CN106278795A - Utilize the method that catalysis drying gas produces ethylbenzene - Google Patents
Utilize the method that catalysis drying gas produces ethylbenzene Download PDFInfo
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- CN106278795A CN106278795A CN201510324493.9A CN201510324493A CN106278795A CN 106278795 A CN106278795 A CN 106278795A CN 201510324493 A CN201510324493 A CN 201510324493A CN 106278795 A CN106278795 A CN 106278795A
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Abstract
The present invention relates to a kind of method utilizing catalysis drying gas to produce ethylbenzene, mainly solve prior art ethylene concentration change contained by catalysis drying gas and cause greatly every section of problem that beds temperature rise is uneven, ethylbenzene yield is low and catalyst utilization is low in reactor.The present invention is comprised the following steps by employing: a) catalysis drying gas containing ethylene is divided into N stock, 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) control each stock dry gas temperature so that every section of beds inlet temperature is identical, 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 utilizing catalysis drying gas to produce 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 for raw material production ethylbenzene, foreign patent have US2939890, US369245,
US702886, US3848012, US4107224, US4459426, GB827830 etc., these
Technology is to the propylene in raw material, H2S、H2O、O2、CO2Strict requirements are had Deng impurity content,
They need to be removed to ppm level 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；And raise at ethylene concentration
Time, after causing reactor again, several sections of bed inlet temperatures exceed design and require temperature, and side reaction increases
Adding, 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
In degree change causes greatly reactor, every section of beds temperature rise is uneven, causes ethylbenzene yield low and urges
The problem that agent utilization rate is low, it is provided that a kind of new method utilizing catalysis drying gas to produce ethylbenzene.Should
In method can make reactor, every section of catalyst inlet temperature is identical with bed temperature rise, has ethylbenzene yield
High and that catalyst utilization is high feature.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of utilization is urged
Change the method that dry gas produces ethylbenzene, comprise the following steps:
A) catalysis drying gas containing ethylene is divided into N stock, and segmentation enters the catalysis of each section of alkylation reactor
Agent bed；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) each stock dry gas temperature is controlled so that every section of beds inlet temperature is identical, and often
Section beds temperature rise is identical.
In technique scheme, it is preferable that by making each stock catalysis drying gas and heat transmission equipment heat exchange control
Make each stock dry gas temperature.
In technique scheme, it is preferable that described heat transmission equipment is provided with temperature control equipment, passes through
Regulation heat transferring medium flow controls each stock dry gas outlet temperature.
In technique scheme, it is preferable that heat transmission equipment is provided with catalysis drying gas bypass, by regulation
Catalysis drying gas bypass flow controls each stock 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 each stock catalysis drying gas respectively after heat-exchanger rig heat exchange,
It is 10～100 DEG C that per share dry gas temperature controls.
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 prior 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 the 1st section of bed
Conjunction reaches reaction and requires that temperature enters reactor reaction, and the low-temperature catalyzed dry gas of the 2nd section～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 is less than design load, can cause
Reactor first paragraph bed temperature rise, and several sections of bed inlet temperatures afterwards require temperature less than design
Degree, ethylbenzene yield reduces；And when in catalysis drying gas, ethylene concentration is higher than design load, can cause again
After reactor, several sections of bed inlet temperatures exceed design and require temperature, and side reaction increases, and catalyst loses
Live and accelerate.
In the present invention, catalysis drying gas averagely or is in proportion divided into N stock (N >=2), per share dry gas thing
Expect that through heat transmission equipment heat exchange, heat transmission equipment is provided with catalysis drying gas and goes out before entering alkylation reactor
Mouth temperature control equipment, dry by regulating per share catalysis when catalytic material dry gas ethylene concentration changes
Gas outlet temperature can make catalyst every section inlet temperature identical with bed temperature rise.When second in catalysis drying gas
When alkene concentration is less than design load, the catalysis being raised each section of beds of entrance by heat-exchanger rig is done
Gas outlet temperature, it is ensured that each section of bed inlet temperatures reaches design temperature, and when second in catalysis drying gas
When alkene concentration is higher than design load, the catalysis of each section of beds can be lowered into by heat-exchanger rig
Dry gas outlet temperature, it is ensured that each section of bed inlet temperatures requires temperature less than design.Use this
Bright method, can make alkylated reaction system adapt to the ethylene concentration change of catalysis drying gas relative broad range,
And every section of beds inlet temperature and bed temperature rise remain essentially identical in reactor, operation spirit
Live simple, ethylbenzene yield 1～20% can be improved, improve catalyst utilization 10～50%, achieve relatively
Good technique effect.
Accompanying drawing explanation
Fig. 1 is present invention process flow process.
Fig. 2 is the technological process of prior art.
In Fig. 1, as a example by catalysis drying gas charging point 4 strands, I～IV is the 1st～the 4th strand of catalysis drying gas
Feed exchanger, V 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, n1～n4 is the 1st～the 4th section of bed benzene charging, and 3 are
Alkylation reactor discharging gas.
In Fig. 1, catalysis drying gas raw material 1 is divided into 4 strands, and per share dry gas is through catalysis drying gas heat-exchanger rig
I～IV heat exchange, under outlet temperature controls device control, respectively enters alkylation reactor V, 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, V 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 V, 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 utilizing catalysis drying gas to produce ethylbenzene, comprises the following steps:
A) catalysis drying gas containing ethylene is divided into N stock, and segmentation enters the catalysis of each section of alkylation reactor
Agent bed；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) each stock dry gas temperature is controlled so that every section of beds inlet temperature is identical, and often
Section beds temperature rise is identical.
The method utilizing catalysis drying gas to produce ethylbenzene the most according to claim 1, its feature exists
In by making each stock catalysis drying gas control each stock dry gas temperature with heat transmission equipment heat exchange.
The method utilizing catalysis drying gas to produce ethylbenzene the most according to claim 2, its feature exists
It is provided with temperature control equipment in described heat transmission equipment, controls each stock by regulation heat transferring medium flow and do
Gas outlet temperature.
The method utilizing catalysis drying gas to produce ethylbenzene the most according to claim 2, its feature exists
It is provided with catalysis drying gas bypass in heat transmission equipment, controls each stock by regulation catalysis drying gas bypass flow and do
Gas outlet temperature.
The method utilizing catalysis drying gas to produce ethylbenzene the most according to claim 1, its feature exists
In catalytic material dry gas, volume of ethylene content is 5～95%.
The method utilizing catalysis drying gas to produce ethylbenzene the most according to claim 1, its feature exists
Being axial multi-stage fixed-bed reactor in described alkylation reactor, catalyst divides 2～8 sections of fillings；
Catalysis drying gas and benzene alkylation reaction are gas phase reaction, and reactor inlet temperature is 250～450 DEG C, instead
Answering device inlet pressure 0.5～2.0MPaG, benzene and ethylene molar ratio is 2～7, and weight ethylene air speed is
0.3～2.0 hour-1。
The method utilizing catalysis drying gas to produce ethylbenzene the most according to claim 1, its feature exists
In each stock catalysis drying gas respectively after heat-exchanger rig heat exchange, it is 10～100 DEG C that per share dry gas temperature controls.
The method utilizing catalysis drying gas to produce ethylbenzene the most according to claim 1, its feature exists
Being divided into N stock to enter reactor in catalysis drying gas, per share feed rate is identical；Described heat transmission equipment is
Tubular heat exchanger.
The method utilizing catalysis drying gas to produce ethylbenzene the most according to claim 1, its feature exists
It it is 250～450 DEG C in every section of beds inlet temperature；Every section of beds 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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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2939890A (en) * | 1958-03-18 | 1960-06-07 | Universal Oil Prod Co | Alkylation of aromatic hydrocarbons |
| CN1150142C (en) * | 1999-12-10 | 2004-05-19 | 北京服装学院 | Benzene and oil refinery dry gas catalyzed alkylation distillation process and equipment of preparing ethylbenzene |
-
2015
- 2015-06-12 CN CN201510324493.9A patent/CN106278795B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2939890A (en) * | 1958-03-18 | 1960-06-07 | Universal Oil Prod Co | Alkylation of aromatic hydrocarbons |
| CN1150142C (en) * | 1999-12-10 | 2004-05-19 | 北京服装学院 | Benzene and oil refinery dry gas catalyzed alkylation distillation process and equipment of preparing ethylbenzene |
Non-Patent Citations (1)
| Title |
|---|
| 邹鹏: "干气进料温度对烷基化反应系统的影响与对策", 《炼油技术与工程》 * |
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