CN101121142A - Catalyst for methylbenzene methanol shape selective alkylation to synthesizing para-xylene - Google Patents

Catalyst for methylbenzene methanol shape selective alkylation to synthesizing para-xylene Download PDF

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CN101121142A
CN101121142A CNA2006100299502A CN200610029950A CN101121142A CN 101121142 A CN101121142 A CN 101121142A CN A2006100299502 A CNA2006100299502 A CN A2006100299502A CN 200610029950 A CN200610029950 A CN 200610029950A CN 101121142 A CN101121142 A CN 101121142A
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catalyst
selective alkylation
shape selective
methylbenzene methanol
zsm
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CN100566833C (en
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朱志荣
陈庆龄
孔德金
邹薇
俞高琴
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a catalyst for a shape-selective alkylation of toluene with methanol to synthesize p-xylene. The present invention mainly solves the problems in the former documents that in the practical application, the reaction stability of the catalyst is bad; the transformation rate of the toluene is low, and a selectivity of the p-xylene is not high. The present invention solves the problems quiet well by adopting a technical proposal that a relevant catalyst is prepared by that an oxide of transition metal elements is loaded on a ZSM-5 catalyst noumenon, and an organosilicon polymer is used for modifying a composite modification. The present invention can be used for the industrial production of the p-xylene, which is synthesized by the shape-selective alkylation of toluene with methanol.

Description

The catalyst of the synthetic paraxylene of methylbenzene methanol shape selective alkylation
Technical field
The present invention relates to the catalyst of the synthetic paraxylene of a kind of methylbenzene methanol shape selective alkylation, particularly about being used for the catalyst of the synthetic paraxylene of methylbenzene methanol phenyl ring alkylation.
Background technology
Methylbenzene methanol phenyl ring methylation reaction can change into toluene the higher dimethylbenzene of using value, and wherein the dimethylbenzene product is the equilibrium composition mixture of its three isomers, and the paraxylene that has the call only accounts for about 24%.Therefore there is the people to propose the methylated new technology of methylbenzene methanol selectivity phenyl ring, makes reaction system optionally generate paraxylene.After the beginning of the seventies, ZSM-5 was synthesized and since it to alkylation, isomerization, phenyl ring methylate, selective cracking process and by reactions such as methanol synthesized gasoline have the uniqueness catalytic performance, extensively paid attention to.The ZSM-5 zeolite constitutes pore canal system by 10 yuan of oxygen rings, has medium sized aperture and aperture.The aperture characteristics permission molecular diameter of ZSM-5 zeolite is that the paraxylene of 0.63 nanometer spreads rapidly, can seriously hinder ortho-xylene and meta-xylene diffusion that molecular diameter is 0.69 nanometer simultaneously.In toluene phenyl ring methylation reaction system, there is following relation in the diffusion coefficient of each species in the ZSM-5 duct: benzene 〉=toluene＞ethylbenzene ≈ paraxylene＞ortho-xylene ≈ meta-xylene, this fact means carries out the possibility that shape is selected to toluene phenyl ring methylation reaction, can obtain to be higher than in the dimethylbenzene product paraxylene content of isomer of thermodynamical equilibrium concentration far away.Because the outer surface acidity position is to the isomerization of the rich contraposition product non-selectivity that diffuses out in the duct, so end product still is equilibrium composition.In order to obtain having the catalyst of higher para-selectivity, the ZSM-5 molecular sieve is carried out modification be necessary.
The early stage method of modifying that adopts mainly is phosphorus, magnesium elements modification, and phosphorus, boron modification can play neutralization and promotor action to the molecular sieve surface acidity, and molecular sieve surface strong acid center is reduced, and the weak acid center increases relatively.Strong acid center forms stable meta-isomer easily, and the weak acid center then helps forming para-isomer.In addition, phosphorus can covering catalyst the strong acid center of outer surface, stop the quick isomerization of paraxylene of coming out in the duct, phosphorus can also make the effective dimensions in duct infall or aperture reduce.Catalyst is after phosphorus, boron modification, and also available halide, carbon dioxide, nitrogen-containing compound, sulfur-containing compound are further handled catalyst to improve para-selectivity.But these processing methods can obviously reduce activity of such catalysts, even reaction is carried out under very high temperature, conversion ratio is still not high, and P elements easy loss under reaction condition also is a defective of this technology.
Proposed modification among american documentation literature US3965210 and the US4145315, promptly reduced port size and shielding outer surface acidity active sites, preparation methylbenzene methanol phenyl ring alkylation catalyst the ZSM-5 molecular sieve structure.The method of modifying is to select silanes or (gathering) siloxane compound for use, and commonly used is polysiloxane-based.Thereby the meeting thermal decomposition under high temperature action of these silicon-containing compounds is converted into siliceous deposits and plays modifying function, compares with estersil commonly used at present, and price is far cheap, easy industrialization simple to operate.The method that silicon-containing compound is deposited on molecular sieve outer surface is that silicon-containing compound is dissolved in the n-hexane solvent, the impregnated zeolite outer surface, and roasting obtains selecting the catalyst of shapeization again.
Summary of the invention
Technical problem to be solved by this invention be in the past in the document methylbenzene methanol phenyl ring alkylation catalyst have the problem that reaction stability is poor, toluene conversion is low and the paraxylene selectivity is not high, a kind of catalyst of the new synthetic paraxylene of alkylation of toluene methanol is provided.This catalyst is used for the alkylation of toluene methanol reaction, has catalyst reaction good stability, active high, the characteristics that the product para-selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the catalyst of the synthetic paraxylene of a kind of methylbenzene methanol shape selective alkylation comprises following component by weight percentage:
A) 30～90%SiO 2/ Al 2O 3Mol ratio is 30～120 ZSM-5 molecular sieve; With carry thereon
B) 0.005～40% metallic element oxide, wherein metallic element is selected from least a oxide in VIB, IIB, VIII or the rare earth element except that cerium or is selected from least a oxide in magnesium, calcium, lanthanum or the Ce elements and is selected from least a hopcalite in VIB, IIB, VIII or the rare earth element except that cerium;
C) 1～60% binding agent.
In the technique scheme, the SiO of ZSM-5 molecular sieve 2/ Al 2O 3The mol ratio preferable range is 40～80, and ZSM-5 molecular sieve consumption preferable range is 50～85% by weight percentage; By weight percentage, the metallic element preferred version is selected from magnesium, iron, lanthanum or the Ce elements at least two kinds; The consumption of metallic element oxide preferable range by weight percentage is 0.01～20%, and more preferably scope is 2～12%; For improving para-selectivity, the catalyst preferred version is handled for flood polysiloxanes again behind shaping of catalyst, the consumption of polysiloxanes is 1～50% of a catalyst weight, and its preferable range is 10～30% of a catalyst weight, and the polysiloxanes preferred version is the methyl amine based polysiloxane.The consumption preferable range of binding agent is 10～50% by weight percentage; The binding agent preferred version is selected from silica, aluminium oxide or its mixture.
Preparation of catalysts method of the present invention is as follows:
With the ZSM-5 molecular sieve is active main body, adopts the method that adds the binding agent extrusion to prepare moulding.The binding agent that adds can be silica, aluminium oxide or its mixture, and the addition of binding agent is counted between 1% to 60% with its percentage in preformed catalyst butt weight.In catalyst preparation process, introduce required transition metal and carry out modification.The existence form of metallic element can be oxide, hydroxide or salt, and the method for introducing can adopt ion-exchange, dipping or mechanical mixture.The catalyst of moulding is selected the shape processing with polysiloxanes, obtains having in methylbenzene methanol phenyl ring methylation reaction the catalyst of very high para-selectivity.
The present invention is by introducing metallic element on Hydrogen HZSM-5 molecular sieve, particularly introduce at least two kinds of oxides or its mixture that are selected from magnesium, iron, lanthanum or the Ce elements oxide and carry out modification, weight space velocity 2.0 hours -1, reaction temperature is 440 ℃, and reaction pressure is 0.5MPa, and hydrogen/hydrocarbon mol ratio is to carry out the examination of methylbenzene methanol phenyl ring methylation reaction under 4.0 conditions.These data declarations ZSM-5 molecular sieve passes through metallic element, after particularly being selected from the modification of at least two kinds of oxides in magnesium, iron, lanthanum or the Ce elements oxide or its mixture, again by after handling with the methyl amine based polysiloxane, can significantly improve the para-selectivity of activity of such catalysts and product simultaneously, the characteristics that reaction stability is good have obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Na 2O content is less than 0.1% (weight), SiO 2/ Al 2O 3Mol ratio is 60, the ammonium type ZSM-5 molecular sieve powder of calcination loss 10% 75.1 grams, with Na 2O content is less than the boehmite (α-Al of 0.15% (weight), 550 ℃ of calcination losses 30% 2O 3H 2O) 24.2 grams fully mix, and mediate extruded moulding, dry back roasting pelletizing, with analyzing pure ferric nitrate [Fe (NO 3) 310H 2O] solution impregnation, oven dry, roasting are with analyzing pure magnesium acetate [Mg (CH 3COO) 24H 2O] solution impregnation, oven dry, roasting.Making weight ratio is: the catalyst A of Fe/Mg/ Hydrogen ZSM-5 molecular sieve/aluminium oxide=5/3/80/20.
[embodiment 2]
Na 2O content is less than 0.1% (weight), SiO 2/ Al 2O 3Mol ratio is ammonium type ZSM-5 molecular sieve powder 75.1 grams of 50,550 ℃ of calcination losses 10%, adds 42.0 gram Ludox (SiO 2Weight percent content 40%) fully mixes, mediate extruded moulding, dry back roasting pelletizing, with analyzing pure lanthanum nitrate [La (NO 3) 3NH 2O] and ferric nitrate [Fe (NO 3) 310H 2O] the mixed solution incipient impregnation, oven dry, roasting.Making weight ratio is: La/Fe/ Hydrogen ZSM-5 molecular sieve/SiO 2=4/11/80/20 catalyst B.
[embodiment 3]
Na 2O content is less than 0.1% (weight), SiO 2/ Al 2O 3Mol ratio is 80, the ammonium type ZSM-5 molecular sieve powder of calcination loss 10% 75.1 grams, adds the boehmite (α-Al of 64.2 grams and embodiment 2 same sizes 2O 3H 2O), fully mix, mediate extruded moulding, dry back roasting pelletizing, earlier with analyzing pure lanthanum nitrate [La (NO 3) 3NH 2O] the solution equivalent impregnation, oven dry, roasting, magnesium acetate [Mg (CH again 3COO) 24H 2O] the solution equivalent impregnation, ferric nitrate [Fe (NO is used in oven dry, roasting at last 3) 310H 2O] solution impregnation, oven dry, roasting.Making weight ratio is: La/Mg/Fe/ Hydrogen ZSM-5 molecular sieve/Al 2O 3=8/2/10/60/40 catalyst C.
[embodiment 4]
Ammonium type ZSM-5 molecular sieve powder 75.2 grams of embodiment 2 add and boehmite 24.3 grams of embodiment 2 same sizes mix the kneading extruded moulding, dry back roasting pelletizing.Earlier analyze pure cerous nitrate [Ce (NO with 0.5N 3) 36H 2O] 95 ℃ of water-baths of solution exchange 0.5 hour, oven dry, roasting, use 0.2N zinc acetate [Zn (CH again 3COO) 26H 2O] 95 ℃ of water-baths of solution exchange 0.5 hour, oven dry, roasting.Making weight ratio is: the catalyst D of Ce/Zn/ Hydrogen ZSM-5 molecular sieve/aluminium oxide=12/2/80/20.
[embodiment 5]
Ammonium type ZSM-5 molecular sieve powder 75.1 grams of embodiment 1, the boehmite of adding 24.2 grams and embodiment 2 same sizes mixes, and mediates extruded moulding, dries the back roasting, makes weight ratio and is: the catalyst E of HZSM-5 molecular sieve/aluminium oxide=75/25.
[embodiment 6～10]
Get 20 gram catalyst A～E respectively, join in the solution that methyl amine based polysiloxane and 30 ml n-hexanes are made into, remove n-hexane.Residue speed with 2 ℃/min in muffle furnace of drying is warming up to 540 ℃, keeps cooling naturally after 3 hours, obtain catalyst F～J respectively, wherein catalyst A, B handle with 2.0 gram methyl amine based polysiloxanes respectively and get catalyst F, G respectively; Catalyst C with 3.5 gram methyl amine based polysiloxanes handle catalyst H; Catalyst D, E respectively with 5.0 gram methyl amine based polysiloxanes handle catalyst I and J.
[embodiment 11～20]
On the fixed bed reaction evaluating apparatus catalyst A～J being carried out toluene phenyl ring methylation reaction activity and selectivity investigates.Loaded catalyst is 5.0 grams, and weight space velocity is 2.0 hours -1, reaction temperature is 440C, and reaction pressure is 0.5MPa, and hydrogen hydrocarbon mol ratio is 4.Reaction result is listed in table 1.
Figure A20061002995000061
Figure A20061002995000071
The toluene phenyl ring of the table 1 catalyst A～J catalytic reaction result that methylates
Instance number Catalyst Toluene conversion, % Para-selectivity, %
11 12 13 14 15 16 17 18 19 20 A B C D E F G H I J 36.3 29.6 28.1 35.5 38.8 33.0 27.7 25.2 29.3 34.5 50.1 74.9 85.4 44.8 24.1 69.2 90.4 94.1 60.3 54.2

Claims (9)

1. the catalyst of the synthetic paraxylene of a methylbenzene methanol shape selective alkylation comprises following composition by weight percentage:
A) 30～90%SiO 2/ Al 2O 3Mol ratio is 30～120 ZSM-5 molecular sieve; With carry thereon
B) 0.005～40% metallic element oxide, wherein metallic element is selected from least a oxide in VIB, IIB, VIII or the rare earth element except that cerium or is selected from least a oxide in magnesium, calcium, lanthanum or the Ce elements and is selected from least a hopcalite in VIB, IIB, VIII or the rare earth element except that cerium;
C) 1～60% binding agent.
2. according to the catalyst of the synthetic paraxylene of the described methylbenzene methanol shape selective alkylation of claim 1, it is characterized in that the SiO of ZSM-5 molecular sieve 2/ Al 2O 3Mol ratio is 40～80, and ZSM-5 molecular sieve consumption is 50～85% by weight percentage.
3. according to the catalyst of the synthetic paraxylene of the described methylbenzene methanol shape selective alkylation of claim 1, it is characterized in that the consumption of metallic element oxide is 0.01～20% by weight percentage.
4. according to the catalyst of the synthetic paraxylene of the described methylbenzene methanol shape selective alkylation of claim 3, it is characterized in that the consumption of metallic element oxide is 2～12% by weight percentage.
5. according to the catalyst of the synthetic paraxylene of the described methylbenzene methanol shape selective alkylation of claim 1, it is characterized in that flooding the polysiloxanes processing again behind the shaping of catalyst, the consumption of polysiloxanes is 1～50% of a catalyst weight.
6. according to the catalyst of the synthetic paraxylene of the described methylbenzene methanol shape selective alkylation of claim 5, the consumption that it is characterized in that polysiloxanes is 10～30% of a catalyst weight.
7. according to the catalyst of the synthetic paraxylene of the described methylbenzene methanol shape selective alkylation of claim 5, it is characterized in that polysiloxanes is the methyl amine based polysiloxane.
8. according to the catalyst of the synthetic paraxylene of the described methylbenzene methanol shape selective alkylation of claim 1, it is characterized in that the consumption of binding agent is 10～50% by weight percentage, binding agent is selected from silica, aluminium oxide or its mixture.
9. according to the catalyst of the synthetic paraxylene of the described methylbenzene methanol shape selective alkylation of claim 1, it is characterized in that metallic element is selected from least two kinds in magnesium, iron, lanthanum or the cerium.
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Cited By (10)

* Cited by examiner, † Cited by third party
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CN101972667A (en) * 2010-10-08 2011-02-16 同济大学 Catalyst used for alkylation of methanol, C10 aromatic hydrocarbons and 2-methylnaphthalene for synthesizing 2,6-dimethylnaphthalene
CN102463084A (en) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 Reaction device for preparing dimethylbenzene from methanol or dimethyl ether and methylbenzene
CN101885662B (en) * 2009-05-13 2013-09-18 中国石油化工股份有限公司 Toluene methanol alkylation method
CN104557375A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Method for co-producing p-methyl-ethylbenzene in production of p-xylene
CN105198691A (en) * 2015-09-08 2015-12-30 山东成泰化工有限公司 Synthesis method for p-xylene
CN105646132A (en) * 2014-11-20 2016-06-08 中国石油化工股份有限公司 Method for preparing xylene through arene alkylation
CN107008488A (en) * 2017-05-24 2017-08-04 兰州理工大学 Preparation method for benzene and the catalyst of methanol alkylation
CN111068756A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Toluene alkylation molecular sieve catalyst and application thereof
CN111068748A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Toluene methylation catalyst and application thereof
CN111068749A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Toluene para-alkylation molecular sieve catalyst and application thereof

Cited By (14)

* Cited by examiner, † Cited by third party
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CN101885662B (en) * 2009-05-13 2013-09-18 中国石油化工股份有限公司 Toluene methanol alkylation method
CN101972667A (en) * 2010-10-08 2011-02-16 同济大学 Catalyst used for alkylation of methanol, C10 aromatic hydrocarbons and 2-methylnaphthalene for synthesizing 2,6-dimethylnaphthalene
CN102463084A (en) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 Reaction device for preparing dimethylbenzene from methanol or dimethyl ether and methylbenzene
CN104557375B (en) * 2013-10-28 2016-07-13 中国石油化工股份有限公司 The method producing xylol co-production p-methyl-ethylbenzene
CN104557375A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Method for co-producing p-methyl-ethylbenzene in production of p-xylene
CN105646132A (en) * 2014-11-20 2016-06-08 中国石油化工股份有限公司 Method for preparing xylene through arene alkylation
CN105198691A (en) * 2015-09-08 2015-12-30 山东成泰化工有限公司 Synthesis method for p-xylene
CN107008488A (en) * 2017-05-24 2017-08-04 兰州理工大学 Preparation method for benzene and the catalyst of methanol alkylation
CN111068756A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Toluene alkylation molecular sieve catalyst and application thereof
CN111068748A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Toluene methylation catalyst and application thereof
CN111068749A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Toluene para-alkylation molecular sieve catalyst and application thereof
CN111068749B (en) * 2018-10-18 2023-01-24 中国石油化工股份有限公司 Toluene para-alkylation molecular sieve catalyst and application thereof
CN111068748B (en) * 2018-10-18 2023-04-07 中国石油化工股份有限公司 Toluene methylation catalyst and application thereof
CN111068756B (en) * 2018-10-18 2023-08-29 中国石油化工股份有限公司 Toluene alkylation molecular sieve catalyst and application thereof

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