CN105085153B - A kind of method of aromatics production benzene,toluene,xylene using carbon more than 9 - Google Patents

A kind of method of aromatics production benzene,toluene,xylene using carbon more than 9 Download PDF

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CN105085153B
CN105085153B CN201410192900.0A CN201410192900A CN105085153B CN 105085153 B CN105085153 B CN 105085153B CN 201410192900 A CN201410192900 A CN 201410192900A CN 105085153 B CN105085153 B CN 105085153B
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China
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palladium
catalyst
reaction
complex carrier
toluene
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CN201410192900.0A
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CN105085153A (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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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to one kind to use C9The method of aromatics production benzene,toluene,xylene above.This method makes C under the palladium series catalyst existence condition containing aluminum oxide titanium oxide compound and beta-molecular sieve complex carrier and the Metal Palladium being supported on the complex carrier9 +Aromatic hydrocarbons carries out hydro-dealkylation reaction to prepare benzene,toluene,xylene, by controlling reaction condition to obtain higher C in course of reaction9 +Higher product BTX yields are obtained while aromatics conversion rate.

Description

A kind of method of aromatics production benzene,toluene,xylene using carbon more than 9

Technical field

The invention belongs to C9 +Aromatic hydrocarbons applied technical field, it is related to one kind and uses (the C of carbon 99) more than aromatics production benzene, first The method of benzene, dimethylbenzene (BTX).

Background technology

The aromatic hydrocarbons of by-product, predominantly C in oil and coal process9And C10Aromatic hydrocarbons, it is referred to as C9 +Aromatic hydrocarbons.Main source In oil plant catalytic reforming unit, ethylene unit by-product drippolene and ethylene bottom oil and coal high-temperature coking by-product coal tar Deng.With being constructed and put into operation for the increase of refining capacity and the large-scale ethene of megaton, C9 +Aromatic production will greatly improve.

The U.S., the former Soviet Union and Japan begin to research and utilization C in the 1950s9 +Aromatic hydrocarbons, it is converted into added value The basic petrochemical materials such as higher benzene,toluene,xylene.At present, external related technique mainly has HAD techniques, DETOL Technique, the technique such as TAC9 techniques and IEOLYST/SK.Catalyst is mainly born using alumina load metallic catalyst or molecular sieve Supported metal catalyst.

China is to C9 +The research on utilization of aromatic hydrocarbons is since the 1970s, compared with foreign countries, China C9 +Aromatic hydrocarbons Using being still in the junior stage.So China is annual still in basic chemical raw materials such as a large amount of import benzene.In consideration of it, in order in face of swashing Strong market competition, develop one kind and utilize C9 +The method of aromatics production benzene,toluene,xylene, to alleviate China, these are basic Industrial chemicals largely relies on the situation of import.

The content of the invention

The technical problems to be solved by the invention are in view of the shortcomings of the prior art, there is provided one kind uses C9And C10Aromatic hydrocarbons is given birth to The method for producing benzene,toluene,xylene.This method is containing aluminium oxide-titanium oxide compound and beta-molecular sieve complex carrier and negative Make C under the palladium series catalyst existence condition for the Metal Palladium being loaded on the complex carrier9And C10It is anti-that aromatic hydrocarbons carries out hydro-dealkylation Benzene,toluene,xylene should be prepared, by controlling reaction condition to obtain higher C in course of reaction9And C10Aromatic hydrocarbons converts The yield of rate and product benzene,toluene,xylene (BTX).

Therefore, the invention provides one kind to use C9And C10The method of aromatics production benzene,toluene,xylene, it is included in Make C under palladium series catalyst effect9And C10Aromatic hydrocarbons carries out hydro-dealkylation reaction to prepare benzene,toluene,xylene, wherein, it is described Palladium series catalyst includes aluminium oxide-titanium oxide compound and beta-molecular sieve complex carrier and is supported on the complex carrier Metal Palladium, and gross weight meter of the content of Metal Palladium based on the palladium series catalyst is 0.3%- in the palladium series catalyst 1.8%.

In above-mentioned course of reaction, make C9 +The charging of aromatic hydrocarbons and hydrogen contacted in reaction unit with the palladium series catalyst into Row hydro-dealkylation reacts.In the charging, hydrogen and C9 +The volume ratio of aromatic hydrocarbons is 600-1000.

According to the present invention, in the complex carrier, the beta-molecular sieve accounts for 30 weight %-70 weight %.

According to the present invention, in the complex carrier, the aluminium oxide-titanium oxide compound accounts for 30 weight %-70 weights Measure %.

In the present invention, described complex carrier shape can be bar shaped, clover shape, preferably sheet, clover shape.

In one embodiment of the invention, in the aluminium oxide-titanium oxide compound, the weight of aluminum oxide and titanium oxide It is 2.3-5 to measure ratio:1.It is preferred that the weight of aluminum oxide and titanium oxide ratio is 4:1.

In the present invention, the ratio surface of the catalyst is 90-240m2/ g, preferably 120-200m2/g.The catalyst Pore volume is 0.7-1.8ml/g, preferably 0.85-1.25ml/g.

According to the present invention, methods described is also including the step of being pre-processed the palladium series catalyst:Including by palladium system Catalyst reduces 10 hours under 120 DEG C of constant temperatures in hydrogen medium, and reduction reaction pressure is normal pressure.

In one embodiment of the invention, the condition of the catalytic hydrogenation reaction is as follows:

The reactor inlet temperature of the hydro-dealkylation reaction is 220-300 DEG C.It is preferred that the reactor inlet temperature For 240-280 DEG C.

The pressure of the hydro-dealkylation reaction is 1.0-3.0MPa.It is preferred that the pressure of the hydro-dealkylation reaction is 1.5-2.5MPa。

The Feed space velocities are 1-5h-1.It is preferred that the Feed space velocities are 2-4h-1

Heretofore described term " C9 +Aromatic hydrocarbons " refers to the aromatic hydrocarbons of by-product in oil and coal process, is C9Virtue above The general designation of hydrocarbon, wherein predominantly C9、C10And C10Aromatic hydrocarbons above, but C10Above aromatic hydrocarbons accounts for very small part.

In the present invention, C of the present invention9 +Aromatic hydrocarbons cracks from oil plant catalytic reforming unit or ethylene unit by-product In gasoline.

Reaction unit used any suitable reactions device known to those skilled in the art in the present invention, for example, can be with Use fixed isothermal bed hydroprocessing reaction unit.

The present inventor has found by lot of experiments, is containing aluminium oxide-titanium oxide compound and beta-molecular sieve Make C under complex carrier and the palladium series catalyst existence condition for the Metal Palladium being supported on the complex carrier9And C10Aromatic hydrocarbons enters Row hydro-dealkylation is reacted to prepare benzene,toluene,xylene, by controlling reaction condition higher in acquisition in course of reaction C9And C10Higher product BTX yields are obtained while aromatics conversion rate.

Embodiment

To make the present invention easier to understand, the present invention is described in detail below in conjunction with embodiment and accompanying drawing, these realities Apply example only serve it is illustrative, it is not limited to application of the invention, NM specific experiment side in the following example Method, generally carried out according to normal experiment method.

Embodiment

Embodiment 1-6

Prepare catalyst of the present invention

1st, the preparation of complex carrier

Than surface it is 160m by 100g2/ g and the cylindrical shaped alumina 50ml titanium sulfates that pore volume is 0.74ml/g 0.6g/ml dilution heat of sulfuric acid is impregnated 4 hours, is dried 10 hours at a temperature of 120 DEG C, and it is small that 6 are calcined at a temperature of 500 DEG C When, 125g alumina-silica titanium carriers are obtained, the wherein weight ratio of aluminum oxide and titanium oxide is 4:1.By a certain amount of beta molecule Sieve and a certain amount of TiO2/Al2O3Mixing, add the aqueous solution of nitric acid kneading that concentration is 2%, extruded moulding, 120 DEG C of dryings, sky 500 DEG C of roastings both obtain complex carrier in 4 hours in gas.

2nd, the preparation of catalyst

Above-mentioned complex carrier is taken, is impregnated with palladium chloride solution, is filtered, dries 8 hours under the conditions of 110 DEG C, in atmosphere 500 It is calcined under the conditions of DEG C 7 hours and both obtains catalyst.Catalyst A, B, C, D, E are denoted as respectively.Catalyst property is shown in Table 1.

The catalyst property of table 1.

Embodiment 1 2 3 4 5 6 Catalyst is numbered A B C D E F Beta-molecular sieve content (weight %) 70 60 50 40 30 65 TiO2/Al2O3Content (weight %) 30 40 50 60 70 35 TiO2:Al2O3 1:4 1:4 1:4 1:4 1:4 1:4 Pd contents (weight %) 0.3 1.2 1.8 0.6 1.6 1.3

Embodiment 6:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst A, reaction temperature is 220 DEG C, reaction pressure For 3.0MPa, Feed space velocities 1.0h-1, BTX yields are shown in Table 2.

Embodiment 7:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst A, reaction temperature is 240 DEG C, reaction pressure For 3.0MPa, Feed space velocities 2.0h-1, BTX yields are shown in Table 2.

Embodiment 8:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst B, reaction temperature is 260 DEG C, reaction pressure For 1.5MPa, Feed space velocities 2.0h-1, BTX yields are shown in Table 2.

Embodiment 9:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst B, reaction temperature is 230 DEG C, reaction pressure For 3.0MPa, Feed space velocities 1.0h-1, BTX yields are shown in Table 2.

Embodiment 10:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst C, reaction temperature is 260 DEG C, reaction pressure For 2.0MPa, Feed space velocities 3.0h-1, BTX yields are shown in Table 2.

Embodiment 11:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst C, reaction temperature is 280 DEG C, reaction pressure For 2.0MPa, Feed space velocities 1.5h-1, BTX yields are shown in Table 2.

Embodiment 12:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst D, reaction temperature is 300 DEG C, reaction pressure For 3.0MPa, Feed space velocities 1.0h-1, BTX yields are shown in Table 2.

Embodiment 13:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst D, reaction temperature is 250 DEG C, reaction pressure For 2.5MPa, Feed space velocities 4.0h-1, BTX yields are shown in Table 2.

Embodiment 14:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst E, reaction temperature is 230 DEG C, reaction pressure For 2.5MPa, Feed space velocities 2.0h-1, BTX yields are shown in Table 2.

Embodiment 15:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst F, reaction temperature is 270 DEG C, reaction pressure For 2.5MPa, Feed space velocities 5.0h-1, BTX yields are shown in Table 2.

Embodiment 16:

Using 100ml isothermal bed hydroprocessing reaction evaluating devices, load catalyst F, reaction temperature is 260 DEG C, reaction pressure For 2.0MPa, Feed space velocities 3.0h-1, BTX yields are shown in Table 2.

BTX yields under the different condition of table 2. (raw material is identical)

Comparative example 1:

Using two sets of 100ml isothermal bed hydroprocessing reaction evaluating devices, it is respectively charged into catalyst D and is urged with domestic similar non-palladium system Agent, C is utilized using same process condition9 +Aromatics production benzene, process conditions are:Reaction temperature is 260 DEG C, and reaction pressure is 2.5MPa, air speed 3.0h-1, benzene yield is shown in Table 3.

Catalyst described in table 3. contrasts with domestic similar catalyst benzene yield

Catalyst title Catalyst D Similar non-palladium series catalyst BTX yields (%) 74.3 60.1

From table 3, under same working condition, C is utilized using the method for the invention9 +Aromatics production benzene, toluene, Dimethylbenzene and the C handled with domestic similar non-palladium series catalyst9 +Aromatic hydrocarbons compares, and its BTX yield is higher.

It is can be seen that from above-described embodiment and comparative example using the inventive method containing aluminium oxide-titanium oxide compound With making C under beta-molecular sieve complex carrier and the palladium series catalyst existence condition for the Metal Palladium being supported on the complex carrier9 +Virtue Hydrocarbon carries out hydro-dealkylation reaction to prepare benzene,toluene,xylene, by controlling reaction condition to obtain in course of reaction Higher C9 +Higher product BTX yields are obtained while aromatics conversion rate.

The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.

Claims (9)

1. one kind uses C9And C10The method of aromatics production benzene,toluene,xylene, it, which is included under palladium series catalyst effect, makes C9 And C10Aromatic hydrocarbons carries out hydro-dealkylation reaction to prepare benzene,toluene,xylene, wherein, the palladium series catalyst is by aluminum oxide-oxygen Change titanium compound to form with beta-molecular sieve complex carrier and the Metal Palladium being supported on the complex carrier, and in the palladium system Gross weight meter of the content of Metal Palladium based on the palladium series catalyst is 0.3%-1.8% in catalyst.
2. according to the method for claim 1, it is characterised in that in the complex carrier, the beta-molecular sieve accounts for 30 weights Measure %-70 weight %.
3. according to the method for claim 1, it is characterised in that in the complex carrier, the aluminium oxide-titanium oxide is answered Compound accounts for 30 weight %-70 weight %.
4. according to the method described in any one in claim 1-3, it is characterised in that methods described is also included the palladium system The step of catalyst is pre-processed:Including palladium series catalyst is reduced into 10 under 120 DEG C of constant temperatures in hydrogen medium Hour.
5. according to the method described in any one in claim 1-3, it is characterised in that the condition of the catalytic hydrogenation reaction For:Reactor inlet temperature is 220-300 DEG C, reaction pressure 1.0-3.0MPa, Feed space velocities 1-5h-1
6. according to the method for claim 5, it is characterised in that the reactor inlet temperature is 240-280 DEG C.
7. according to the method for claim 5, it is characterised in that the reaction pressure is 1.5-2.5MPa.
8. according to the method for claim 5, it is characterised in that the Feed space velocities are 2-4h-1
9. according to the method described in any one in claim 1-3, it is characterised in that the C9And C10The conversion ratio of aromatic hydrocarbons is big In 60%.
CN201410192900.0A 2014-05-08 2014-05-08 A kind of method of aromatics production benzene,toluene,xylene using carbon more than 9 CN105085153B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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ITMI20040077A1 (en) * 2004-01-22 2004-04-22 Polimeri Europa Spa Method for the catalytic hydrodealkylation of alkylaromatic hydrocarbons
CN101348405B (en) * 2007-07-18 2011-01-19 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

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Publication number Priority date Publication date Assignee Title
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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