CN106278797A - Catalysis drying gas produces the method for ethylbenzene - Google Patents
Catalysis drying gas produces the method for ethylbenzene Download PDFInfo
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- CN106278797A CN106278797A CN201510324512.8A CN201510324512A CN106278797A CN 106278797 A CN106278797 A CN 106278797A CN 201510324512 A CN201510324512 A CN 201510324512A CN 106278797 A CN106278797 A CN 106278797A
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Abstract
The present invention relates to a kind of method that catalysis drying gas produces ethylbenzene, every section of problem that beds temperature rise is uneven, ethylbenzene yield is low and catalyst utilization is low in mainly ethylene concentration change causes greatly reactor contained by catalysis drying gas in solution prior art.The present invention is comprised the following steps by employing: a) catalysis drying gas containing ethylene is divided into N stock after at least one heat transmission equipment heat exchange, and segmentation enters each section of beds of alkylation reactor；Wherein N >=2；B) benzene feedstock is all added by alkylation reactor first paragraph, or is divided into N stock section to add alkylation reactor；Wherein N >=2；C) described heat transmission equipment is provided with catalysis drying gas outlet temperature control device, during the change of catalytic material dry gas ethylene concentration, make every section of beds inlet temperature identical by regulation catalysis drying gas outlet temperature, and the identical technical scheme of every section of beds temperature rise preferably solves this problem, can be used in the commercial production that catalysis drying gas produces ethylbenzene.
Description
Technical field
The present invention relates to a kind of method that catalysis drying gas produces ethylbenzene.
Background technology
Catalysis drying gas is the by-product of petroleum industry catalytic cracking, its key component be ethylene, propylene,
Hydrogen, ethane etc., along with being significantly increased of the annual petroleum consumption in the whole world, contain in by-product dry gas
The anxious utilization to be transformed of ethylene resource.Before this due to the reason such as technology and cost, this part precious resources
Substantially being burnt as fuel, while waste resource, also discharge great amount of carbon dioxide is polluted
Environment.
Utilize the ethylene production ethylbenzene in catalysis drying gas, abroad the most open at the fifties in last century end
Beginning to explore, the seventies enters the industrial experiment stage.Wherein there is Mobil/Badger company of the U.S.
Cooperative development with ZSM-5 silica-rich zeolite be Catalyst Production ethylbenzene Mobil/Badger gas phase divide
Sub-riddler's skill, Uop Inc. exploitation with Al2O3-BF3ALKar work for Catalyst Production ethylbenzene
Skill and the catalytic distillation technology of exploitation later thereof, separately have Monsanto in its pure ethylene second improved
The catalysis drying gas process for preparing ethylbenzene of exploitation on the basis of benzene process.
With catalysis drying gas catalysis drying gas for raw material production ethylbenzene, foreign patent have US2939890,
US369245、US702886、US3848012、US4107224、US4459426、GB827830
Deng, these technology are to the propylene in raw material, H2S、H2O、O2、CO2Have strictly Deng impurity content
Requirement, they need to be removed to ppm level and just can apply.
Recent year also develops catalysis drying gas ethylbenzene technology, and relevant patent has
ZL200610046750.8、ZL200510105256.X、ZL200410037433.0、
ZL200410021102.8, ZL201110105517.3 etc., these technology remove third at catalysis drying gas
After alkene, all it is directly entered alkylation reactor with single temperature, but due to plant catalytic dry gas
In ethylene contents unstable, usual ethylene contents can cause alkyl 10～50% fluctuation
In changing reactor, every section of beds entrance is difficult to control in mutually synthermal and identical temperature rise, generally
When ethylene concentration reduces, reactor first paragraph bed temperature rise can be caused, and several sections of beds afterwards
Layer inlet temperature is difficult to reach design and requires temperature, and ethylbenzene yield reduces；When ethylene concentration raises,
After causing reactor again, several sections of bed inlet temperatures exceed design and require temperature, and side reaction increases,
Catalysqt deactivation is accelerated.
Summary of the invention
The technical problem to be solved is that in prior art, ethylene contained by catalysis drying gas is dense
Degree change causes greatly in reactor every section, and beds temperature rise is uneven, ethylbenzene yield is low and catalyst
The problem that utilization rate is low, it is provided that a kind of method that new catalysis drying gas produces ethylbenzene.The method can make
In reactor, every section of catalyst inlet temperature is identical with bed temperature rise, has ethylbenzene yield height and catalysis
The feature that agent utilization rate is high.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of catalysis is dry
Gas produces the method for ethylbenzene, comprises the following steps:
A) catalysis drying gas containing ethylene is divided into N stock, segmentation after at least one heat transmission equipment heat exchange
Enter each section of beds of alkylation reactor；Wherein N >=2；
B) benzene feedstock is all added by alkylation reactor first paragraph, or is divided into N stock section to add alkane
Glycosylation reaction device；Wherein N >=2；
C) described heat transmission equipment is provided with catalysis drying gas outlet temperature control device, catalytic material dry gas second
During alkene concentration change, make every section of beds entrance temperature by regulation catalysis drying gas outlet temperature
Spend identical, and every section of beds temperature rise is identical.
In technique scheme, it is preferable that control dry gas outlet temperature by regulation heat transferring medium flow
Degree.
In technique scheme, it is preferable that described heat transmission equipment is provided with catalysis drying gas bypass, passes through
Regulation catalysis drying gas bypass flow controls dry gas outlet temperature.
In technique scheme, it is preferable that in catalytic material dry gas, volume of ethylene content is 5～95%.
In technique scheme, it is preferable that alkylation reactor is axial multi-stage fixed-bed reactor,
Catalyst divides 2～8 sections of fillings.
In technique scheme, it is preferable that catalysis drying gas and benzene alkylation reaction are gas phase reaction,
Reactor inlet temperature 250～450 DEG C, reactor inlet pressure 0.5～2.0MPaG, benzene and ethylene rub
Your ratio is 2～7, and weight ethylene air speed is 0.3～2.0 hour-1。
In technique scheme, it is preferable that catalysis drying gas is after one or more heat transmission equipment heat exchange
Temperature be 10～100 DEG C.
In technique scheme, it is preferable that catalysis drying gas be divided into N stock enter reactor, per share enter
Stream amount is identical；Described heat transmission equipment is tubular heat exchanger.
In technique scheme, it is preferable that every section of beds inlet temperature is 250～450 DEG C；
Every section of beds temperature rise is 5～30 DEG C.It is highly preferred that every section of beds inlet temperature is
300～400 DEG C；Every section of beds temperature rise is 10～25 DEG C.
In conventional art, catalysis drying gas use absorption and desorption method removing propylene after, generally with
10～40 DEG C of single temperature divide multiply to enter alkylation reactor, mix with benzene feedstock at first paragraph bed
Conjunction reaches reaction and requires that temperature enters reactor reaction, and the low-temperature catalyzed dry gas of second segment～N section enters
After material mixes with the high-temperature reacting gas from the preceding paragraph beds, reaction temperature drops to requirement
Temperature enter next section of beds, by catalysis drying gas ethylene contents design temperature and charging
Amount ensure that every section of beds inlet temperature keeps identical with temperature rise, it is ensured that can obtain higher
Ethylbenzene yield and the high usage of catalyst.But due to the ethylene contents in plant catalytic dry gas also
Instability, usual ethylene contents can cause in alkylation reactor every section 10～50% fluctuation
Beds is difficult to control to mutually synthermal due to the significantly change of ethylene concentration, entrance, catalysis
Agent bed temperature rise also differs relatively big, when in catalysis drying gas, ethylene concentration less than design load constantly, can be made
Become reactor first paragraph bed temperature rise, and several sections of bed inlet temperatures afterwards are less than design requirement
Temperature, ethylbenzene yield reduces, and when in catalysis drying gas, ethylene concentration is higher than design load, can make again
Becoming several sections of bed inlet temperatures after reactor to exceed design and require temperature, side reaction increases, catalyst
Inactivation is accelerated.
In the present invention, catalysis drying gas, before entering alkylation reactor, is provided with one or more changing
Hot equipment, heat transmission equipment is provided with catalysis drying gas outlet temperature and controls device, in catalytic material dry gas second
Catalyst every section inlet temperature and bed can be made by regulation catalysis drying gas outlet temperature during alkene concentration change
Layer temperature rise is identical.When in catalysis drying gas, ethylene concentration is less than design load, raised by heat-exchanger rig
Catalysis drying gas outlet temperature, it is ensured that each section of bed inlet temperatures reaches design temperature, and when catalysis is dry
When ethylene concentration is higher than design load in gas, catalysis drying gas outlet temperature can be reduced by heat-exchanger rig,
Ensure that each section of bed inlet temperatures requires temperature less than design.Use the inventive method, alkane can be made
Glycosylation reaction system adapts to the ethylene concentration change of catalysis drying gas relative broad range, and in reactor every section
Catalyst inlet temperature and bed temperature rise remain essentially identical, can improve ethylbenzene yield 1～20%, carry
High catalyst utilization rate 10～50%, achieves preferable technique effect.
Accompanying drawing explanation
Fig. 1 is the technological process using technical solution of the present invention.
Fig. 2 produces ethylbenzene prior art response system technological process for using typical catalysis drying gas.
In Fig. 1, I is alkylation reactor, and II is catalysis drying gas heat-exchanger rig, and III is dry for catalysis
Gas outlet temperature controls device, and 1 is catalysis drying gas raw material, and 2 is benzene, N1～N4 is the 1st～the 4th
Section bed catalyst dry gas charging (as a example by 4 sections of beds), n1～n4 is the 1st～the 4th section of bed benzene
Charging, 3 is alkylation reactor discharging gas.
In Fig. 1, catalysis drying gas raw material 1 is through catalysis drying gas heat-exchanger rig II heat exchange, in outlet temperature control
Device processed controls lower point 4 strands (as a example by 4 sections of beds) and respectively enters alkylation reactor I, former
Material benzene is all added by reactor first paragraph, or points 4 stock sections add alkylation reactors, the
One section of bed, catalysis drying gas N1 and benzene n1 is mixed into first paragraph bed, afterwards every section of bed,
Catalysis drying gas N2～N4 and reacting gas and benzene charging n2～n4 from the preceding paragraph bed mix,
Entering catalyst bed reaction, final alkylation reactor discharging gas 3 leaves reaction gas and enters follow-up
Workshop section.
In Fig. 2, I is alkylation reactor, and 1 is catalysis drying gas raw material, and 2 is benzene, N1～N4 is
1st～the 4th section of bed catalyst dry gas charging (as a example by 4 sections of beds), n1～n4 is the 1st～the 4th
Section bed benzene charging, 3 is alkylation reactor discharging gas.
In Fig. 2, catalysis drying gas raw material 1 point 4 strands (as a example by 4 sections of beds) respectively enters alkyl
Changing reactor I, benzene feedstock is all added by reactor first paragraph, or point 4 stock sections add alkyl
Changing reactor, at first paragraph bed, catalysis drying gas N1 and benzene n1 is mixed into first paragraph bed,
Every section of bed afterwards, catalysis drying gas N2～N4 and reacting gas and benzene from the preceding paragraph bed enter
Material n2～n4 mixing, enters catalyst bed reaction, and final alkylation reactor discharging gas 3 leaves
Reaction gas enters follow-up workshop section.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Certain 100,000 tons/year of catalysis drying gas produces Benzene Devices (year operation hour 8000 hours), adopts
By the technique of Fig. 1, main operating mode and ruuning situation are shown in Table 1.
Table 1
[embodiment 2]
Certain 100,000 tons/year of catalysis drying gas produces Benzene Devices (year operation hour 8000 hours), adopts
By the technique of Fig. 1, main operating mode and ruuning situation are shown in Table 2.
Table 2
[embodiment 3]
Certain 100,000 tons/year of catalysis drying gas produces Benzene Devices (year operation hour 8000 hours), adopts
By the technique of Fig. 1, main operating mode and ruuning situation are shown in Table 3.
Table 3
[comparative example 1]
Certain 100,000 tons/year of catalysis drying gas produces Benzene Devices (year operation hour 8000 hours), adopts
By the technique of Fig. 2, main operating mode and ruuning situation are shown in Table 4.
Table 4
Claims (10)
1. the method that catalysis drying gas produces ethylbenzene, comprises the following steps:
A) catalysis drying gas containing ethylene is divided into N stock, segmentation after at least one heat transmission equipment heat exchange
Enter each section of beds of alkylation reactor；Wherein N >=2；
B) benzene feedstock is all added by alkylation reactor first paragraph, or is divided into N stock section to add alkane
Glycosylation reaction device；Wherein N >=2；
C) described heat transmission equipment is provided with catalysis drying gas outlet temperature control device, catalytic material dry gas second
During alkene concentration change, make every section of beds entrance temperature by regulation catalysis drying gas outlet temperature
Spend identical, and every section of beds temperature rise is identical.
Catalysis drying gas the most according to claim 1 produces the method for ethylbenzene, it is characterised in that logical
Overregulate heat transferring medium flow and control dry gas outlet temperature.
Catalysis drying gas the most according to claim 1 produces the method for ethylbenzene, it is characterised in that institute
State heat transmission equipment and be provided with catalysis drying gas bypass, control dry gas by regulation catalysis drying gas bypass flow and go out
Mouth temperature.
Catalysis drying gas the most according to claim 1 produces the method for ethylbenzene, it is characterised in that former
In material catalysis drying gas, volume of ethylene content is 5～95%.
Catalysis drying gas the most according to claim 1 produces the method for ethylbenzene, it is characterised in that alkane
Glycosylation reaction device is axial multi-stage fixed-bed reactor, and catalyst divides 2～8 sections of fillings.
Catalysis drying gas the most according to claim 1 produces the method for ethylbenzene, it is characterised in that urge
Change dry gas and benzene alkylation reaction is gas phase reaction, reactor inlet temperature 250～450 DEG C, reactor
Inlet pressure 0.5～2.0MPaG, benzene and ethylene molar ratio are 2～7, and weight ethylene air speed is 0.3～2.0
Hour-1。
Catalysis drying gas the most according to claim 1 produces the method for ethylbenzene, it is characterised in that urge
Changing dry gas temperature after one or more heat transmission equipment heat exchange is 10～100 DEG C.
Catalysis drying gas the most according to claim 1 produces the method for ethylbenzene, it is characterised in that urge
Changing dry gas is divided into N stock to enter reactor, and per share feed rate is identical.
Catalysis drying gas the most according to claim 1 produces the method for ethylbenzene, it is characterised in that anti-
In answering device, every section of beds inlet temperature is identical, and temperature range is 250～450 DEG C, every section of catalysis
Agent bed temperature rise is identical, and limit of temperature rise is 5～30 DEG C.
The method utilizing catalysis drying gas to produce ethylbenzene the most according to claim 9, its feature
It is that every section of beds inlet temperature is 300～400 DEG C；Every section of beds temperature rise is
10～25 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108299143A (en) * | 2017-12-27 | 2018-07-20 | 北方华锦化学工业股份有限公司 | Ethylbenzene vapor phase alkylation device opens, stop during recovered material method |
| CN109351289A (en) * | 2018-10-18 | 2019-02-19 | 中石化广州工程有限公司 | A method of control alkylation reactor bed temperature rise |
| CN111560267A (en) * | 2020-05-14 | 2020-08-21 | 洛阳市科创石化科技开发有限公司 | Method for producing high-octane low-benzene gasoline |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299143A (en) * | 2017-12-27 | 2018-07-20 | 北方华锦化学工业股份有限公司 | Ethylbenzene vapor phase alkylation device opens, stop during recovered material method |
| CN109351289A (en) * | 2018-10-18 | 2019-02-19 | 中石化广州工程有限公司 | A method of control alkylation reactor bed temperature rise |
| CN111560267A (en) * | 2020-05-14 | 2020-08-21 | 洛阳市科创石化科技开发有限公司 | Method for producing high-octane low-benzene gasoline |
| CN111560267B (en) * | 2020-05-14 | 2021-10-12 | 洛阳市科创石化科技开发有限公司 | Method for producing high-octane low-benzene gasoline |
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