CN105085153A - Method for producing benzene, toluene and xylene by using arene with more than 9 carbon atoms - Google Patents

Method for producing benzene, toluene and xylene by using arene with more than 9 carbon atoms Download PDF

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Publication number
CN105085153A
CN105085153A CN201410192900.0A CN201410192900A CN105085153A CN 105085153 A CN105085153 A CN 105085153A CN 201410192900 A CN201410192900 A CN 201410192900A CN 105085153 A CN105085153 A CN 105085153A
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reaction
xylene
toluene
series catalyst
palladium
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CN105085153B (en
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季静
柴忠义
纪玉国
张富春
任玉梅
杜周
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • 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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Abstract

The invention relates to a method for producing benzene, toluene and xylene by using arene with more than 9 carbon atoms. According to the method disclosed by the invention, under the conditions that an aluminum oxide-titania composition exists, a beta molecular sieve composite carrier exists, and a pd-based catalyst for metal pd, loaded on the composite carrier exists, hydrogenation dealkylation is performed on C9+ arenes, so that benzene, toluene and xylene are prepared. In the reaction process, the reaction conditions are controlled, so that the high conversion rate of the C9+ arenes can be obtained, and besides, a higher product BTX yield is obtained.

Description

A kind of method using the aromatics production benzene,toluene,xylene of carbon more than 9
Technical field
The invention belongs to C 9 +aromatic hydrocarbons applied technical field, relates to a kind of use carbon 9 (C 9) more than the method for aromatics production benzene,toluene,xylene (BTX).
Background technology
In oil and the coal course of processing, the aromatic hydrocarbons of by-product, is mainly C 9and C 10aromatic hydrocarbons, is referred to as C 9 +aromatic hydrocarbons.Be mainly derived from refinery catalytic reforming unit, ethylene unit by-product pyrolysis gasoline and ethylene bottom oil and coal high-temperature coking by-product coal tar wet goods.Along with the increase of oil-refining capacity and being constructed and put into operation of the large-scale ethene of megaton, C 9 +aromatic production will significantly improve.
The U.S., USSR (Union of Soviet Socialist Republics) and Japan just begin one's study and utilize C in the 1950's 9 +aromatic hydrocarbons, transforms basic petrochemical materialss such as generating the higher benzene,toluene,xylene of added value.At present, external relevant technique mainly contains HAD technique, DETOL technique, the techniques such as TAC9 technique and IEOLYST/SK.Catalyzer mainly adopts alumina load metal catalyst or molecular sieve carried metal catalyst.
China is to C 9 +the research on utilization of aromatic hydrocarbons from 20 century 70s, compared with abroad, China C 9 +the utilization of aromatic hydrocarbons is still in the junior stage.So China is annual still at basic chemical raw materials such as a large amount of import benzene.Given this, in order in the face of fierce market competition, develop one and utilize C 9 +the method of aromatics production benzene,toluene,xylene, alleviates the situation of a large amount of dependence on import of these basic chemical raw materials of China.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, provides a kind of and uses C 9and C 10the method of aromatics production benzene,toluene,xylene.The method makes C under the palladium series catalyst existence condition containing aluminium oxide-titanium oxide mixture and beta-molecular sieve complex carrier and the palladium metal of load on described complex carrier 9and C 10aromatic hydrocarbons carries out hydro-dealkylation reaction and prepares benzene,toluene,xylene, can obtain higher C by controlling reaction conditions in reaction process 9and C 10the yield of aromatics conversion rate and product benzene,toluene,xylene (BTX).
For this reason, the invention provides a kind of use C 9and C 10the method of aromatics production benzene,toluene,xylene, it makes C under being included in palladium series catalyst effect 9and C 10aromatic hydrocarbons carries out hydro-dealkylation reaction and prepares benzene,toluene,xylene, wherein, described palladium series catalyst comprises aluminium oxide-titanium oxide mixture and beta-molecular sieve complex carrier and the palladium metal of load on described complex carrier, and the content of palladium metal is 0.3%-1.8% based on the total weight of described palladium series catalyst in described palladium series catalyst.
In above-mentioned reaction process, make C 9 +aromatic hydrocarbons contacts with described palladium series catalyst with the charging of hydrogen and carries out hydro-dealkylation reaction in reaction unit.In described charging, hydrogen and C 9 +the volume ratio of aromatic hydrocarbons is 600-1000.
According to the present invention, in described complex carrier, described beta-molecular sieve accounts for 30 % by weight-70 % by weight.
According to the present invention, in described complex carrier, described aluminium oxide-titanium oxide mixture accounts for 30 % by weight-70 % by weight.
In the present invention, described complex carrier shape can be bar shaped, clover shape, sheet, preferred clover shape.
In one embodiment of the invention, in described aluminium oxide-titanium oxide mixture, the weight ratio of aluminum oxide and titanium oxide is 2.3-5:1.The weight ratio of preferential oxidation aluminium and titanium oxide is 4:1.
In the present invention, the specific surface of described catalyzer is 90-240m 2/ g, is preferably 120-200m 2/ g.The pore volume of described catalyzer is 0.7-1.8ml/g, is preferably 0.85-1.25ml/g.
According to the present invention, described method also comprises carries out pretreated step by described palladium series catalyst: comprise and being reduced 10 hours in hydrogen medium under 120 DEG C of constant temperatures by palladium series catalyst, reduction reaction pressure is normal pressure.
In one embodiment of the invention, the condition of described catalytic hydrogenation reaction is as follows:
The reactor inlet temperature of described hydro-dealkylation reaction is 220-300 DEG C.Preferred described reactor inlet temperature is 240-280 DEG C.
The pressure of described hydro-dealkylation reaction is 1.0-3.0MPa.The pressure of preferred described hydro-dealkylation reaction is 1.5-2.5MPa.
Described Feed space velocities is 1-5h -1.Preferred described Feed space velocities is 2-4h -1.
" the C of term described in the present invention 9 +aromatic hydrocarbons " refer to the aromatic hydrocarbons of by-product in oil and the coal course of processing, be C 9the general designation of above aromatic hydrocarbons, is wherein mainly C 9, C 10and C 10above aromatic hydrocarbons, but C 10above aromatic hydrocarbons accounts for a very little part.
In the present invention, C of the present invention 9 +aromatic hydrocarbons derives from refinery catalytic reforming unit or ethylene unit by-product pyrolysis gasoline.
Any suitable reactions device that in the present invention, reaction unit used is known to those skilled in the art, such as, can use fixing isothermal bed hydroprocessing reaction unit.
The present inventor finds through lot of experiments, under the palladium series catalyst existence condition containing aluminium oxide-titanium oxide mixture and beta-molecular sieve complex carrier and the palladium metal of load on described complex carrier, make C 9and C 10aromatic hydrocarbons carries out hydro-dealkylation reaction and prepares benzene,toluene,xylene, can obtain higher C by controlling reaction conditions in reaction process 9and C 10higher product B TX yield is obtained while aromatics conversion rate.
Embodiment
For making the present invention easier to understand, describe the present invention in detail below in conjunction with embodiment and accompanying drawing, these embodiments only play illustrative effect, are not limited to range of application of the present invention, NM specific experiment method in the following example, conveniently experimental technique carries out usually.
Embodiment
Embodiment 1-6
Prepare catalyzer of the present invention
1, the preparation of complex carrier
Be 160m by 100g specific surface 2/ g and pore volume are that the 0.6g/ml dilution heat of sulfuric acid of the cylindrical shaped alumina 50ml titanium sulfate of 0.74ml/g floods 4 hours, drying 10 hours at the temperature of 120 DEG C, at the roasting temperature 6 hours of 500 DEG C, obtain 125g alumina-silica titanium carrier, wherein the weight ratio of aluminum oxide and titanium oxide is 4:1.By a certain amount of beta-molecular sieve and a certain amount of TiO 2/ Al 2o 3mixing, adds the aqueous nitric acid kneading that concentration is 2%, extruded moulding, 120 DEG C of dryings, and in air, 500 DEG C of roastings both obtained complex carrier in 4 hours.
2, the preparation of catalyzer
Get above-mentioned complex carrier, with palladium chloride solution dipping, filter, drying 8 hours under 110 DEG C of conditions, under 500 DEG C of conditions, roasting both obtains catalyzer in 7 hours in atmosphere.Be denoted as catalyst A, B, C, D, E respectively.Catalyst property is in table 1.
Table 1. catalyst property
Embodiment 1 2 3 4 5 6
Catalyzer is numbered A B C D E F
Beta-molecular sieve content (% by weight) 70 60 50 40 30 65
TiO 2/Al 2O 3Content (% by weight) 30 40 50 60 70 35
TiO 2:Al 2O 3 1:4 1:4 1:4 1:4 1:4 1:4
Pd content (% by weight) 0.3 1.2 1.8 0.6 1.6 1.3
Embodiment 6:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyst A, temperature of reaction is 220 DEG C, and reaction pressure is 3.0MPa, and Feed space velocities is 1.0h -1, BTX yield is in table 2.
Embodiment 7:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyst A, temperature of reaction is 240 DEG C, and reaction pressure is 3.0MPa, and Feed space velocities is 2.0h -1, BTX yield is in table 2.
Embodiment 8:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyst B, temperature of reaction is 260 DEG C, and reaction pressure is 1.5MPa, and Feed space velocities is 2.0h -1, BTX yield is in table 2.
Embodiment 9:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyst B, temperature of reaction is 230 DEG C, and reaction pressure is 3.0MPa, and Feed space velocities is 1.0h -1, BTX yield is in table 2.
Embodiment 10:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyzer C, temperature of reaction is 260 DEG C, and reaction pressure is 2.0MPa, and Feed space velocities is 3.0h -1, BTX yield is in table 2.
Embodiment 11:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyzer C, temperature of reaction is 280 DEG C, and reaction pressure is 2.0MPa, and Feed space velocities is 1.5h -1, BTX yield is in table 2.
Embodiment 12:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyzer D, temperature of reaction is 300 DEG C, and reaction pressure is 3.0MPa, and Feed space velocities is 1.0h -1, BTX yield is in table 2.
Embodiment 13:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyzer D, temperature of reaction is 250 DEG C, and reaction pressure is 2.5MPa, and Feed space velocities is 4.0h -1, BTX yield is in table 2.
Embodiment 14:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyzer E, temperature of reaction is 230 DEG C, and reaction pressure is 2.5MPa, and Feed space velocities is 2.0h -1, BTX yield is in table 2.
Embodiment 15:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyzer F, temperature of reaction is 270 DEG C, and reaction pressure is 2.5MPa, and Feed space velocities is 5.0h -1, BTX yield is in table 2.
Embodiment 16:
Use 100ml isothermal bed hydroprocessing reaction evaluating device, load catalyzer F, temperature of reaction is 260 DEG C, and reaction pressure is 2.0MPa, and Feed space velocities is 3.0h -1, BTX yield is in table 2.
BTX yield (raw material is identical) under table 2. different condition
Comparative example 1:
Use two cover 100ml isothermal bed hydroprocessing reaction evaluating devices, be respectively charged into catalyzer D and domestic similar non-palladium series catalyst, use same process condition to utilize C 9 +aromatics production benzene, processing condition are: temperature of reaction is 260 DEG C, and reaction pressure is 2.5MPa, and air speed is 3.0h -1, benzene yield is in table 3.
Catalyzer described in table 3. and domestic similar catalyst benzene yield contrast
Catalyzer title Catalyzer D Similar non-palladium series catalyst
BTX yield (%) 74.3 60.1
From table 3, under same working condition, the method for the invention is used to utilize C 9 +aromatics production benzene,toluene,xylene and the C with domestic similar non-palladium series catalyst process 9 +aromatic hydrocarbons compares, and its BTX yield is higher.
As can be seen from above-described embodiment and comparative example, the inventive method is adopted to make C under the palladium series catalyst existence condition containing aluminium oxide-titanium oxide mixture and beta-molecular sieve complex carrier and the palladium metal of load on described complex carrier 9 +aromatic hydrocarbons carries out hydro-dealkylation reaction and prepares benzene,toluene,xylene, can obtain higher C by controlling reaction conditions in reaction process 9 +higher product B TX yield is obtained while aromatics conversion rate.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (9)

1. one kind uses C 9and C 10the method of aromatics production benzene,toluene,xylene, it makes C under being included in palladium series catalyst effect 9and C 10aromatic hydrocarbons carries out hydro-dealkylation reaction and prepares benzene,toluene,xylene, wherein, described palladium series catalyst comprises aluminium oxide-titanium oxide mixture and beta-molecular sieve complex carrier and the palladium metal of load on described complex carrier, and the content of palladium metal is 0.3%-1.8% based on the total weight of described palladium series catalyst in described palladium series catalyst.
2. method according to claim 1, is characterized in that, in described complex carrier, described beta-molecular sieve accounts for 30 % by weight-70 % by weight.
3. method according to claim 1 and 2, is characterized in that, in described complex carrier, described aluminium oxide-titanium oxide mixture accounts for 30 % by weight-70 % by weight.
4. according to the method in claim 1-3 described in any one, it is characterized in that, described method also comprises carries out pretreated step by described palladium series catalyst: comprise and being reduced 10 hours in hydrogen medium under 120 DEG C of constant temperatures by palladium series catalyst.
5. according to the method in claim 1-4 described in any one, it is characterized in that, the condition of described catalytic hydrogenation reaction is: reactor inlet temperature is 220-300 DEG C, and reaction pressure is 1.0-3.0MPa, and Feed space velocities is 1-5h -1.
6. according to the method in claim 1-5 described in any one, it is characterized in that, described reactor inlet temperature is 240-280 DEG C.
7. according to the method in claim 1-6 described in any one, it is characterized in that, described reaction pressure is 1.5-2.5MPa.
8. according to the method in claim 1-7 described in any one, it is characterized in that, described Feed space velocities is 2 -4h -1.
9. according to the method in claim 1-8 described in any one, it is characterized in that, described C 9and C 10the transformation efficiency of aromatic hydrocarbons is greater than 60%.
CN201410192900.0A 2014-05-08 2014-05-08 A kind of method of aromatics production benzene,toluene,xylene using carbon more than 9 Active CN105085153B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906272A (en) * 2004-01-22 2007-01-31 波利玛利欧洲股份公司 Process for the catalytic hydrodealkylation of alkylaromatic hydrocarbons
CN101348405A (en) * 2007-07-18 2009-01-21 中国石油化工股份有限公司 Method for preparing light arene and light alkane from hydrocarbon raw material
KR101377050B1 (en) * 2011-04-18 2014-03-24 인하대학교 산학협력단 Method for selective dealkylation of alkyl-substituted C9+ aromatic compound
CN103721711A (en) * 2012-10-10 2014-04-16 中国石油化工股份有限公司 Heavy aromatic hydrodealkylation palladium catalyst and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906272A (en) * 2004-01-22 2007-01-31 波利玛利欧洲股份公司 Process for the catalytic hydrodealkylation of alkylaromatic hydrocarbons
CN101348405A (en) * 2007-07-18 2009-01-21 中国石油化工股份有限公司 Method for preparing light arene and light alkane from hydrocarbon raw material
KR101377050B1 (en) * 2011-04-18 2014-03-24 인하대학교 산학협력단 Method for selective dealkylation of alkyl-substituted C9+ aromatic compound
CN103721711A (en) * 2012-10-10 2014-04-16 中国石油化工股份有限公司 Heavy aromatic hydrodealkylation palladium catalyst and preparation method thereof

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