometer.The paraxylene that the aperture feature of ZSM-5 zeolite allows molecular diameter to be 0.63 nanometer spreads rapidly, while can hinder point
The ortho-xylene and meta-xylene diffusion limited of a diameter of 0.69 nanometer of son are larger.In toluene disproportionation process system, each species
The following relation of diffusion rate in ZSM-5 ducts：Benzene >=toluene ＞ ethylbenzene ≈ paraxylene ＞ ortho-xylene ≈ meta-xylenes
＞ p-methyl-ethylbenzenes, the significantly larger than paraxylene isomery of thermodynamical equilibrium concentration can be obtained in xylene products using the molecular sieve
Body and p-methyl-ethylbenzene content.Because molecular sieve outer surface acidity position aligns product non-selectivity to the richness diffused out from duct
Isomerization, therefore final product still be equilibrium composition.Therefore, the catalysis with para-selectivity higher is expected
Agent, must be modified to ZSM-5 molecular sieve.Inside molecular sieve, because two kinds of duct connecting places are larger, and at this exist compared with
Big space, paraxylene diffusion can at once be isomerizated into xylene isomer herein, and a part is converted into ethylbenzene, to selection
Property disproportionation cause large effect.The disclosure that p-methyl-ethylbenzene is synthesized from toluene and ethylbenzene is reported and studies less.
Proposed in document USP5367099, USP5607888, WO97/46636 and prepare toluene selective disproportionation catalyst side
Method.The method of its modification is, from the macromolecular compound with thermolysis property, molecular sieve to be deposited on by certain method
Outer surface, then by high-temperature process, by the thermal decomposition of these macromolecular compounds, inert coatings are converted into, shield molecular sieve appearance
The acid centre in face, while also reducing port size to a certain extent.Although catalyst prepared by the method is reached to diformazan
The requirement of benzene selective, but the use due to catalyst routine ZSM-5 molecular sieve containing aluminium, the more carbon nine of Catalyst Production
And the aromatic hydrocarbons of the above.The by-product aromatic hydrocarbons of the generation, is easier to cracking, generates non-aromatic and benzene, reduces the yield of dimethylbenzene.
In United States Patent (USP) 6486373, employ compound molecule screen method to improve the activity of toluene selective disproportionation catalyst,
Boron element is employed in framework of molecular sieve.It passes through ZSM-5 molecular sieve for matrix, and other pore passage structures are formed in its surface
Combination, is then molded again, carries out follow-up modified, is reached and is reduced modified requirement and improve reactivity.But due to
In skeleton, the 3 D pore canal intersection cavity of ZSM-5 molecular sieve is further increased boron, makes dimethylbenzene continue to react, side reaction
Increase.
The invention aims to overcome in previous literature in aromatic hydrocarbons selective disproportionation catalyst, due to 3 D pore canal duct
Intersection cavity is larger, and reaction causes benzene to be easily diffused into outside molecular sieve, and paraxylene and p-methyl-ethylbenzene are selectively low, the choosing of product benzene
Selecting property problem higher.The present invention is by using boron oxide compound is used in catalyst preparation process, obtaining aromatic hydrocarbons selective disproportionation
Catalyst, preferably solves the problem.
The content of the invention
The technical problems to be solved by the invention be in existing disproportionation process catalyst modification all using outside zeolite crystal
Surface is modified, and causes benzene to align aromatic hydrocarbons and is easily diffused into outside molecular sieve, and contraposition aromatics yield is low, and product benzene yield technology higher is asked
Topic, the present invention provides a kind of new kind toluene and ethylbenzene selective disproportionation method, and the method is by using in catalyst preparation process
Middle use boron enters in molecular sieve pore passage to aromatic hydrocarbons selective disproportionation catalyst with oxide, selects the aromatic hydrocarbons occurred on catalyst
Shape disproportionated reaction generates dimethylbenzene and first ethylbenzene product to be increased, and is selectively improved with paraxylene and p-methyl-ethylbenzene, while also
Improve the activity benefit of catalyst purpose product reaction.
The present invention uses the technical scheme of the preparation method of selective disproportionation catalyst as follows：A kind of toluene and ethylbenzene are shape-selective
Disproportionation process, with toluene and ethylbenzene as raw material, 300~500 DEG C of reaction condition temperature, pressure 0.1MPa~10MPa, hydrogen-hydrocarbon ratio 0
~10,0.1~10h of weight space velocity- 1Lower operation, raw material is contacted with catalyst, used catalyst by weight percentage, including
Following component：
a）40~95% SiO2/Al2O3Molecular proportion is 12~100 ZSM-5 molecular sieve；
b）4.9~59.9% binding agent selected from silica, aluminum oxide or the combination of the two composition；
c）Containing 0.1%~15% boron element or its oxide；
In for above-mentioned offer technical scheme, because the zeolite matrix of methylbenzene shape-selective disproportionation reaction requirement is with higher
Active pharmaceutical, the ZSM-5 molecular sieve that general industry catalyst is used uses ZSM-5 molecular sieve as active basis, the present invention, its
SiO2/Al2O3Molecular proportion is 12~100.Molecular sieve silica alumina ratio is lower, and activated centre is more, but too low Zeolite synthesis are difficult,
Crystallization of molecular sieves rate is relatively low, is not suitable for being modified.Therefore ZSM-5 molecular sieve preferably SiO2/Al2O3Molecular proportion is 20~70.
Catalyst modification precursor is obtained after molecular sieve and silica or alumina binder shaping and roasting.Silica or and
The molding adhesive for being used as molecular sieve of aluminum oxide.Binding agent silica or account for weight with aluminum oxide knot in the catalyst
5~60%.
Boron enters the inside of molecular sieve in the catalyst, mainly on the intersection duct in molecular sieve ZSM-5, oxygenous
The boron oxide compound being fired into atmosphere.Boron is combined with framework of molecular sieve, forms a part for cell walls.Can also be in the atmosphere of anaerobic
Lower roasting, exists in molecular sieve in the form of boron.Actually prepare in can also part of boron outside zeolite crystal.Catalyst
In boron can also be introduced in sieve synthesis procedure.Because boron is weaker to aromatic disproportion and isomerization reaction, therefore to molecule
The modified influence of the selectivity of sieve is smaller, can boron into before catalyst or and after carry out catalyst and improve Selectivity for paraxylene
It is modified.
In actually preparing, boron in catalyst can by boron compound can selected from borane, borine, borane derivative,
One or more roastings of halogenation boron, boric acid are obtained.In actually roasting, in controllable scope, above-mentioned boron compound leads to
After crossing the method for exchange, impregnating, then aoxidized or cracked, less boron or and oxidation are obtained inside and outside molecular sieve pore passage
Thing.In above-mentioned toluene selective disproportionation catalyst, boron or with the weight % of boron oxide compound content 0.01%~15.
Catalyst is prepared according to the technical program, can be used for ethylbenzene selectivity disproportionated reaction, methylbenzene selective alkylation instead
Should.
According to the technical program, can continue using other method of modifying metals or its oxide or two containing B catalyst
Silica modified method is modified.Such as containing also containing Zn, Cu, Pt, Pb, Mg and other alkaline-earth metal in B catalyst, with
Catalyst weight percent meter, content is 0 ~ 12%.
According to the technical program, the concentration that is modified is impregnated 1-4 time using 1%-40% organic silicon solutions, after drying, 200~
600 DEG C for the treatment of 0.1-40h roastings.Preferred technical scheme is that the concentration that is modified is using 2%-20% organic silicon solutions dipping 1 ~ 3
It is secondary, after drying, 0.2-20h is calcined at 300~500 DEG C.
According to the technical program, reaction can carry out technique adjustment according to raw material proportioning difference.
Catalyst is prepared according to the technical program, 300~500 DEG C of reaction condition temperature, pressure 0.1MPa~10MPa,
Hydrogen-hydrocarbon ratio 0~10,0.1~10h of weight space velocity- 1Lower operation.Wherein toluene can be in 0.001-99.999 with the mol ratio of ethylbenzene.
Diameter in above-mentioned technical proposal due to boron element is smaller, can enter in molecular sieve pore passage, simultaneously because this yuan
The acidic site that element is formed is weaker, weaker to reaction and side reaction activity, can be with very effective blunt during catalyst reaction
Change or formed the effect of spatial selectivity.
In aromatic hydrocarbons selective disproportionation catalyst, ZSM-5 molecular sieve is the three-dimensional pore passage structure for communicating, and is connected in duct
Place, aperture reaches 1.0 nanometers, and the paraxylene and p-methyl-ethylbenzene for reacting generation occur isomerization reaction, while the activity at this
Centre bit is higher to disproportionated reaction activity, can continue the first and second benzene of reaction generation, diethylbenzene and benzene-like compounds, naphthalenes chemical combination
Thing etc. reacts.And the aromatic hydrocarbons of the higher molecular weight of toluene side reaction generation, cracking reaction is susceptible to, non-aromatic and benzene is produced, increase
Add ring damage, reduce the yield of contraposition aromatic hydrocarbons.While the duct of ZSM-5, toluene and benzene product can be very fast by straight hole road
Diffusion at zeolite crystal.
Entered at larger duct by the element of boron, duct is substantially reduced, and can effectively prevent such side reaction
Occur.Although relatively low toluene conversion, due to hindering the generation of side reaction, methylbenzene shape selective disproportionation is greatly reduced secondary anti-
The carrying out answered.Simultaneously because the presence of boron, toluene increased the residence time, adds somewhat to the conversion ratio of toluene.Cause
This catalyst for employing the technical program preparation can greatly improve the performance of catalyst, and dimethylbenzene yield increases.
By the way that using following specific embodiment, the invention will be further elaborated：
Specific embodiment
【Embodiment 1】
By ZSM-5 molecular sieve and the contoured body 100g of 20% weight silica that silicon-aluminum containing molecular proportion is 25, use
The 90# solvents containing borine 10wt% are the maceration extract of solvent under nitrogen atmosphere（Hereinafter use identical alkane solvent）100g soaks
Stain body, after filtering, normal temperature in a nitrogen atmosphere dry after containing 1%（Oxygen volume ratio）Nitrogen and oxygen atmosphere under
500 DEG C are calcined 3 hours, obtain catalyst intermediate.500 DEG C of roastings after being dried using 10wt%DC550 silicone oil 120g immersion filtrations
Burn 6 and obtain catalyst h4 times.Last catalyst mass containing B 6.0%.
5.0 grams of obtained catalytic amount is taken, aromatic hydrocarbons is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio
99.99:1）Disproportionated reaction activity and selectivity is investigated（All examples below all uses the method evaluation）.It is in weight space velocity
4.0h- 1, reaction temperature is 400 DEG C, and reaction pressure is 2.8MPa, and hydrogen hydrocarbon mol ratio is 2.Reaction result toluene conversion
26.0%, conversion of ethylbenzene 10%, Selectivity for paraxylene 93.1%, p-methyl-ethylbenzene 98.5%, p-Diethylbenzene selectivity 99.9%,
Benzene/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）1.05.
Wherein（Following examples are same）：
Toluene conversion=（Enter the weight of the reactor outlet toluene of weight one of reactor toluene）/ (enter reactor toluene
Weight) * 100%
Conversion of ethylbenzene=（Enter the weight of the reactor outlet ethylbenzene of weight one of reactor ethylbenzene）/ (enter reactor ethylbenzene
Weight) * 100%
Paraxylene para-selectivity=（Paraxylene mass percent in product）/ (dimethylbenzene in product
Mass percent) * 100%
P-methyl-ethylbenzene para-selectivity=（P-methyl-ethylbenzene mass percent in product）/ (the first and second benzene in product
Mass percent) * 100%
P-Diethylbenzene ethylbenzene para-selectivity=（P-Diethylbenzene mass percent in product）/ (two in product
Ethylbenzene mass percent) * 100%
Benzene/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）=（React the benzene mole number of generation）/ (the diformazan of reaction generation
The benzene of benzene+the first and second+diethylbenzene molal quantity)
【Embodiment 2】
By ZSM-5 molecular sieve and the contoured body 100g of 60% weight silica that silicon-aluminum containing molecular proportion is 15, use
The maceration extract 100g dipping bodies of the 20wt% of boron containing ethane under nitrogen atmosphere, after filtering, after normal temperature is dried in a nitrogen atmosphere, often
Temperature in a nitrogen atmosphere dry after nitrogen atmosphere under 600 DEG C be calcined 2 hours, obtain catalyst intermediate.Continue to use
500 DEG C of roastings obtain catalyst secondary time after 40wt%DC550 silicone oil 120g immersion filtrations are dried.Last catalyst matter containing B
Amount 5.2%.
5.0 grams of obtained catalytic amount is taken, aromatic hydrocarbons is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio
99:1）Disproportionated reaction activity and selectivity is investigated.It is 8.0h in weight space velocity- 1, reaction temperature is 400 DEG C, and reaction pressure is
5.0MPa, hydrogen hydrocarbon mol ratio is 4.Conversion of ethylbenzene 30%, Selectivity for paraxylene 93.1%, p-methyl-ethylbenzene 97.5%, to diethyl
Benzene selective 99.9%, benzene/（（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mol ratio 1.02.
【Embodiment 3】
By ZSM-5 molecular sieve and the contoured body 100g of 30% weight silica that silicon-aluminum containing molecular proportion is 99, use
The 0.5wt% maceration extracts 100g containing borine ethamine impregnates body in a nitrogen atmosphere, after normal temperature is filtered in a nitrogen atmosphere, in nitrogen
After being dried under gas atmosphere, containing 3%（Oxygen volume ratio）Nitrogen and oxygen atmosphere under after 600 DEG C be calcined 2 hours, obtain catalyst
Intermediate.200 DEG C of roastings once obtain catalyst in 40 hours after continuing to be dried using 1wt%DC550 silicone oil 200g immersion filtrations.
Last catalyst mass containing B 0.01%.
5.0 grams of obtained catalytic amount is taken, aromatic hydrocarbons is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio
90:10）Disproportionated reaction activity and selectivity is investigated.It is 10.0h in weight space velocity- 1, reaction temperature is 500 DEG C, and reaction pressure is
10.0MPa, reaction result toluene conversion 12.0%, conversion of ethylbenzene 30%, Selectivity for paraxylene 94.0%, p-methyl-ethylbenzene
99.0%, p-Diethylbenzene selectivity 99.5%, product benzene/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mol ratio 1.15.
【Embodiment 4】
By ZSM-5 molecular sieve and the contoured body 100g of 5% weight silica that silicon-aluminum containing molecular proportion is 50, using
The maceration extract 100g of boron chloride 5% dippings body, after normal temperature is filtered in a nitrogen atmosphere, dries in a nitrogen atmosphere under nitrogen atmosphere
Afterwards, containing 15%（Oxygen volume ratio）Nitrogen and oxygen atmosphere it is lower 550 DEG C be calcined 2 hours, obtain catalyst intermediate.Continue to adopt
400 DEG C are calcined 6 hours after being dried with 10wt%DC550 silicone oil 120g immersion filtrations, and repetition is secondary to obtain catalyst.Last urges
Agent mass containing B 1.1%.
5.0 grams of obtained catalytic amount is taken, aromatic hydrocarbons is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio
1:1000）Disproportionated reaction activity and selectivity is investigated.It is 6.0h in weight space velocity- 1, hydrogen-hydrocarbon ratio 2.0, reaction temperature is 300 DEG C,
Reaction pressure is 3.0MPa, reaction result toluene conversion 8.0%, conversion of ethylbenzene 30%, Selectivity for paraxylene 95.2%,
P-methyl-ethylbenzene 99.5%, p-Diethylbenzene selectivity 99.7%, benzene/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mol ratio 1.01.
【Embodiment 5】
By ZSM-5 molecular sieve and the contoured body 100g of 15% weight silica that silicon-aluminum containing molecular proportion is 30, use
Body is impregnated at 100g95 DEG C of boronic acid containing 3wt% aqueous impregnations liquid, after filtering, 500 DEG C are calcined 3 hours after drying, and are urged
Agent intermediate.500 DEG C are calcined 3 hours after continuing to be dried using 20wt%DC550 silicone oil 120g immersion filtrations, obtain in triplicate
To catalyst.The catalyst quality of last B oxides contains 2.3%.
5.0 grams of obtained catalytic amount is taken, aromatic hydrocarbons is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio
60:40）Disproportionated reaction activity and selectivity is investigated.It is 6.0h in weight space velocity- 1, hydrogen-hydrocarbon ratio 1.0, reaction temperature is 350 DEG C,
Reaction pressure is 1.0MPa, reaction result toluene conversion 15.0%, conversion of ethylbenzene 35%, Selectivity for paraxylene 90.1%,
P-methyl-ethylbenzene 98.0%, p-Diethylbenzene selectivity 99.7%, benzene/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mol ratio 1.10.
【Embodiment 6】
By ZSM-5 molecular sieve that silicon-aluminum containing molecular proportion is 30 and the shaping sheet of 15% weight silica and 3% re-oxidation aluminium
Body 100g, using the two borane 20wt% and maceration extract 100g of monoborane 3% dipping bodies are contained in a nitrogen atmosphere, normal temperature is in nitrogen
After being filtered under gas atmosphere, after drying in a nitrogen atmosphere, containing 3%（Oxygen volume ratio）Nitrogen and oxygen atmosphere it is lower 600 DEG C roasting
Burn 2 hours, obtain catalyst intermediate.530 DEG C of roastings 3 after continuing to be dried using 22wt%DC550 silicone oil 120g immersion filtrations
Hour, catalyst is obtained in triplicate.Last catalyst mass containing B 14.9%.
5.0 grams of obtained catalytic amount is taken, aromatic hydrocarbons is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio
2:100）Disproportionated reaction activity and selectivity is investigated.It is 2.0h in weight space velocity- 1, hydrogen-hydrocarbon ratio 0.5, reaction temperature is 420 DEG C,
Reaction pressure is 0.6MPa, reaction result toluene conversion 22.0%, conversion of ethylbenzene 39.0%, Selectivity for paraxylene
90.5%, p-methyl-ethylbenzene 98.9%, p-Diethylbenzene selectivity 99.8%, benzene/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mole
Than 1.10.
【Embodiment 7】
By the shaping of ZSM-5 molecular sieve and 15% weight silica and 10% re-oxidation aluminium that silicon-aluminum containing molecular proportion is 30
Body 100g, body, normal temperature mistake in a nitrogen atmosphere are impregnated using the maceration extracts of 10wt%100g containing borane in a nitrogen atmosphere
After filter, after drying in a nitrogen atmosphere, containing 1%（Oxygen volume ratio）Nitrogen and oxygen atmosphere it is lower 700 DEG C be calcined 2 hours, obtain
To catalyst intermediate.530 DEG C are calcined 3 hours after continuing to be dried using 22wt%DC550 silicone oil 120g immersion filtrations, repeat three
It is secondary to obtain catalyst.Last catalyst mass containing B 6.1%.
5.0 grams of obtained catalytic amount is taken, aromatic hydrocarbons is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio
99.5:1）Disproportionated reaction activity and selectivity is investigated.It is 3.0h in weight space velocity- 1, hydrogen-hydrocarbon ratio 3.0, reaction temperature is 420 DEG C,
Reaction pressure is 0.1MPa, reaction result toluene conversion 28.0%, conversion of ethylbenzene 6%, Selectivity for paraxylene 91.2%,
P-methyl-ethylbenzene 99.5%, benzene/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mol ratio 1.10.
【Embodiment 8】
By ZSM-5 molecular sieve and the contoured body 100g of 30% weight silica that silicon-aluminum containing molecular proportion is 100, use
The maceration extracts of 2wt%100g containing borane impregnate body in a nitrogen atmosphere, after normal temperature is filtered in a nitrogen atmosphere, in nitrogen atmosphere
After lower drying, containing 1%（Oxygen volume ratio）Nitrogen and oxygen atmosphere it is lower 540 DEG C be calcined 1 hour, obtain catalyst intermediate.
600 DEG C are calcined 0.1 hour after continuing to be dried using 5wt%DC550 silicone oil 120g immersion filtrations, and repetition is secondary to obtain catalyst.
Last catalyst mass containing B 1.1%.
5.0 grams of obtained catalytic amount is taken, is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio 1:
99）Disproportionated reaction activity and selectivity is investigated.It is 0.1h in ethylbenzene weight air speed- 1, reaction temperature is 400 DEG C, and reaction pressure is
8.0MPa, reaction result conversion of ethylbenzene 33.0%, toluene conversion 10%, Selectivity for paraxylene 93.1%, p-methyl-ethylbenzene
98.0%, p-Diethylbenzene selectivity 98.7%, benzene in product/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mol ratio 30.5.
【Embodiment 9】
By the shaping that silicon-aluminum containing molecular proportion is the 70, ZSM-5 molecular sieve of boracic weight 1.0% and 30% weight silica
Body 100g, body is impregnated using the maceration extracts of 4wt%100g containing borane in a nitrogen atmosphere, and normal temperature is filtered in a nitrogen atmosphere
Afterwards, after drying in a nitrogen atmosphere, containing 1%（Oxygen volume ratio）Nitrogen and oxygen atmosphere it is lower 540 DEG C be calcined 1 hour, obtain
Catalyst intermediate.Last catalyst mass containing B 2.6%.
550 DEG C are calcined 6 hours after continuing to be dried using 5wt%DC550 silicone oil 120g immersion filtrations, repeat secondary being urged
Agent.5.0 grams of obtained catalytic amount is taken, is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio 99.5:1）
Disproportionated reaction activity and selectivity is investigated.It is 0.1h in weight space velocity- 1, reaction temperature is 300 DEG C, and reaction pressure is 8.0MPa,
Reaction result toluene conversion 11.0%, conversion of ethylbenzene 5%, Selectivity for paraxylene 97.0%, p-methyl-ethylbenzene 99.7%, benzene/
（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mol ratio 1.01.
【Embodiment 10】
The silicon-aluminum containing molecular proportion that crystallization is synthesized is 70, ZSM-5 molecular sieve and 30% weight silica shaping sheet
Body 100g, body is impregnated using the maceration extracts of 2wt%100g containing borane in a nitrogen atmosphere, and normal temperature is filtered in a nitrogen atmosphere
Afterwards, after drying in a nitrogen atmosphere, containing 2%（Oxygen volume ratio）Nitrogen and oxygen atmosphere it is lower 540 DEG C be calcined 1 hour, obtain
Intermediate.Continue using the dippings of the maceration extracts of 2wt%100g containing borane 100g in a nitrogen atmosphere, repeat condition is in 540 DEG C of roastings
Burn 1 hour, the catalyst intermediate for obtaining.550 DEG C of roastings 6 after continuing to be dried using 5wt%DC550 silicone oil 120g immersion filtrations
Hour, repetition is secondary to obtain catalyst.Last catalyst mass containing B 1.8%.
5.0 grams of obtained catalytic amount is taken, is carried out on fixed bed reaction evaluating apparatus（Toluene and ethylbenzene mol ratio
99.5:1）Disproportionated reaction activity and selectivity is investigated.It is 1.0h in weight space velocity- 1, reaction temperature is 400 DEG C, and reaction pressure is
10.0MPa, reaction result toluene conversion 34.5%, conversion of ethylbenzene 8%, Selectivity for paraxylene 97.3%, p-methyl-ethylbenzene
99.8%, product benzene/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mol ratio 1.01.
【Comparative example 1】
By ZSM-5 molecular sieve and the contoured body A 100g of 20% weight silica that silicon-aluminum containing molecular proportion is 25, adopt
500 DEG C of roastings obtain catalyst three times after being dried with 20wt%DC550 silicone oil 120g immersion filtrations.Take obtained catalytic amount
5.0 grams, disproportionated reaction activity and selectivity investigation is carried out on fixed bed reaction evaluating apparatus.In aromatic hydrocarbons（Toluene and ethylbenzene rub
You compare 99.5:1）Weight space velocity is 4.0h- 1, reaction temperature is 400 DEG C, and reaction pressure is 2.8MPa, and hydrogen hydrocarbon mol ratio is 2.Instead
Answer result toluene conversion 30.0%, conversion of ethylbenzene 2%, Selectivity for paraxylene 90.1%, p-methyl-ethylbenzene 96.9%, to two
The benzene of methylbenzene selective 93.1%/（First and second benzene+dimethylbenzene+diethylbenzene mol ratio）Mol ratio 1.29.
Claims (9)
1. a kind of toluene and ethylbenzene selective disproportionation method, with toluene and ethylbenzene as raw material, 320~460 DEG C of reaction condition temperature, pressure
Power 0.5MPa~6.0MPa, hydrogen-hydrocarbon ratio 0.5~4,1~6h of weight space velocity- 1Lower operation, raw material is contacted with catalyst, catalysis used
Agent by weight percentage, including following component：
A) 40~95% SiO2/Al2O3Molecular proportion is 12~100 ZSM-5 molecular sieve；
B) 4.9~59.9% binding agent selected from silica, aluminum oxide or the combination of the two composition；
C) containing 0.1%~15% boron simple substance or its oxide；
Wherein, the boron simple substance or its oxide in catalyst are obtained by boron compound roasting, in roasting, above-mentioned boronation are closed
Thing is after impregnating, then is aoxidized or cracked, and boron or/and oxide are obtained inside and outside molecular sieve pore passage；Boron draws in catalyst
After entering preceding or introducing, selectivity is carried out to molecular sieve with silica modified.
2. toluene and ethylbenzene selective disproportionation method according to claim 1, it is characterised in that the SiO of ZSM-5 molecular sieve2/
Al2O3Molecular proportion is 20~70；Boron is present in molecular sieve crystal or/and outside molecular sieve crystal.
3. toluene and ethylbenzene selective disproportionation method according to claim 1, it is characterised in that the boron in catalyst is in molecular sieve
Introduced in building-up process.
4. toluene and ethylbenzene selective disproportionation method according to claim 1, it is characterised in that in boron element in shaping of catalyst
It is re-introduced into afterwards or/and using metallic element is selectively modified.
5. toluene and ethylbenzene selective disproportionation method according to claim 1, it is characterised in that boron compound be selected from borane,
At least one of borine, borane derivative, halogenation boron and boric acid.
6. toluene and ethylbenzene selective disproportionation method according to claim 1, it is characterised in that toluene is with the mol ratio of ethylbenzene
0.001-99.999。
7. toluene and ethylbenzene selective disproportionation method according to claim 1, it is characterised in that in catalyst also containing Zn, Cu,
At least one in Pt, Pb, Mg metallic element, in terms of catalyst weight percent, content is 0.01-12%.
8. toluene and ethylbenzene selective disproportionation method according to claim 1, it is characterised in that modified concentration is using 1%-40 weights
Amount % organic silicon solutions impregnate 1~4 time, after drying, 0.1-40h roastings are processed at 200~600 DEG C.
9. toluene and ethylbenzene selective disproportionation method according to claim 8, it is characterised in that modified concentration is using 2%-20 weights
Amount % organic silicon solutions impregnate 1~3 time, after drying, 0.2-20h roastings are processed at 300~500 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310286132.0A CN104276924B (en) | 2013-07-09 | 2013-07-09 | Toluene and ethylbenzene selective disproportionation method |
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| CN107754848B (en) * | 2016-08-23 | 2020-12-29 | 中国石油化工股份有限公司 | Catalyst for synthesizing p-methyl ethyl benzene by shape-selective catalysis of carbon octaene |
| CN112777609B (en) * | 2019-11-08 | 2022-10-11 | 国家能源投资集团有限责任公司 | Composite twin crystal ZSM-5 molecular sieve, and preparation method and application thereof |
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| US4709110A (en) * | 1983-08-15 | 1987-11-24 | Mobil Oil Corporation | Catalytic conversion with boron trifluoride treated zeolite |
| CN103121913A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing catalyst for shape-selective disproportionation of methylbenzene |
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| US4709110A (en) * | 1983-08-15 | 1987-11-24 | Mobil Oil Corporation | Catalytic conversion with boron trifluoride treated zeolite |
| CN103121913A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing catalyst for shape-selective disproportionation of methylbenzene |
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