CN106278798A - Catalysis drying gas produces method and the purposes of described derivant of olefin-based derivative - Google Patents
Catalysis drying gas produces method and the purposes of described derivant of olefin-based derivative Download PDFInfo
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Abstract
The present invention relates to a kind of catalysis drying gas and produce method and the purposes of described derivant of olefin-based derivative, mainly solve ethylene and propylene contained by catalysis drying gas in prior art and be difficult to fully utilized problem.The present invention is comprised the following steps by employing a) to be provided containing ethylene and the catalysis drying gas of propylene；B) described catalysis drying gas is the most treated, directly enter alkylation reactor with containing benzene raw materials logistics, obtains gaseous stream after reaction；C) described gaseous stream enters reaction gas absorption plant, and be absorbed after contacting with absorbent liquid；D) described absorbing liquid enters benzene knockout tower, and tower top obtains mainly containing the logistics of benzene, and tower reactor obtains the technical scheme of the logistics containing described olefin-based derivative and preferably solves this problem, can be used in the commercial production that catalysis drying gas produces olefin-based derivative.
Description
Technical field
The present invention relates to a kind of catalysis drying gas and produce the method for olefin-based derivative and described derivant
Purposes.
Background technology
Catalysis drying gas is petroleum industry catalytic cracking or catalytic pyrolysis or the by-product of thermal cracker,
Its key component is ethylene, propylene, hydrogen, ethane etc., along with the annual petroleum consumption in the whole world
It is significantly increased, the anxious utilization to be transformed of the ethylene resource contained in by-product dry gas.Before this due to technology with become
This etc. reason, this part precious resources substantially burnt as fuel, while waste resource,
Also discharge great amount of carbon dioxide pollutes 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
Dilute ethylbenzene manufactured from ethylene technique of exploitation on the basis of benzene process.
With the dilute ethylene of 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., although these technology are in catalysis drying gas
Contained H2S、H2O、O2、CO2Require to relax Deng impurity content, but be guard catalyst and fall
Low benzene consumes, and is designed with removing propylene flow process in technique.For obtaining more ethylbenzene, except ethylene and benzene are anti-
Outside the alkylation reactor answered, also set many ethylbenzene and the transalkylation reactor of benzene reaction, separate single
Unit, in addition to setting benzene knockout tower, also sets ethylbenzene tower, propyl benzene tower, many ethylbenzene towers, and flow process is complicated, energy consumption
The highest with investment.
Summary of the invention
One of the technical problem to be solved be in prior art ethylene contained by catalysis drying gas and
Propylene is difficult to fully utilized problem, it is provided that a kind of new catalysis drying gas produces olefin-based derivative
Method.The method have the ethylene, propylene resource that can make full use of in catalysis drying gas, plant investment low,
The feature that energy consumption is low.The two of the technical problem to be solved are to provide a kind of for solution technology
The purposes of the olefin-based derivative that the method synthesis that one of problem is used obtains.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows: one is urged
Change the method that dry gas produces olefin-based derivative, comprise the following steps:
A) provide containing ethylene and the catalysis drying gas of propylene；
B) described catalysis drying gas is the most treated, directly enter alkylation reactor with containing benzene raw materials logistics,
Gaseous stream is obtained after reaction；
C) described gaseous stream enters reaction gas absorption plant, and be absorbed after contacting with absorbent liquid；
D) described absorbing liquid enters benzene knockout tower, and tower top obtains mainly containing the logistics of benzene, and tower reactor obtains
Logistics containing described olefin-based derivative.
In technique scheme, it is preferable that in described catalysis drying gas, volume of ethylene content is 5～95%,
Propylene volume content is 0.5～10%, H2S volume content ＜ 1000ppm.
In technique scheme, it is preferable that described containing benzene raw materials source streams in the stone of petroleum cracking
Oil benzene or the crude benzol of coking of coal, wherein benzene mass content is more than 90%, and toluene mass content is less than
10%.
In technique scheme, it is preferable that the logistics containing benzene that described benzene knockout tower tower top obtains follows
Loopback alkylation reactor.
In technique scheme, it is preferable that described gaseous stream do not enter transalkylation reactor,
At least one equipment in ethylbenzene separation column, propyl benzene knockout tower or many ethylbenzene separation column.
In technique scheme, it is preferable that described olefin-based derivative contains ethylbenzene, propyl benzene, diethyl
Benzene, the first and second benzene and dimethylbenzene.
In technique scheme, it is preferable that catalysis drying gas and benzene alkylation reaction are gas phase reaction,
Reaction temperature 250～450 DEG C, reaction pressure 0.5～2.0MPaG, benzene and ethylene molar ratio are 1～6,
Weight ethylene air speed is 0.3～2.0 hour-1。
In technique scheme, it is preferable that catalyst for alkylation reaction is SiO2/AlO3Mol ratio is
The ZSM-5 molecular sieve of 50～300, preferably scope are 80～120.
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 described absorbent is benzene or benzene knockout tower tower bottoms,
Absorbing temperature is 0～40 DEG C, and pressure is 0.5～2.0MPaG, absorbent and the stream of described gaseous stream
Amount mass ratio is 1～5.
In technique scheme, it is preferable that benzene knockout tower operation pressure is 0.5～2.0MPaG, and tower is managed
Opinion plate number is 20～50, and reflux ratio is 1～6.
In order to solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: described alkene
Alkyl derivative is as gasoline blend component.
In prior art, utilizing the ethylene production ethylbenzene in catalysis drying gas, ethylbenzene is that unique objects produces
Thing, must set the pretreatment processes such as more complicated de-propylene for this raw material dry gas；Receive for improving ethylbenzene
Rate, reduces and generates the by-product such as dimethylbenzene, diethylbenzene, and alkylated reaction must be at high benzene alkene mole
Operate under the conditions of Bi, usually 6～8；Must be to benzene, ethylbenzene, propyl benzene, many ethylbenzene in separation process
Carry out accurate separation；For obtaining more ethylbenzene, the alkyl also setting many ethylbenzene and benzene reaction in flow process turns
Move reactor.On the whole, this technology causes equipment investment and energy consumption the highest, the most only profit
With the part ethylene in dry gas, ethylene utilization rate is less than 90%, and propylene is not obtained by, warp
Ji benefit is greatly affected.
In the present invention, catalytic material dry gas is made without process and is directly entered alkylation reactor,
Requirement to benzene feedstock is the harshest, petrobenzene, coking benzene, or the benzene containing more toluene is all
Can react as raw material and the ethylene in dry gas, propylene obtain ethylbenzene, propyl benzene, the first and second benzene, two
Toluene, diethylbenzene etc., these products all have higher octane number, are extraordinary blended gasolines
Raw material, therefore alkylated reaction can operate under relatively low benzene alkene mol ratio (usually 1～5),
Separation process is only to benzene knockout tower, it is not necessary to transalkylation reactor, benzene knockout tower tower bottoms
It is the product that we need.Using the inventive method, ethylene and propylene in raw material dry gas utilize
Rate can be close to 100%, and energy consumption is only the 50% of traditional mode of production ethylbenzene process, and investment is only tradition ethylbenzene
The 40% of technique, achieves preferable technique effect.
Accompanying drawing explanation
Fig. 1 is the technological process using the inventive method.
Fig. 2 produces ethylbenzene prior art processes flow process for using typical catalysis drying gas.
In Fig. 1, I is alkylation reactor, and II is absorption plant, and III is benzene knockout tower, and 1 for urging
Changing dry gas raw material, 2 is fresh benzene raw material, and 3 is the benzene charging of alkylation reactor I, and 4 is reaction
Device is worked off one's feeling vent one's spleen, and 5 is absorption plant II tail gas, and 6 is absorbent, and 7 is absorbing liquid, and 8 separate for benzene
Tower III overhead stream benzene, 9 is benzene knockout tower III tower bottoms.
In Fig. 1, catalysis drying gas raw material 1 and benzene charging 3 mixes and is directly entered alkylation reactor I,
Reacted reactor device is worked off one's feeling vent one's spleen 4 entrance absorption plants II, and absorbent 6 counter current contacting, no
Absorbent tail gas 5 discharges battery limit (BL), and the absorbing liquid 7 absorbed enters benzene knockout tower III, tower top
Logistics benzene 8 and fresh feed benzene 2 are mixed into alkylation reactor I, and tower bottoms 9 is as product
Output battery limit (BL).
In Fig. 2, I is alkylation reactor, and II is absorption plant, and III is benzene knockout tower, and IV is
Pretreatment system, V is ethylbenzene tower, and VI is propyl benzene tower, and VII is many ethylbenzene towers, and VIII is transalkylation
Reactor, 1 is catalysis drying gas raw material, and 2 is fresh benzene raw material, and 3 is the benzene of alkylation reactor I
Charging, 4 is reactor outlet gas, and 5 is absorption plant II tail gas, and 6 is absorbent, and 7 for absorbing
Liquid, 8 is benzene knockout tower III overhead stream benzene, and 9 is benzene knockout tower III tower bottoms, and 10 for after pretreatment
Catalysis drying gas, 11 is benzene separating III tower top dereaction system recycle benzene logistics, and 12 turn for removing alkyl
Moving the benzene logistics of reactor VIII, 13 is ethylbenzene tower V overhead stream ethylbenzene, and 14 is ethylbenzene tower V tower reactor
Liquid, 15 is propyl benzene column overhead stream propyl benzene, and 16 is propyl benzene tower tower bottoms, and 17 is many ethylbenzene tower VII towers
The top many ethylbenzene of logistics, 18 is many ethylbenzene tower VII tower reactor high-boiling components, and 19 feed for transalkylation reactor,
20 is transalkylation reactor discharging.
In Fig. 2, catalysis drying gas raw material 1 first preprocessed system IV, after removing the impurity such as propylene
Logistics 10 is mixed into alkylation reactor I with benzene charging 3, and reacted reactor device is worked off one's feeling vent one's spleen
4 enter absorption plant II, with absorbent 6 counter current contacting, it is impossible to the tail gas 5 of absorption discharges battery limit (BL),
The absorbing liquid 7 absorbed enters benzene knockout tower III, and overhead stream benzene 8 is divided into 2 strands, and wherein 1
Stock logistics 11 and fresh feed benzene 2 are mixed into alkylation reactor I, another burst of logistics 12 with
Many ethylbenzene towers tower bottoms 17 is mixed into transalkylation reactor VIII, and reacted logistics 20 returns
Benzene knockout tower III, benzene knockout tower tower bottoms 9 enters ethylbenzene tower V, and tower top obtains ethylbenzene 13, tower reactor
Liquid 14 enters propyl benzene tower VI, and propyl benzene column overhead obtains propyl benzene 15, and tower bottoms 16 enters many ethylbenzene towers
VII, many ethylbenzene towers tower bottoms is high-boiling components 18.
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 produce olefin-based derivative units (year operation hour 8000 little
Time), its catalytic material dry gas composition and flow are shown in Table 1, and benzene uses petrobenzene, purity 99.8%,
The technique using Fig. 1, prevailing operating conditions and economic indicator are shown in Table 2.Benzene knockout tower tower bottoms octane
Value is 108, can be as gasoline blend component.
Table 1 catalytic material dry gas specification
| Component | Catalytic material dry gas (v%) |
| Hydrogen | 27.4 |
| Nitrogen | 24.4 |
| Oxygen | 1.0 |
| Carbon monoxide | 1.1 |
| Carbon dioxide | 3.3 |
| Methane | 19.6 |
| Ethane | 9.0 |
| Ethylene | 12.4 |
| Propylene | 1.1 |
| Propane | 0.2 |
| Carbon four | 0.3 |
| Carbon five | 0.1 |
| Flow (ton hour) | 18 |
Table 2 prevailing operating conditions and economic indicator
| Alkylation reactor operation pressure MPaG | 0.8 |
| Alkylation reactor operation temperature DEG C | 320 |
| Alkylation reactor benzene alkene mol ratio | 4 |
| Catalyst SiO2/AlO3Mol ratio | 50 |
| Alkylation reactor catalyst hop count | 4 |
| Absorptive tower absorbent | Benzene column tower bottoms |
| Absorption tower absorbs temperature DEG C | 10 |
| Benzene knockout tower tower top operation pressure MPaG | 0.7 |
| Benzene knockout tower tower top operation temperature DEG C | 151 |
| Ethylene utilization rate % | 99.5 |
| Propylene utilization rate % | 99.0 |
| Comprehensive energy consumption kilogram mark oil/ton product | 60 |
| Plant investment ten thousand yuan | 7000 |
| Benzene knockout tower tower bottoms octane number | 108 |
[embodiment 2]
Certain 100,000 tons/year of catalysis drying gas produce olefin-based derivative units (year operation hour 8000 little
Time), its catalytic material dry gas composition and flow are shown in Table 3, and benzene uses coking benzene, purity 99.6%,
The technique using Fig. 1, prevailing operating conditions and economic indicator are shown in Table 4.Benzene knockout tower tower bottoms octane
Value is 108.4, can be as gasoline blend component.
Table 3 catalytic material dry gas specification
| Component | Catalytic material dry gas (v%) |
| Hydrogen | 12.4 |
| Nitrogen | 20.2 |
| Oxygen | 0.8 |
| Carbon monoxide | 1.0 |
| Carbon dioxide | 3.4 |
| Methane | 19.7 |
| Ethane | 9.0 |
| Ethylene | 31.2 |
| Propylene | 2.0 |
| Propane | 0.1 |
| Carbon four | 0.1 |
| Carbon five | 0.1 |
| Flow (ton hour) | 8.0 |
Table 4 prevailing operating conditions and economic indicator
| Alkylation reactor operation pressure MPaG | 1.0 |
| Alkylation reactor operation temperature DEG C | 340 |
| Alkylation reactor benzene alkene mol ratio | 3.5 |
| Catalyst SiO2/AlO3Mol ratio | 200 |
| Alkylation reactor catalyst hop count | 5 |
| Absorptive tower absorbent | Benzene |
| Absorption tower absorbs temperature DEG C | 5 |
| Benzene knockout tower tower top operation pressure MPaG | 0.9 |
| Benzene knockout tower tower top operation temperature DEG C | 170 |
| Ethylene utilization rate % | 99.2 |
| Propylene utilization rate % | 98.5 |
| Comprehensive energy consumption kilogram mark oil/ton product | 50 |
| Plant investment ten thousand yuan | 5800 |
| Benzene knockout tower tower bottoms octane number | 108.4 |
[embodiment 3]
Certain 100,000 tons/year of catalysis drying gas produce olefin-based derivative units (year operation hour 8000 little
Time), its catalytic material dry gas composition and flow are shown in Table 5, benzene feedstock purity 90%, containing toluene 10%,
The technique using Fig. 1, prevailing operating conditions and economic indicator are shown in Table 6.Benzene knockout tower tower bottoms octane
Value is 109, can be as gasoline blend component.
Table 5 catalytic material dry gas specification
| Component | Catalytic material dry gas (v%) |
| Hydrogen | 21.4 |
| Nitrogen | 19.2 |
| Oxygen | 0.9 |
| Carbon monoxide | 1.2 |
| Carbon dioxide | 3.6 |
| Methane | 20.7 |
| Ethane | 9.5 |
| Ethylene | 21.4 |
| Propylene | 1.6 |
| Propane | 0.3 |
| Carbon four | 0.1 |
| Carbon five | 0.1 |
| Flow (ton hour) | 9.5 |
Table 6 prevailing operating conditions and economic indicator
| Alkylation reactor operation pressure MPaG | 0.5 |
| Alkylation reactor operation temperature DEG C | 400 |
| Alkylation reactor benzene alkene mol ratio | 2.5 |
| Catalyst SiO2/AlO3Mol ratio | 300 |
| Alkylation reactor catalyst hop count | 4 |
| Absorptive tower absorbent | Benzene column tower bottoms |
| Absorption tower absorbs temperature DEG C | 15 |
| Benzene knockout tower tower top operation pressure MPaG | 0.45 |
| Benzene knockout tower tower top operation temperature DEG C | 140 |
| Ethylene utilization rate % | 99.1 |
| Propylene utilization rate % | 98.0 |
| Comprehensive energy consumption kilogram mark oil/ton product | 40 |
| Plant investment ten thousand yuan | 5500 |
| Benzene knockout tower tower bottoms octane number | 109 |
[embodiment 4]
Certain 100,000 tons/year of catalysis drying gas produce olefin-based derivative units (year operation hour 8000 little
Time), its catalytic material dry gas composition and flow are shown in Table 7, benzene feedstock purity 99.6%, containing toluene 0.4%,
The technique using Fig. 1, prevailing operating conditions and economic indicator are shown in Table 8.Benzene knockout tower tower bottoms octane
Value is 108.8, can be as gasoline blend component.
Table 7 catalytic material dry gas specification
| Component | Catalytic material dry gas (v%) |
| Hydrogen | 18.6 |
| Nitrogen | 15.6 |
| Oxygen | 0.9 |
| Carbon monoxide | 1.5 |
| Carbon dioxide | 4.2 |
| Methane | 22.7 |
| Ethane | 10.8 |
| Ethylene | 24.7 |
| Propylene | 0.8 |
| Propane | 0.1 |
| Carbon four | 0.1 |
| Carbon five | 0 |
| Flow (ton hour) | 14.0 |
Table 8 prevailing operating conditions and economic indicator
| Alkylation reactor operation pressure MPaG | 2.0 |
| Alkylation reactor operation temperature DEG C | 360 |
| Alkylation reactor benzene alkene mol ratio | 2 |
| Catalyst SiO2/AlO3Mol ratio | 150 |
| Alkylation reactor catalyst hop count | 6 |
| Absorptive tower absorbent | Benzene column tower bottoms |
| Absorption tower absorbs temperature DEG C | 0 |
| Benzene knockout tower tower top operation pressure MPaG | 1.0 |
| Benzene knockout tower tower top operation temperature DEG C | 180 |
| Ethylene utilization rate % | 99.6 |
| Propylene utilization rate % | 99.1 |
| Comprehensive energy consumption kilogram mark oil/ton product | 25 |
| Plant investment ten thousand yuan | 5400 |
| Benzene knockout tower tower bottoms octane number | 108.8 |
[comparative example 1]
Certain 100,000 tons/year of catalysis drying gas produces Benzene Devices (year operation hour 8000 hours), its
Catalytic material dry gas composition and flow, with table 1, benzene feedstock purity 99.9%, containing toluene 0.05%, are adopted
It is shown in Table 9 by the technique of Fig. 2, prevailing operating conditions and economic indicator.
Table 9 prevailing operating conditions and economic indicator
| Alkylation reactor operation pressure MPaG | 1.0 |
| Alkylation reactor operation temperature DEG C | 380 |
| Alkylation reactor benzene alkene mol ratio | 7.0 |
| Catalyst | Zeolite |
| Ethylene utilization rate % | 85 |
| Propylene utilization rate % | Return catalysis |
| Comprehensive energy consumption kilogram mark oil/ton product | 210 |
| Plant investment ten thousand yuan | 16000 |
Claims (10)
1. the method that catalysis drying gas produces olefin-based derivative, comprises the following steps:
A) provide containing ethylene and the catalysis drying gas of propylene；
B) described catalysis drying gas is the most treated, directly enter alkylation reactor with containing benzene raw materials logistics,
Gaseous stream is obtained after reaction；
C) described gaseous stream enters reaction gas absorption plant, and be absorbed after contacting with absorbent liquid；
D) described absorbing liquid enters benzene knockout tower, and tower top obtains mainly containing the logistics of benzene, and tower reactor obtains
Logistics containing described olefin-based derivative.
Catalysis drying gas the most according to claim 1 produces the method for olefin-based derivative, and it is special
Levy and be in described catalysis drying gas that volume of ethylene content is 5～95%, propylene volume content be 0.5～
10%, H2S volume content ＜ 1000ppm；Described containing benzene raw materials source streams in the stone of petroleum cracking
Oil benzene or the crude benzol of coking of coal, wherein benzene mass content is more than 90%, and toluene mass content is less than
10%；Described olefin-based derivative is containing ethylbenzene, propyl benzene, diethylbenzene, the first and second benzene and dimethylbenzene.
Catalysis drying gas the most according to claim 1 produces the method for olefin-based derivative, and it is special
Levy and be that the logistics containing benzene that described benzene knockout tower tower top obtains loops back alkylation reactor.
Catalysis drying gas the most according to claim 1 produces the method for olefin-based derivative, and it is special
Levy and be that described gaseous stream does not enter transalkylation reactor, ethylbenzene separation column, propyl benzene knockout tower
Or at least one equipment in many ethylbenzene separation column.
Catalysis drying gas the most according to claim 1 produces the method for olefin-based derivative, and it is special
Levy and be that catalysis drying gas and benzene alkylation reaction are gas phase reaction, reaction temperature 250～450 DEG C, reaction
Pressure 0.5～2.0MPaG, benzene and ethylene molar ratio are 1～6, and weight ethylene air speed is 0.3～2.0 little
Time-1。
Catalysis drying gas the most according to claim 1 produces the method for olefin-based derivative, and it is special
Levy and be that catalyst for alkylation reaction is SiO2/AlO3Mol ratio is the ZSM-5 molecular sieve of 50～300.
Catalysis drying gas the most according to claim 1 produces the method for olefin-based derivative, and it is special
Levying and be that alkylation reactor is axial multi-stage fixed-bed reactor, catalyst divides 2～8 sections of fillings.
Catalysis drying gas the most according to claim 1 produces the method for olefin-based derivative, and it is special
Levying and be that described absorbent is benzene or benzene knockout tower tower bottoms, absorbing temperature is 0～40 DEG C, pressure
Being 0.5～2.0MPaG, absorbent is 1～5 with the flow mass ratio of described gaseous stream.
Catalysis drying gas the most according to claim 1 produces the method for olefin-based derivative, and it is special
Levying and be that benzene knockout tower operation pressure is 0.5～2.0MPaG, tower number of theoretical plate is 20～50, reflux ratio
It is 1～6.
10. the olefin-based derivative that claim 1～9 either method obtains is as gasoline blend component.
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| JP2014015466A (en) * | 2005-03-31 | 2014-01-30 | Exxonmobile Chemical Patents Inc | Multiphase alkylaromatics production |
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| CN104560233A (en) * | 2015-01-19 | 2015-04-29 | 广汉市天舟航空发动机燃料科技有限公司 | Low-lead aviation gasoline and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6063976A (en) * | 1997-08-18 | 2000-05-16 | Exxon Chemical Patent Inc. | Process to alkylate an aromatic with a dilute stream comprising propylene and ethylene |
| CN1227833A (en) * | 1997-09-22 | 1999-09-08 | 中国石化集团洛阳石油化工工程公司 | Process for preparing ethyl benzene and propyl benzene by reaction of dilute ethylene, propene and benzene |
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Application publication date: 20170104 |