CN107673946A - The method that continuity method isomerization produces durol - Google Patents

The method that continuity method isomerization produces durol Download PDF

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Publication number
CN107673946A
CN107673946A CN201711098119.7A CN201711098119A CN107673946A CN 107673946 A CN107673946 A CN 107673946A CN 201711098119 A CN201711098119 A CN 201711098119A CN 107673946 A CN107673946 A CN 107673946A
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China
Prior art keywords
oxide
durol
prehnitene
isodurene
isomerization
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CN201711098119.7A
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Inventor
吴增才
许飞
潘学林
任倩
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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 CN201711098119.7A priority Critical patent/CN107673946A/en
Publication of CN107673946A publication Critical patent/CN107673946A/en
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    • 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
    • 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
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of method of continuity method isomerization production durol, comprise the following steps：By the solution containing durol, isodurene and prehnitene, the fixed bed reactors for being filled with isomerization catalyst are sent into；Then by reaction product, rectifier unit is sent into, separates and collects prehnitene, isomerization catalyst, 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, present invention employs the fixed bed reactors for having loaded isomerization catalyst, in the reaction product for reacting acquisition, the weight percent content of each component is：Durol 43 ~ 45%, isodurene 19 ~ 22%, prehnitene 1 ~ 6%, selectively reach 91.2%, yield reaches 54.7%, successive reaction, is suitable for industrialized production.

Description

The method that continuity method isomerization produces durol
Technical field
The present invention relates to the method for production durol.
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 purpose of the present invention is to disclose a kind of method of continuity method isomerization production durol, to overcome prior art to deposit The defects of.
The method of the present invention, 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 m3/(m3 Catalyst h), h can be reduced to-1。
Described isomerization catalyst, 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
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 isomerization catalyst, it is infusion process, specifically, is prepared using equi-volume impregnating, wraps Include following steps：
By nickel soluble-salt or palladium soluble-salt, cerium soluble-salt, alum soluble-salt, copper soluble-salt and manganese soluble-salt, use Water dissolves, and 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, 8~16h are stood in 30~50 DEG C of constant temperature, 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 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：
Present invention employs the fixed bed reactors for having loaded described isomerization catalyst, in the reaction product for reacting acquisition, The weight percent content of each component is：Durol 43 ~ 45%, isodurene 19 ~ 22%, prehnitene 1 ~ 6%, selection Property reaches more than 91.2%, and yield reaches more than 54.7 %, successive reaction, is suitable for industrialized production.
Term：Yield ", " selectivity ", " conversion ratio " 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, cerium soluble-salt, alum 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；
The method that continuity method isomerization produces durol：
By the solution containing durol, isodurene and prehnitene, 300 DEG C are heated to, is sent into and is filled with described isomery Change the fixed bed reactors reaction of catalyst；
Then by reaction product, rectifier unit is sent into, separates and collects prehnitene；
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%；
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；
The method that continuity method isomerization produces durol：
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；
Then by reaction product, rectifier unit is sent into, separates and collects prehnitene；
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%；
Selectivity reaches 91.1%, and yield reaches 54.2%.

Claims (9)

1. the method that continuity method isomerization produces durol, it is characterised in that comprise the following steps：Will contain durol, The solution of isodurene and prehnitene, it is sent into the fixed bed reactors for being filled with isomerization catalyst；
Then by reaction product, rectifier unit is sent into, separates and collects prehnitene；
Described isomerization catalyst, 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.
2. according to the method for claim 1, it is characterised in that 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）.
3. according to the method for claim 1, it is characterised in that reaction pressure 0.1-2.0MPA.
4. according to the method for claim 1, it is characterised in that reaction velocity 0.8-1~1.5h-1。
5. according to the method for claim 3, it is characterised in that reaction velocity 0.8-1~1.5h-1。
6. according to the method for claim 1, it is characterised in that the preparation method of the isomerization catalyst, be infusion process.
7. according to the method for claim 1, it is characterised in that be heated to 300-350 DEG C, feeding is filled with isomerization catalytic The fixed bed reactors of agent.
8. according to the method described in any one of claim 1 ~ 7, it is characterised in that described contains durol, isodurene With the solution of prehnitene, the component containing following percentage by weight：
Durol 15 ~ 16%
Isodurene 30 ~ 35%
Prehnitene 18 ~ 19%.
9. according to the method for claim 8, it is characterised in that described contains durol, isodurene and company's tetramethyl The solution of benzene derives from reformed C 10, durol pregnant solution is obtained by using rectificating method, after freezing and crystallizing separation Mother liquor.
CN201711098119.7A 2017-11-09 2017-11-09 The method that continuity method isomerization produces durol Pending CN107673946A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN113042097A (en) * 2019-12-26 2021-06-29 中国石油天然气股份有限公司 Molecular sieve catalyst, preparation method thereof and application of molecular sieve catalyst
CN115433051A (en) * 2022-10-09 2022-12-06 连云港鹏辰特种新材料有限公司 Method for separating durene from durene enrichment liquid

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1102360A (en) * 1993-11-05 1995-05-10 中国石油化工总公司 Alleyl aromatics isomerizating catalyzer
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
CN102304011A (en) * 2011-07-22 2012-01-04 镇江正丹化学工业有限公司（中外合资） Method for producing 1,2,4-trimethylbenzene by C9 aromatic hydrocarbon isomerization
CN103611564A (en) * 2013-11-21 2014-03-05 中国科学院山西煤炭化学研究所 Catalyst for durene conversion as well as preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1102360A (en) * 1993-11-05 1995-05-10 中国石油化工总公司 Alleyl aromatics isomerizating catalyzer
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
CN102304011A (en) * 2011-07-22 2012-01-04 镇江正丹化学工业有限公司（中外合资） Method for producing 1,2,4-trimethylbenzene by C9 aromatic hydrocarbon isomerization
CN103611564A (en) * 2013-11-21 2014-03-05 中国科学院山西煤炭化学研究所 Catalyst for durene conversion as well as preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113042097A (en) * 2019-12-26 2021-06-29 中国石油天然气股份有限公司 Molecular sieve catalyst, preparation method thereof and application of molecular sieve catalyst
CN113042097B (en) * 2019-12-26 2023-09-26 中国石油天然气股份有限公司 Molecular sieve catalyst, preparation method and application thereof
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
CN115433051A (en) * 2022-10-09 2022-12-06 连云港鹏辰特种新材料有限公司 Method for separating durene from durene enrichment liquid

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