CN106582799A - Pretreatment method of catalyst for disproportionation and transalkylation of aromatic compounds - Google Patents

Pretreatment method of catalyst for disproportionation and transalkylation of aromatic compounds Download PDF

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Publication number
CN106582799A
CN106582799A CN201510674619.5A CN201510674619A CN106582799A CN 106582799 A CN106582799 A CN 106582799A CN 201510674619 A CN201510674619 A CN 201510674619A CN 106582799 A CN106582799 A CN 106582799A
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catalyst
transalkylation
preprocess method
molecular sieve
hours
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李经球
李华英
郭宏利
孔德金
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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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    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7469—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
    • 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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • 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
    • B01J29/80—Mixtures of different zeolites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • 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
    • 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
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/74—Noble metals
    • 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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a catalyst for disproportionation and transalkylation of aromatic compounds as well as a pretreatment method. The catalyst mainly solves the problems of low xylene selectivity and low methyl utilization rate and the like in the prior art. The catalyst for disproportionation and transalkylation of aromatic compounds comprises the following components: (a) 10-90 parts of at least one of ZSM-5, ZSM-12, mordenite and beta-zeolite molecular sieve, and materials loaded thereon; (b) 0.01-5 parts of at least one which is selected from metal components in VIIIB or VIIB group; (c) 10-50 parts of a binder aluminum oxide. The catalyst employs a technical scheme of water vapour and acid solution pretreatment, in order to better solve the problem, and the method can be applied to disproportionation and transalkylation industrial production of toluene and heavy aromatics.

Description

Aromatics disproportionation and transalkylation catalyst preprocess method
Technical field
The present invention relates to a kind of aromatic compound disproportionation and transalkylation catalyst and its preprocess method, specifically Say, be related to a kind of method that water vapour and acid treatment are carried out to acidic molecular sieve component.
Background technology
Using toluene and C9+A transalkylation reaction increasing production of xylol is that effectively utilizes heavy aromatics carrys out increasing production of xylol Method, be widely used.But when the content of carbon nine and its above heavy arene in reaction raw materials is higher, especially It is C10+The content of A is higher, the easier coking and deactivation of catalyst.Therefore, traditional alkyl transfering process In to the C10 in reaction raw materials+A has strict restriction.
To improve the stability of heavy aromatics transalkylation catalyst, anti-product typically can be added in catalytic component Charcoal hydrogenation metal component of good performance, such as CN1122571 discloses a kind of molecular sieve catalytic containing noble metal Agent, the catalyst with 10-80% (weight) modenites or the ZSM-5 of β zeolites and 0-70% (weight), γ-the Al2O3 of 5-90% (weight) are carrier, load 0.001-0.5 weight portions platinum and 0.01-10.0 weight portions Tin or 0.01-7.0 weight portion lead.The catalyst can process high C9+A raw materials, and improve mixed xylenes product Rate and catalyst stability.But the introducing of noble metal is not referred to the impact that product ring loses.
US005763720A discloses a kind of transalkylation catalyst of platinum metal, and the catalyst steams through water Vapour or sulphuring treatment, with preferable stability and relatively low hydrogenation side reaction, but heavy aromatics conversion ratio is low.
US20080221375 discloses a kind of catalyst of rhenium-containing metal, and the catalyst carries out sulphur after reduction Change and process to suppress the hydrogenation activity of rhenium metal, catalyst to show preferable stability, and with higher two Toluene yield.
Another kind of method for improving catalyst stability is that acidic molecular sieve is pre-processed, and such as carries out appropriate bone The dealuminzation of frame, it is therefore intended that modulation its surface acidic strength, and increase the surface area of molecular sieve, forms abundant Secondary pore, it is to avoid hole plug inactivation occurs.CN1022420 discloses a kind of the compound of isomerization of paraffinic hydrocarbons and urges Agent and preparation method thereof, the method mainly carries out acid treatment to the complex carrier after shaping, compound to improve Catalyst surface area is.The catalyst shows good stability.
Above-mentioned document only lays particular emphasis on metal-modified or acidic zeolite modulation aspect, and does not consider metal hydrogenation The Rational Matching of performance and acidic zeolite matter.
The content of the invention
One of the technical problem to be solved is that have that dimethylbenzene selective is low, methyl in prior art The low problem of utilization rate, there is provided a kind of new aromatic disproportion and transalkylation catalyst.The catalyst is used to be disproportionated With transalkylation reaction, have the advantages that dimethylbenzene selective and methyl utilization rate are high.
The two of the technical problem to be solved are to provide a kind of corresponding with one of technical problem is solved The preprocess method of catalyst.
To solve one of above-mentioned technical problem, the present invention is as follows using technical scheme, a kind of aromatics disproportionation With transalkylation catalyst and its preprocess method, catalyst include following components：
At least one ZSM-5 through dealumination treatment of a) 10-90 parts, ZSM-12, modenite and β boilings Stone molecular sieve, and load thereon；
B) 0.01～5 part of at least one metal component for being selected from VIII B or VII B races；
C) 10～50 parts of binding agent aluminum oxide.
In above-mentioned technical proposal, molecular sieve component be ammonium type, Hydrogen or sodium form, selected molecular sieve SiO2/Al2O3 Molecular proportion is 10～200, and molecular sieve content is 30～80 parts.Metal component is selected from platinum, palladium, rhenium extremely Few one kind.Metal component content is 0.01～2 part.In preferred catalyst scheme, molecular sieve is MOR, metal For rhenium.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：
A) acidic molecular sieve and binding agent are molded, roasting 1～4 is little at 400～600 DEG C under air atmosphere When；
B) catalyst after step a) process is carried out into steam treatment 1～6 hour at a temperature of 300-700 DEG C；
C) step b) process rear catalysts are carried out into acid treatment, and in 300～600 DEG C of roastings in oxidizing atmosphere 1～4 hour；
D) metal component is incorporated into into step c) in modes such as solution impregnation, chemical precipitation or ion exchanges to process In rear catalyst；
The steam treatment temperature is 400～600 DEG C, and water vapor concentration is 1-20vol%；The acid solution is salt Acid, nitric acid or citric acid.The acid solutions are 0.1～10mol/L, and acid treatment temperature is 40～150 DEG C. In preferred scheme, catalyst water vapour pretreatment temperature is 550 DEG C, and Pretreatment atmosphere is water containing 10vol% The air of steam, pretreatment time 5 hours；In preferred technical scheme, acid is carried out using aqueous citric acid solution Process, acid concentration is 2mol/L, acid treatment temperature is 90 DEG C.
In the present invention, by carrying out steam treatment to catalyst, can effectively deviate from the part framework aluminum of molecular sieve, Reduce molecular sieve strong acid center amount.Sour extracting process is subsequently carried out, non-framework aluminum content in duct can be reduced, and Further improve the surface area and pore volume of catalyst.By introducing appropriate metal component, make metal hydrogenation activity with Acidic zeolite reaches rational matching, under the reaction condition of optimization, can effectively improve methyl utilization rate, reaches To the purpose of increasing production of xylol.In preferred version, reaction total conversion reaches 46.3wt%, and dimethylbenzene selective reaches 71.9wt%, methyl conservation rate reaches 97.2wt%.
Below by the description to embodiment, the present invention is further illustrated but not limited：
Specific embodiment
【Embodiment 1】
By 66.7 grams of Na2Ammonium type ZSM-12 molecular sieve and 57.1 gram Nas of the O content less than 0.1% (weight)2O Al of the content less than 0.1% (weight)2O3·H2O uniformly mixes, and is subsequently adding a certain amount of dust technology, field Mountain valley with clumps of trees and bamboo powder is mediated uniformly, and extruded moulding, roasting make carrier I.Carrier I is used at 550 DEG C and contains 10vol% The air of water vapour is heat-treated 5 hours, then processes 4 under the conditions of 90 DEG C with aqueous citric acid solution containing 2mol/L Hour, catalyst 2 hours prepared pretreated carrier S1 of roasting under 500 DEG C and air atmosphere again.S1 pelletizings After be placed in steeper, will metering palladium chloride solution impregnated in carrier surface, 120 DEG C of dryings 4 hours, 500 DEG C 3 hours prepared catalyst A1 of roasting.
Take 10 grams of catalyst A1 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 120% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, first and second Benzene 29.04%, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 2】
By 66.7 grams of Na2Ammonium type modenite and 57.1 gram Nas of the O content less than 0.1% (weight)2O contains Al of the amount less than 0.1% (weight)2O3·H2O uniformly mixes, and is subsequently adding a certain amount of dust technology, Tian Qing Powder is mediated uniformly, and extruded moulding, roasting make carrier II.Carrier II is used under the conditions of 550 DEG C and contains 10vol% The air of water vapour is heat-treated 5 hours, then processes 4 under the conditions of 90 DEG C with aqueous citric acid solution containing 2mol/L Hour, catalyst 2 hours prepared pretreated carrier S2 of roasting under 500 DEG C and air atmosphere again.S2 pelletizings After be placed in steeper, metering ammonium perrhenate solution be impregnated in into carrier surface, 120 DEG C of dryings 4 hours, 500 DEG C of roastings, 3 hours prepared catalyst A2.
Take 10 grams of catalyst A2 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 20% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 3】
By 26 grams of Na2Ammonium type ZSM-5 molecular sieve, 40 gram Nas of the O content less than 0.1% (weight)2O contains Ammonium type Beta molecular sieve and 57.1 gram Nas of the amount less than 0.1% (weight)2O content is less than 0.1% (weight) Al2O3·H2O uniformly mixes, and is subsequently adding a certain amount of dust technology, field mountain valley with clumps of trees and bamboo powder and mediates uniformly, extruded moulding, Carrier III is made in roasting.Carrier III is heat-treated into 5 under the conditions of 550 DEG C with the air containing 10vol% water vapours Hour, then processed 4 hours under the conditions of 90 DEG C with aqueous citric acid solution containing 2mol/L, catalyst is again at 500 DEG C And 2 hours prepared pretreated carrier S3 of roasting under air atmosphere.It is placed in after S3 pelletizings in steeper, will counts The platinum acid chloride solution of amount impregnated in carrier surface, and 120 DEG C of dryings 4 hours, 500 DEG C of roastings are obtained catalysis in 3 hours Agent A3.
Take 10 grams of catalyst A3 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 4】
By 66.7 grams of Na2Ammonium type MOR and 57.1 gram Nas of the O content less than 0.1% (weight)2O content is little Uniformly mix in the Al2O3H2O of 0.1% (weight), be subsequently adding a certain amount of dust technology, field mountain valley with clumps of trees and bamboo powder and pinch Close uniform, extruded moulding, roasting make carrier IV.Carrier IV is steamed under the conditions of 550 DEG C with water containing 10vol% The air of vapour is heat-treated 5 hours, then is processed 4 hours under the conditions of 90 DEG C with aqueous citric acid solution containing 2mol/L, Catalyst 2 hours prepared pretreated carrier S4 of roasting under 500 DEG C and air atmosphere again.It is placed in after S4 pelletizings In steeper, metering platinum acid chloride solution be impregnated in into carrier surface, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 3 hours prepared catalyst A4.
Take 10 grams of catalyst A4 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 5】
According to embodiment 2 prepare catalyst carrier II, by carrier II under the conditions of 550 DEG C use water containing 10vol% The air of steam is heat-treated 10 hours, then processes 4 under the conditions of 90 DEG C with aqueous citric acid solution containing 2mol/L Hour, then 2 hours prepared pretreated carrier S5 of roasting under 500 DEG C and air atmosphere.It is placed in after S5 pelletizings In steeper, the ammonium perrhenate solution of metering be impregnated in into carrier surface, 120 DEG C of dryings 4 hours, 500 DEG C 3 hours prepared catalyst A5 of roasting.
Take 10 grams of catalyst A5 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 6】
According to embodiment 2 prepare catalyst carrier II, by carrier II under the conditions of 550 DEG C use water containing 20vol% The air of steam is heat-treated 5 hours, then that 4 are processed under the conditions of 90 DEG C with aqueous citric acid solution containing 2mol/L is little When, then 2 hours prepared pretreated carrier S6 of roasting under 500 DEG C and air atmosphere.Leaching is placed in after S6 pelletizings In stain container, the ammonium perrhenate solution of metering be impregnated in into carrier surface, 120 DEG C of dryings are roasted for 4 hours, 500 DEG C Burn 3 hours prepared catalyst A6.
Take 10 grams of catalyst A6 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 7】
According to embodiment 2 prepare catalyst carrier II, by carrier II under the conditions of 600 DEG C use water containing 10vol% The air of steam is heat-treated 5 hours, then that 4 are processed under the conditions of 90 DEG C with aqueous citric acid solution containing 2mol/L is little When, then 2 hours prepared pretreated carrier S7 of roasting under 600 DEG C and air atmosphere.Leaching is placed in after S7 pelletizings In stain container, the ammonium perrhenate solution of metering be impregnated in into carrier surface, 120 DEG C of dryings are roasted for 4 hours, 500 DEG C Burn 3 hours prepared catalyst A7.
Take 10 grams of catalyst A7 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 8】
According to embodiment 2 prepare catalyst carrier II, by carrier II under the conditions of 550 DEG C use water containing 10vol% The air of steam is heat-treated 5 hours, then that 4 are processed under the conditions of 90 DEG C with the aqueous solution of nitric acid for containing 2mol/L is little When, then 2 hours prepared pretreated carrier S8 of roasting under 500 DEG C and air atmosphere.Leaching is placed in after S8 pelletizings In stain container, the ammonium perrhenate solution of metering be impregnated in into carrier surface, 120 DEG C of dryings are roasted for 4 hours, 500 DEG C Burn 3 hours prepared catalyst A8.
Take 10 grams of catalyst A8 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 9】
According to embodiment 2 prepare catalyst carrier II, by carrier II under the conditions of 550 DEG C use water containing 10vol% The air of steam is heat-treated 5 hours, then processes 4 under the conditions of 90 DEG C with the aqueous solution of nitric acid containing 0.5mol/L Hour, then 2 hours prepared pretreated carrier S9 of roasting under 500 DEG C and air atmosphere.It is placed in after S9 pelletizings In steeper, the ammonium perrhenate solution of metering be impregnated in into carrier surface, 120 DEG C of dryings 4 hours, 500 DEG C 3 hours prepared catalyst A9 of roasting.
Take 10 grams of catalyst A9 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 10】
According to embodiment 2 prepare catalyst carrier II, by carrier II under the conditions of 550 DEG C use water containing 10vol% The air of steam is heat-treated 5 hours, then processes 4 under the conditions of 60 DEG C with the aqueous solution of nitric acid containing 0.5mol/L Hour, then 2 hours prepared pretreated carrier S10 of roasting under 500 DEG C and air atmosphere.S10 pelletizings are rearmounted In steeper, the ammonium perrhenate solution of metering be impregnated in into carrier surface, 120 DEG C of dryings 4 hours, 500 DEG C 3 hours prepared catalyst A10 of roasting.
Take 10 grams of catalyst A10 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Embodiment 11】
According to embodiment 2 prepare catalyst carrier II, by carrier II under the conditions of 550 DEG C use water containing 10vol% The air of steam is heat-treated 5 hours, then processes 4 under the conditions of 60 DEG C with the aqueous hydrochloric acid solution containing 0.5mol/L Hour, then 2 hours prepared pretreated carrier S11 of roasting under 500 DEG C and air atmosphere.S11 pelletizings are rearmounted In steeper, the ammonium perrhenate solution of metering be impregnated in into carrier surface, 120 DEG C of dryings 4 hours, 500 DEG C 3 hours prepared catalyst A11 of roasting.
Take 10 grams of catalyst A11 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
【Comparative example】
Catalyst carrier II is prepared according to embodiment 2, is placed in steeper after the pelletizing of carrier II, will be measured Ammonium perrhenate solution impregnated in carrier surface, 120 DEG C of dryings 4 hours, 500 DEG C of roastings are obtained catalysis in 3 hours Agent A12.
Take 10 grams of catalyst A12 to fill in fixed bed reactors.Hydrogen is passed through, 450 DEG C are warming up to, is blown Reduction activation in 2 hours is swept, is 400 DEG C in reaction temperature, reaction pressure 3.0MPa, WHSV=3.0h-1、 Hydrogen hydrocarbon molecule ratio is 3.0 operating mode charging reaction, and reaction raw materials weight consists of toluene/C9 +A=50/50.It is former Material C9 +C containing 15% (weight) in A10 +A。C9A raw material weights are consisted of：Propyl benzene 4.2%, the first and second benzene 29.04%th, trimethylbenzene 59.6%, C10 +A weight is consisted of：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, Methyl propyl benzene 2.32%, durene 28.84%, methyl naphthalene 14.49%, dimethylnaphthalene 11.16%, other 12.90%. Catalyst composition is as shown in table 1, and as shown in table 2, catalyst reaction performance is as shown in table 3 for pretreatment condition.
Table 1
Catalyst Molecular sieve M/wt%
A1 ZSM-12 Pd/0.05
A2 MOR Re/0.1
A3 ZSM-5-Beta Pt/0.05
A4 MOR Pt/0.05
A5 MOR Re/0.1
A6 MOR Re/0.1
A7 MOR Re/0.1
A8 MOR Re/0.1
A9 MOR Re/0.1
A10 MOR Re/0.1
A11 MOR Re/0.1
A12 MOR Re/0.1
Table 2
Table 3

Claims (10)

1. a kind of aromatics disproportionation and transalkylation catalyst and its preprocess method, catalyst includes following components：
A) at least one of 10-90 parts is selected from ZSM-5, ZSM-12, modenite and beta-zeolite molecular sieve, and loads thereon；
B) 0.01～5 part of at least one metal component for being selected from VIII B or VII B races；
C) 10～50 parts of binding agent aluminum oxide；
The catalyst is processed through water vapour and acid solution.
2. aromatics disproportionation according to claim 1 and transalkylation catalyst and its preprocess method, it is characterised in that the molecular sieve is ammonium type, Hydrogen or sodium form molecular sieve.
3. aromatics disproportionation according to claim 1 and transalkylation catalyst and its preprocess method, it is characterised in that the molecular sieve SiO2/Al2O3 molecular proportions are 10～200.
4. aromatics disproportionation according to claim 2 and transalkylation catalyst and its preprocess method, it is characterised in that the molecular sieve content is 30～80 parts.
5. aromatics disproportionation according to claim 1 and transalkylation catalyst and its preprocess method, it is characterised in that at least one of the hydrogenation metal component in platinum, palladium, rhenium.
6. aromatics disproportionation according to claim 1 and transalkylation catalyst and its preprocess method, it is characterised in that the metal component content is 0.01～2 part.
7. aromatics disproportionation according to claim 1 and transalkylation catalyst and its preprocess method, it is characterised in that catalyst preconditioning process includes：
A) above-mentioned molecular sieve and binding agent are molded, under air atmosphere at 400～600 DEG C roasting 1～4 hour；
B) catalyst after step a) process is carried out into steam treatment 0.5～6 hour at a temperature of 300-700 DEG C；
C) catalyst after step b) process is carried out into acid treatment, and in 300～600 DEG C of roastings 1～4 hour in oxidizing atmosphere；
D) metal component is incorporated into into step c) in modes such as solution impregnation, chemical precipitation, ion exchanges to process in rear catalyst.
8. aromatics disproportionation according to claim 7 and transalkylation catalyst and its preprocess method, it is characterised in that steam treatment temperature is 400～600 DEG C, and water vapor concentration is 1-20vol%.
9. aromatics disproportionation according to claim 7 and transalkylation catalyst and its preprocess method, it is characterised in that the acid solution is hydrochloric acid, nitric acid or citric acid.
10. aromatics disproportionation according to claim 7 and transalkylation catalyst and its preprocess method, it is characterised in that the acid solutions are 0.1～10mol/L, and acid treatment temperature is 40～150 DEG C.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114425424A (en) * 2020-09-27 2022-05-03 中国石油化工股份有限公司 Aromatic hydrocarbon conversion catalyst, preparation method thereof and aromatic hydrocarbon conversion method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1162502A (en) * 1996-02-09 1997-10-22 法国石油公司 Catalyst comprising zeolite of structure type mazzite and its use for dismutation and/or transalkylation of alkylaromatic hydrocarbons
CN1230942A (en) * 1996-09-18 1999-10-06 三菱石油株式会社 Selective catalytic conversion of C9 aromatic feedstock containing substantial amounts of ethyl substituted aromatic components to product rich in toluene and/or xylenes
JP2002167359A (en) * 2000-11-30 2002-06-11 Teijin Ltd Method for producing aromatic carbonate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1162502A (en) * 1996-02-09 1997-10-22 法国石油公司 Catalyst comprising zeolite of structure type mazzite and its use for dismutation and/or transalkylation of alkylaromatic hydrocarbons
CN1230942A (en) * 1996-09-18 1999-10-06 三菱石油株式会社 Selective catalytic conversion of C9 aromatic feedstock containing substantial amounts of ethyl substituted aromatic components to product rich in toluene and/or xylenes
JP2002167359A (en) * 2000-11-30 2002-06-11 Teijin Ltd Method for producing aromatic carbonate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114425424A (en) * 2020-09-27 2022-05-03 中国石油化工股份有限公司 Aromatic hydrocarbon conversion catalyst, preparation method thereof and aromatic hydrocarbon conversion method
CN114425424B (en) * 2020-09-27 2024-05-03 中国石油化工股份有限公司 Aromatic hydrocarbon conversion catalyst, preparation method thereof and aromatic hydrocarbon conversion method

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