CN107649171A - Continuity method isomerization produces the catalyst of durol - Google Patents

Continuity method isomerization produces the catalyst of durol Download PDF

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Publication number
CN107649171A
CN107649171A CN201711098907.6A CN201711098907A CN107649171A CN 107649171 A CN107649171 A CN 107649171A CN 201711098907 A CN201711098907 A CN 201711098907A CN 107649171 A CN107649171 A CN 107649171A
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CN
China
Prior art keywords
oxide
salt
soluble
durol
catalyst
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Pending
Application number
CN201711098907.6A
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Chinese (zh)
Inventor
吴义彪
许飞
任倩
潘学林
苏勇
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JIANGSU HUALUN CHEMICAL INDUSTRY Co Ltd
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JIANGSU HUALUN CHEMICAL INDUSTRY Co Ltd
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Priority to CN201711098907.6A priority Critical patent/CN107649171A/en
Publication of CN107649171A publication Critical patent/CN107649171A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
    • C07C5/2732—Catalytic processes
    • C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • C07C2529/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium

Abstract

The invention discloses a kind of catalyst of continuity method isomerization production durol, include the component of following percentage by weight：The oxide of nickel or the oxide 4 ~ 7% of palladium, the oxide 2 ~ 5% of cerium, the oxide 2 ~ 3% of alum, the oxide of copper and the oxide 3 ~ 7% of manganese, wherein：The oxide of copper: oxide=1 of manganese: 2 ~ 3, weight ratio, the oxidation 5 ~ 6% of potassium, carrier surplus, continuity method isomerization produces the catalyst of durol, and in the reaction product of acquisition, the weight percent content of each component is：Durol 43 ~ 45%, isodurene 19 ~ 22%, prehnitene 1 ~ 6%, selectively reach more than 91.2 %, yield reaches more than 54.7 %, can successive reaction, be suitable for industrialized production.

Description

Continuity method isomerization produces the catalyst of durol
Technical field
The present invention relates to the method for production durol, and in particular to catalyst.
Background technology
Durol is a kind of important chemical industry raw material, in numerous fields, is widely used, available for making Standby pyromellitic acid anhydride, extends downwardly and polyimide resin is made, plasticizer, dyestuff, surfactant, while is also one kind Important medicine intermediate.
At present, described durol, prepared by initiation material of reformed C 10, basic process route is such as Under：
Using rectificating method, the light component before C10 is removed, durol pregnant solution is then obtained by rectificating method again, it is cold Freeze crystallization kettle, separate out durol crystal, then filter, collect the durol finished product that content is 99%；
But the caused mother liquor in filtering, the also component containing following percentage by weight：
Durol 15 ~ 16%, isodurene 30 ~ 35%, prehnitene 18 ~ 19%, how by the small prehnitene of added value The high durol of economic value added is changed into isodurene, then reuse again, is always problem of concern.
By isomerization reaction, described prehnitene and isodurene are converted into durol, are one conventional Method, still, the catalyst of current isomerization reaction, selectivity and conversion ratio be not high, generally, is selectively 30-60%, conversion ratio 20-30%, it is impossible to meet the needs of industrialized production.
The content of the invention
The catalyst of continuity method isomerization production durol of the present invention, include the group of following percentage by weight Point：
The oxide of nickel or the oxide 4 ~ 7% of palladium
The oxide 2 ~ 5% of cerium
The oxide 2 ~ 3% of alum
The oxide of copper and the oxide 3 ~ 7% of manganese
Wherein：The oxide of copper: oxide=1 of manganese: 2 ~ 3, weight ratio
The oxidation 5 ~ 6% of potassium
Carrier surplus
Described carrier is modenite；n（SiO2）:n（Al2O3）=20-28, ω（Na2O）=1%-5%, specific surface area 400- 600m2.g-1, crystal grain（100-300nm）.
The preparation method of the catalyst of the continuity method isomerization production durol, is infusion process, specifically, is used Prepared by equi-volume impregnating, comprise the following steps：
By nickel or palladium soluble-salt, cerium soluble-salt, the soluble-salt of alum, copper soluble-salt and manganese soluble-salt, dissolved with water, The dosage of water determines according to by carrier water absorption rate, then adds carrier, successively in 40~80 DEG C of 1~4h of heating stirring, 30~ 50 DEG C of constant temperature stand 8~16h, in 100~120 DEG C of dry 8~16h, in 200~300 DEG C of 2~4h of constant temperature calcining, 350~ 700 DEG C of roasting 3~6h, preferably 450~600 DEG C, you can obtain described isomerization catalyst；
Described nickel soluble-salt is selected from nickel chloride；
Described palladium soluble-salt is selected from palladium bichloride；
Described cerium soluble-salt is selected from cerium chloride；
The soluble-salt of the V is selected from vanadium trichloride；
The soluble-salt of the copper is selected from copper chloride；
The soluble-salt of described manganese is selected from manganese chloride；
The soluble-salt of described potassium is selected from potassium chloride；
The catalyst of continuity method isomerization of the present invention production durol, it can be used for isodurene and prehnitene Isomerization, reaction generation durol, specifically comprises the following steps：
By the solution containing durol, isodurene and prehnitene, 300-350 DEG C is heated to, feeding is filled with isomerization The fixed bed reactors of catalyst；
Then by reaction product, rectifier unit is sent into, separates and collects prehnitene；
Reaction pressure 0.1-2.0MPA；
Reaction velocity is 0.8-1~1.5h-1
Reaction velocity refer to as defined under the conditions of, unit interval per volume of catalyst processing amount of liquid, unit is m3/ (m3 Catalyst h), h can be reduced to-1。
The described solution containing durol, isodurene and prehnitene, the component containing following percentage by weight：
Durol 15 ~ 16%
Isodurene 30 ~ 35%
Prehnitene 18 ~ 19%
The described solution containing durol, isodurene and prehnitene derives from reformed C 10, by using essence Evaporate method and obtain durol pregnant solution, the mother liquor after freezing and crystallizing separation.
The beneficial effects of the invention are as follows：
The catalyst of continuity method isomerization of the present invention production durol, in the reaction product of acquisition, each component Weight percent content is：Durol 43 ~ 45%, isodurene 19 ~ 22%, prehnitene 1 ~ 6%, selectively reach 91.2 Above %, yield reach more than 54.7 %, can successive reaction, be suitable for industrialized production.
Term：" yield ", " selectivity ", " yield " are defined as follows：
Inclined prehnitene conversion ratio %=［ in raw material（Partially+even）In-product（Partially+even）In ］/raw material（Partially+even）×100；
Durol selectivity %=equal four increment/［ in raw material（Partially+even）In-product（Partially+even）］ × 100
In durol yield %=equal four increments/raw material（Partially+even）×100.
Embodiment
Embodiment 1
Isomerization catalyst, include the component of following percentage by weight：
The oxide of nickel or the oxide 4% of palladium
The oxide 5% of cerium
The oxide 2% of alum
The oxide of copper and the oxide 7% of manganese
Wherein：The oxide of copper: oxide=1 of manganese: 2, weight ratio
The oxidation 6% of potassium
Carrier surplus
Described carrier is modenite；n（SiO2）:n（Al2O3）=20, ω（Na2O）=5%, specific surface area 400m2.g-1, crystal grain （100nm）；
Preparation method：
By nickel soluble-salt, platinum soluble-salt, cerium soluble-salt, copper soluble-salt and manganese soluble-salt, dissolved with water, the use of water Amount is determined according to by carrier water absorption rate, then adds carrier, and successively in 40 DEG C of heating stirring 1h, 16h is stood in 30 DEG C of constant temperature, 100 DEG C of dry 16h, in 200 DEG C of constant temperature calcinings 4h, 450 DEG C of roasting 6h, you can obtain described isomerization catalyst；
Wire examination method：
By the solution containing durol, isodurene and prehnitene, 300 DEG C are heated to, feeding is filled with isomerization catalytic The fixed bed reactors of agent；
Reaction pressure 1.0MPA；Mass space velocity 1.0h of the material in isomerization fixed bed reactors-1；
Solution containing durol, isodurene and prehnitene, include the component of following percentage by weight：
Durol 15.3%
Isodurene 33.4%
Prehnitene 18.1%
In the reaction product obtained by fixed bed reactors reaction, the weight percent content of each component is：Durol 36.8%, isodurene 21.3%, prehnitene 6.1%, selectively reach 89.2%, yield reaches 41.7%.
Embodiment 2
Isomerization catalyst, include the component of following percentage by weight：
The oxide of nickel or the oxide 7% of palladium
The oxide 2% of cerium
The oxide 3% of alum
The oxide of copper and the oxide 3% of manganese
Wherein：The oxide of copper: oxide=1 of manganese: 3, weight ratio
The oxidation 5% of potassium
Carrier surplus
Carrier is modenite；n（SiO2）:n（Al2O3）=28, ω（Na2O）=1%%, specific surface area 600m2.g-1, crystal grain （300nm）；
Preparation method：
By nickel or palladium soluble-salt, cerium soluble-salt, alum soluble-salt, copper soluble-salt and manganese soluble-salt, dissolved with water, water Dosage determined according to by carrier water absorption rate, then add carrier, successively in 80 DEG C of heating stirring 4h, stood in 50 DEG C of constant temperature 8h, in 120 DEG C of dry 8h, in 300 DEG C of constant temperature calcining 2h, 600 DEG C are calcined 3h, you can obtain described isomerization catalyst；
Wire examination method：
By the solution containing durol, isodurene and prehnitene, 350 DEG C are heated to, feeding is filled with isomerization catalytic The fixed bed reactors of agent；
Reaction pressure 1.0MPA；Mass space velocity 1.0h of the material in isomerization fixed bed reactors-1；
Solution containing durol, isodurene and prehnitene, include the component of following percentage by weight：Durol 15.3%, isodurene 33.4%, prehnitene 18.1%；
In the reaction product obtained by fixed bed reactors reaction, the weight percent content of each component is：Durol 43.2%, isodurene 19.4%, prehnitene 1.5%, selectively reach 91.1%, yield reaches 54.2%.

Claims (5)

1. continuity method isomerization produces the catalyst of durol, it is characterised in that includes the component of following percentage by weight：
The oxide of nickel or the oxide 4 ~ 7% of palladium
The oxide 2 ~ 5% of cerium
The oxide 2 ~ 3% of alum
The oxide of copper and the oxide 3 ~ 7% of manganese
Wherein：The oxide of copper: oxide=1 of manganese: 2 ~ 3, weight ratio
The oxidation 5 ~ 6% of potassium
Carrier surplus.
2. the catalyst of continuity method isomerization production durol according to claim 1, it is characterised in that described load Body is modenite；n（SiO2）:n（Al2O3）=20-28, ω（Na2O）=1%-5%, specific surface area 400-600m2.g-1, crystal grain （100-300nm）.
3. the preparation method of the catalyst of continuity method isomerization production durol according to claim 1 or 2, its feature It is, is equi-volume impregnating.
4. according to the method for claim 3, it is characterised in that comprise the following steps：
By nickel or palladium soluble-salt, cerium soluble-salt, the soluble-salt of alum, copper soluble-salt and manganese soluble-salt, dissolved with water, The dosage of water determines according to by carrier water absorption rate, then adds carrier, successively in 40~80 DEG C of 1~4h of heating stirring, 30~ 50 DEG C of constant temperature stand 8~16h, in 100~120 DEG C of dry 8~16h, in 200~300 DEG C of 2~4h of constant temperature calcining, 350~ 700 DEG C of roasting 3~6h, preferably 450~600 DEG C, you can obtain described isomerization catalyst.
5. according to the method for claim 4, it is characterised in that described nickel soluble-salt is selected from nickel chloride；Described palladium Soluble-salt is selected from palladium bichloride；Described cerium soluble-salt is selected from cerium chloride；
The soluble-salt of the V is selected from vanadium trichloride；The soluble-salt of the copper is selected from copper chloride；The soluble-salt of described manganese Selected from manganese chloride；The soluble-salt of described potassium is selected from potassium chloride.
CN201711098907.6A 2017-11-09 2017-11-09 Continuity method isomerization produces the catalyst of durol Pending CN107649171A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109336728A (en) * 2018-11-19 2019-02-15 鹏辰新材料科技股份有限公司 A kind of process for effectively purifying of 1,2,4,5- durene
CN112094167A (en) * 2020-10-09 2020-12-18 大连龙缘化学有限公司 Preparation method and application of catalyst for producing durene by isomerizing mixed durene

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD137703A1 (en) * 1978-07-12 1979-09-19 Karl Becker METHOD OF ISOMERIZING TETRAMETHYLBENZENE
CN1183317A (en) * 1996-11-25 1998-06-03 中国科学院山西煤炭化学研究所 Method for preparing catalyst for synthesis of 1, 2, 4, 5 -tetramethylbenzene
CN1370620A (en) * 2001-02-27 2002-09-25 中国石油化工股份有限公司天津分公司研究院 Prepn of catalyst for tetramethylbenzene isomerization to prepare durene
CN105457669A (en) * 2015-12-10 2016-04-06 中国海洋石油总公司 Methanol to durene catalyst and preparation method thereof
CN106076404A (en) * 2016-06-08 2016-11-09 中石化炼化工程（集团）股份有限公司 Catalyst and preparation method thereof, application and the preparation method of durol
CN106565406A (en) * 2016-10-28 2017-04-19 华东理工大学 Method of preparing durene through one-step method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD137703A1 (en) * 1978-07-12 1979-09-19 Karl Becker METHOD OF ISOMERIZING TETRAMETHYLBENZENE
CN1183317A (en) * 1996-11-25 1998-06-03 中国科学院山西煤炭化学研究所 Method for preparing catalyst for synthesis of 1, 2, 4, 5 -tetramethylbenzene
CN1370620A (en) * 2001-02-27 2002-09-25 中国石油化工股份有限公司天津分公司研究院 Prepn of catalyst for tetramethylbenzene isomerization to prepare durene
CN105457669A (en) * 2015-12-10 2016-04-06 中国海洋石油总公司 Methanol to durene catalyst and preparation method thereof
CN106076404A (en) * 2016-06-08 2016-11-09 中石化炼化工程（集团）股份有限公司 Catalyst and preparation method thereof, application and the preparation method of durol
CN106565406A (en) * 2016-10-28 2017-04-19 华东理工大学 Method of preparing durene through one-step method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109336728A (en) * 2018-11-19 2019-02-15 鹏辰新材料科技股份有限公司 A kind of process for effectively purifying of 1,2,4,5- durene
CN112094167A (en) * 2020-10-09 2020-12-18 大连龙缘化学有限公司 Preparation method and application of catalyst for producing durene by isomerizing mixed durene

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