CN106278795B - The method for producing ethylbenzene using catalysis drying gas - Google Patents
The method for producing ethylbenzene using catalysis drying gas Download PDFInfo
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- CN106278795B CN106278795B CN201510324493.9A CN201510324493A CN106278795B CN 106278795 B CN106278795 B CN 106278795B CN 201510324493 A CN201510324493 A CN 201510324493A CN 106278795 B CN106278795 B CN 106278795B
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- drying gas
- catalysis drying
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- temperature
- catalyst bed
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- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 67
- 238000001035 drying Methods 0.000 title claims abstract description 66
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000005977 Ethylene Substances 0.000 claims abstract description 29
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 27
- 230000029936 alkylation Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000011218 segmentation Effects 0.000 claims abstract description 4
- 230000005540 biological transmission Effects 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000010574 gas phase reaction Methods 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 66
- 239000002994 raw material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 241000282346 Meles meles Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of method producing ethylbenzene using catalysis drying gas, mainly solve the problems, such as that the prior art causes greatly every section of catalyst bed temperature liter unevenness, ethylbenzene yield in reactor low low with catalyst utilization due to ethylene concentration variation contained by catalysis drying gas.The present invention is by using including the following steps：A) catalysis drying gas containing ethylene is divided into N strands, and segmentation enters each section of catalyst bed of alkylation reactor；Wherein N >=2；B) benzene feedstock is all added by alkylation reactor first segment, or is divided into N stock sections and alkylation reactor is added；Wherein N >=2；C) each stock dry gas temperature is controlled so that every section of catalyst bed inlet temperature is identical, and every section of catalyst bed temperature rises identical technical solution and preferably solves the problems, such as this, can be used in the industrial production of catalysis drying gas production ethylbenzene.
Description
Technical field
The present invention relates to a kind of methods producing ethylbenzene using catalysis drying gas.
Background technology
Catalysis drying gas is the by-product of petroleum industry catalytic cracking, and key component is ethylene, propylene, hydrogen, ethane etc.,
With being significantly increased for global annual petroleum consumption, the ethylene resource contained in by-product dry gas suddenly utilization to be transformed.Before this due to
The reasons such as technology and cost, this part precious resources is substantially burnt up as fuel, and while waste of resource, also discharge is big
Measure carbon dioxide pollution environment.
Using the ethylene production ethylbenzene in catalysis drying gas, foreign countries have just started to explore at last century the fifties end, and 70
Age enters the industrial experiment stage.Wherein have Mobil/Badger companies of the U.S. develop cooperatively be with ZSM-5 silica-rich zeolites
Catalyst produce ethylbenzene Mobil/Badger gas molecule in space riddler's skills, Uop Inc. exploitation with Al2O3-BF3It is given birth to for catalyst
The catalytic distillation technology for producing the ALKar techniques of ethylbenzene and its developing later separately has pure ethylene second of the Monsanto in its improvement
The catalysis drying gas process for preparing ethylbenzene developed on the basis of benzene process.
Using catalysis drying gas as raw material produce ethylbenzene, foreign patent have US2939890, US369245, US702886,
US3848012, US4107224, US4459426, GB827830 etc., these technologies are to propylene, the H in raw material2S、H2O、O2、CO2
Equal impurity contents have strict requirements, they need to be removed to ppm grades can just apply.
Recent year also develops catalysis drying gas ethylbenzene technology, relevant patent have ZL200610046750.8,
ZL200510105256.X, ZL200410037433.0, ZL200410021102.8, ZL201110105517.3 etc., these skills
Art is all directly entered alkylation reactor after catalysis drying gas removes propylene with single temperature, but since plant catalytic is dry
Ethylene contents in gas are simultaneously unstable, and usual ethylene contents can cause every in alkylation reactor in 10~50% fluctuations
Section catalyst bed entrance is difficult to control in mutually synthermal and phase equality of temperature liter.In general, when ethylene concentration reduces, can cause to react
Device first segment bed temperature increases, and several sections of bed inlet temperatures later are difficult to reach design requirement temperature, and ethylbenzene yield reduces；
And when ethylene concentration increases, and it is more than design requirement temperature that can cause several sections of bed inlet temperatures after reactor, and side reaction increases
Add, catalyst inactivation is accelerated.
Invention content
The technical problem to be solved by the present invention is in the prior art since ethylene concentration variation contained by catalysis drying gas is made greatly
Unevenness is risen at every section of catalyst bed temperature in reactor, leads to the low problem low with catalyst utilization of ethylbenzene yield, provides one
The new method for producing ethylbenzene using catalysis drying gas of kind.This method can make every section of catalyst inlet temperature and bed temperature in reactor
Liter is identical, has the characteristics that ethylbenzene high income and catalyst utilization are high.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：It is a kind of to produce second using catalysis drying gas
The method of benzene, includes the following steps：
A) catalysis drying gas containing ethylene is divided into N strands, and segmentation enters each section of catalyst bed of alkylation reactor；Wherein N
≥2；
B) benzene feedstock is all added by alkylation reactor first segment, or is divided into N stock sections and alkylation reactor is added；Its
Middle N >=2；
C) each stock dry gas temperature is controlled so that every section of catalyst bed inlet temperature is identical, and every section of catalyst bed
Temperature rises identical.
In above-mentioned technical proposal, it is preferable that control each stock dry gas temperature by making each stock catalysis drying gas exchange heat with heat transmission equipment
Degree.
In above-mentioned technical proposal, it is preferable that the heat transmission equipment is equipped with temperature control equipment, by adjusting heat exchanging medium flow
Amount controls each stock dry gas outlet temperature.
In above-mentioned technical proposal, it is preferable that heat transmission equipment is bypassed equipped with catalysis drying gas, by adjusting catalysis drying gas by-pass
Amount controls each stock dry gas outlet temperature.
In above-mentioned technical proposal, it is preferable that volume of ethylene content is 5~95% in catalytic material dry gas.
In above-mentioned technical proposal, it is preferable that alkylation reactor is axial multi-stage fixed-bed reactor, catalyst point 2~8
Section filling.
In above-mentioned technical proposal, it is preferable that catalysis drying gas and benzene alkylation reaction are gas phase reaction, reactor inlet temperature
250~450 DEG C, 0.5~2.0MPaG of reactor inlet pressure, benzene and ethylene molar ratio are 2~7, and weight ethylene air speed is 0.3
~2.0 hours-1。
In above-mentioned technical proposal, it is preferable that each stock catalysis drying gas is respectively after heat-exchanger rig exchanges heat, per share dry gas temperature control
It is made as 10~100 DEG C.
In above-mentioned technical proposal, it is preferable that catalysis drying gas is divided into N strands and enters reactor, and per share feed rate is identical；It is described
Heat transmission equipment is tubular heat exchanger.
In above-mentioned technical proposal, it is preferable that every section of catalyst bed inlet temperature is 250~450 DEG C；Every section of catalyst bed
Layer temperature is upgraded to 5~30 DEG C.It is highly preferred that every section of catalyst bed inlet temperature is 300~400 DEG C；Every section of catalyst bed temperature
It is upgraded to 10~25 DEG C.
In the prior art, after catalysis drying gas is using absorption and desorption method removing propylene, usually with 10~40 DEG C of single temperature
A degree point multiply enters alkylation reactor, mixes to reach in paragraph 1 bed and benzene feedstock and reacts that require temperature to enter reactor anti-
It answers, after the charging of the 2nd section~N sections of low-temperature catalyzed dry gas is mixed with the high-temperature reacting gas from the preceding paragraph catalyst bed,
The temperature that reaction temperature drops to requirement enters next section of catalyst bed, the temperature by the design of catalysis drying gas ethylene contents and charging
Amount ensure that every section of catalyst bed inlet temperature is identical with temperature liter holding, guarantee to obtain higher ethylbenzene yield and catalyst
High usage.But due to ethylene contents in plant catalytic dry gas and unstable, usual ethylene contents can be 10~50%
Fluctuation causes the significantly change of every section of catalyst bed in alkylation reactor due to ethylene concentration, entrance to be difficult to control
Mutually synthermal, catalyst bed Wen Sheng also differs larger, when ethylene concentration is less than design value in catalysis drying gas, can cause anti-
Device first segment bed temperature is answered to increase, and several sections of bed inlet temperatures later are less than design requirement temperature, ethylbenzene yield reduces；And
When ethylene concentration is higher than design value in catalysis drying gas, and it is more than design requirement that can cause several sections of bed inlet temperatures after reactor
Temperature, side reaction increase, and catalyst inactivation is accelerated.
In the present invention, catalysis drying gas is average or is divided into proportion N strands (N >=2), and per share dry gas material is entering alkylation instead
It before answering device, exchanges heat through heat transmission equipment, heat transmission equipment is equipped with catalysis drying gas outlet temperature control device, in catalytic material dry gas ethylene
Every section of inlet temperature of catalyst and bed temperature liter can be made identical by adjusting per share catalysis drying gas outlet temperature when concentration changes.When
When ethylene concentration is less than design value in catalysis drying gas, gone out by the catalysis drying gas that heat-exchanger rig is increased into each section of catalyst bed
Mouth temperature ensures that each section of bed inlet temperatures reach design temperature, and when ethylene concentration is higher than design value in catalysis drying gas, it can
It is lowered into the catalysis drying gas outlet temperature of each section of catalyst bed by heat-exchanger rig, ensures that each section of bed inlet temperatures do not surpass
Cross design requirement temperature.Using the method for the present invention, the ethylene that alkylated reaction system adapts to catalysis drying gas wider range can be made dense
Degree variation, and every section of catalyst bed inlet temperature and bed temperature liter remain essentially identical in reactor, operation is flexibly simple, can
Ethylbenzene yield 1~20% is improved, catalyst utilization 10~50% is improved, achieves preferable technique effect.
Description of the drawings
Fig. 1 is present invention process flow.
Fig. 2 is the technological process of the prior art.
In Fig. 1, by taking catalysis drying gas charging points 4 strands as an example, I~IV is the 1st~4th strand of catalysis drying gas feed exchanger, V
It is catalysis drying gas raw material for alkylation reactor, 1,2 be benzene, and N1~N4 is that the 1st~4th section of bed catalyst dry gas is fed, n1~
N4 is that the 1st~4th section of bed benzene is fed, and 3 be alkylation reactor discharging gas.
In Fig. 1, it is 4 strands that catalysis drying gas raw material 1, which divides, and per share dry gas exchanges heat through catalysis drying gas heat-exchanger rig I~IV, is exporting
Under temperature control equipment control, alkylation reactor V is respectively enterd, benzene feedstock is all added by reactor first segment, or divides 4
Alkylation reactor is added in stock section, and in first segment bed, catalysis drying gas N1 and benzene n1 is mixed into first segment bed, often later
Section bed, catalysis drying gas N2~N4 and the reaction gas from the preceding paragraph bed and benzene charging n2~n4 mixing, into catalysis
Agent bed reacts, and 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 be benzene, and N1~N4 is that the 1st~4th section of bed is urged
Change dry gas charging (by taking 4 sections of beds as an example), n1~n4 are that the 1st~4th section of bed benzene is fed, and 3 be alkylation reactor discharging gas.
In Fig. 2, catalysis drying gas raw material 1 divides 4 strands to respectively enter alkylation reactor V, benzene feedstock (by taking 4 sections of beds as an example)
All be added by reactor first segment, or alkylation reactor is added in point 4 stock sections, in first segment bed, catalysis drying gas N1 with
Benzene n1 is mixed into first segment bed, later every section of bed, catalysis drying gas N2~N4 and the reaction gas from the preceding paragraph bed
And benzene charging n2~n4 mixing, into catalyst bed reaction, final alkylation reactor discharging gas 3 leaves reaction gas entrance
Follow-up workshop section.
Below by embodiment, the present invention is further elaborated.
Specific implementation mode
【Embodiment 1】
Certain 100,000 tons/year of catalysis drying gas production Benzene Device (year operation hour 8000 hours), it is main using the technique of Fig. 1
Operating mode and operating condition is wanted to be shown in Table 1.
Table 1
【Embodiment 2】
Certain 100,000 tons/year of catalysis drying gas production Benzene Device (year operation hour 8000 hours), it is main using the technique of Fig. 1
Operating mode and operating condition is wanted to be shown in Table 2.
Table 2
【Embodiment 3】
Certain 100,000 tons/year of catalysis drying gas production Benzene Device (year operation hour 8000 hours), it is main using the technique of Fig. 1
Operating mode and operating condition is wanted to be shown in Table 3.
Table 3
【Comparative example 1】
Certain 100,000 tons/year of catalysis drying gas production Benzene Device (year operation hour 8000 hours), it is main using the technique of Fig. 2
Operating mode and operating condition is wanted to be shown in Table 4.
Table 4
Claims (7)
1. a kind of method producing ethylbenzene using catalysis drying gas, includes the following steps：
A) catalysis drying gas containing ethylene is divided into N strands, and segmentation enters each section of catalyst bed of alkylation reactor；Wherein N >=2；
B) benzene feedstock is all added by alkylation reactor first segment, or is divided into N stock sections and alkylation reactor is added；Wherein N
≥2；
C) each stock dry gas temperature is controlled so that every section of catalyst bed inlet temperature is identical, and every section of catalyst bed Wen Sheng
It is identical；
Wherein, each stock dry gas temperature is controlled by making each stock catalysis drying gas and heat transmission equipment exchange heat, the heat transmission equipment is equipped with temperature
Control device is spent, each stock dry gas outlet temperature is controlled by adjusting heat transferring medium flow；When ethylene concentration is less than in catalysis drying gas
When design value, the catalysis drying gas outlet temperature for entering each section of catalyst bed is increased by heat transmission equipment, ensures that each section of bed enters
Mouth temperature reaches design temperature, and when ethylene concentration is higher than design value in catalysis drying gas, it is lowered into respectively by heat transmission equipment
The catalysis drying gas outlet temperature of section catalyst bed ensures that each section of bed inlet temperatures are no more than design requirement temperature.
2. the method according to claim 1 for producing ethylbenzene using catalysis drying gas, it is characterised in that in catalytic material dry gas
Volume of ethylene content is 5~95%.
3. the method according to claim 1 for producing ethylbenzene using catalysis drying gas, it is characterised in that the alkylated reaction
Device is axial multi-stage fixed-bed reactor, 2~8 sections of fillings of catalyst point；Catalysis drying gas and benzene alkylation reaction are gas phase reaction,
Reactor inlet temperature is 250~450 DEG C, 0.5~2.0MPaG of reactor inlet pressure, and benzene and ethylene molar ratio are 2~7, second
Alkene weight space velocity is 0.3~2.0 hour-1。
4. the method according to claim 1 for producing ethylbenzene using catalysis drying gas, it is characterised in that each stock catalysis drying gas point
Not after heat-exchanger rig exchanges heat, per share dry gas temperature control is 10~100 DEG C.
5. the method according to claim 1 for producing ethylbenzene using catalysis drying gas, it is characterised in that catalysis drying gas is divided into N strands
Into reactor, per share feed rate is identical；The heat transmission equipment is tubular heat exchanger.
6. the method according to claim 1 for producing ethylbenzene using catalysis drying gas, it is characterised in that every section of catalyst bed
Inlet temperature is 250~450 DEG C；Every section of catalyst bed temperature is upgraded to 5~30 DEG C.
7. the method according to claim 6 for producing ethylbenzene using catalysis drying gas, it is characterised in that every section of catalyst bed
Inlet temperature is 300~400 DEG C；Every section of catalyst bed temperature is upgraded to 10~25 DEG C.
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| CN201510324493.9A CN106278795B (en) | 2015-06-12 | 2015-06-12 | The method for producing ethylbenzene using catalysis drying gas |
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|---|---|---|---|
| CN201510324493.9A CN106278795B (en) | 2015-06-12 | 2015-06-12 | The method for producing ethylbenzene using catalysis drying gas |
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| CN106278795B true CN106278795B (en) | 2018-10-23 |
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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 | Method and apparatus for producing ethylbenzene by alkylation of benzene and refinery dry gas catalytic distillation |
-
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 | Method and apparatus for producing ethylbenzene by alkylation of benzene and refinery dry gas catalytic distillation |
Non-Patent Citations (1)
| Title |
|---|
| 干气进料温度对烷基化反应系统的影响与对策;邹鹏;《炼油技术与工程》;20140514;第44卷(第4期);第28-30页 * |
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