CN1348945A - Ether product producing process - Google Patents

Ether product producing process Download PDF

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Publication number
CN1348945A
CN1348945A CN00123957A CN00123957A CN1348945A CN 1348945 A CN1348945 A CN 1348945A CN 00123957 A CN00123957 A CN 00123957A CN 00123957 A CN00123957 A CN 00123957A CN 1348945 A CN1348945 A CN 1348945A
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tower
alcohol
product
bed reactor
catalytic distillation
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CN1202060C (en
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郝兴仁
杨宗仁
高步良
王伟
吕爱梅
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China Petroleum and Chemical Corp
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Qilu Petrochemical Co of Sinopec
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

This invention relates to a production method for ether products. After the tert-olefine-contained light hydrocarbon undergoes etherification reaction with alcohol in a (pre-) etherification reactor to reach a certain conversion rate, the resultant ferther enters a product separation tower or catalytic distilaltion tower for reaction and/or separation, the product ether leaves the product separation tower or catalytic distillation tower, and the unreacted light hydrocarbon and alcohol flow out from the tower top and enter alcohol recovering tower. The azoetropic mixture of alcohol and light hydrocarbon flowing out from the alcohol recovering tower top is cyclically used; and the unreacted light hydrocarbon fraction in the tower, one part of it as reflux of product separation tower or catalytic distillation tower flows back and another part as product or raw material for further processing is discharged. The said method simplifies alcohol recovery and the ether product basically contains no alcohol.

Description

A kind of production method of ether product
The production method of a kind of ether product that the present invention relates to is particularly with the production method of the lighter hydrocarbons that contain tertiary olefin with the synthetic corresponding ethers of alcohol reaction.
In traditional ether product production technique, in order to guarantee the transformation efficiency of tertiary olefin, the mol ratio of alfin is higher than 1.0 generally speaking, contains excessive alcohol in the unreacted lighter hydrocarbons.As with mixed c 4 and methyl alcohol reaction synthesize methyl tert-butyl ether (MTBE) time, contain a certain amount of methyl alcohol in the effluent carbon four of catalytic distillation tower or product separation cat head, remove methyl alcohol in the carbon four by the water extraction tower, methanol aqueous solution enters and reclaims methyl alcohol in the methanol distillation column then, the methyl alcohol that reclaims flows out from cat head and recycles, and enters the water extraction tower from the effusive water of tower still and recycles.Have plenty of the absorption of the methyl alcohol in the effluent carbon four of catalytic distillation tower or product separation cat head is reclaimed, the carbon four that contains methyl alcohol enters in the adsorption tower that sorbent material is housed, methyl alcohol is attracted to the surface of sorbent material, when reaching the capacity of sorbent material, by fresh carbon four desorption methyl alcohol, and be circulated to reactor inlet or head tank.But when with ethanol being raw material production Ethyl Tertisry Butyl Ether ether products such as (ETBE), when the alcohol that contains in the unreacted lighter hydrocarbons adopts the water method of extraction to reclaim, because ethanol can form azeotrope with water, and is moisture in the ethanol of recovery, brings new problem to production process.
The production method that the purpose of this invention is to provide a kind of ether product makes in the production process recovery of alcohol simplify greatly and more effective.
A kind of embodiment of the present invention is: alcohol reacts in the fixed bed etherification reactor to certain transformation efficiency with the lighter hydrocarbons that contain tertiary olefin, enter again and carry out product separation in the product separation tower, the ether product of producing goes out device at the bottom of the tower of product separation tower, and unreacted lighter hydrocarbons and alcohol flow out the laggard pure recovery tower of going into from cat head.The cat head effluent of alcohol recovery tower is the azeotrope of alcohol and lighter hydrocarbons, and be circulated in the methyltertiarvbutyl ether reactor and recycle, and the tower still is unreacted lighter hydrocarbons, extract wherein a part of backflow out as the product separation tower, turn back in the product separation tower, the raw material that another part can be used as product or Chemical Manufacture goes out still.
In order further to improve the transformation efficiency of tertiary olefin, another embodiment of the present invention is to adopt pre-etherification reaction and the placed in-line technology of catalytic distillation, at this moment catalytic distillation tower both can make the unreacted tertiary olefin that comes out from the pre-methyltertiarvbutyl ether reactor of fixed bed further react with alcohol, can make ether products and reactants separate again, at the bottom of the tower of catalytic distillation tower, obtain not containing substantially the ether product of alcohol, and unreacted lighter hydrocarbons and alcohol flow out the laggard pure recovery tower of going into from cat head.The cat head effluent of alcohol recovery tower is the azeotrope of alcohol and lighter hydrocarbons, and be circulated in the pre-methyltertiarvbutyl ether reactor and recycle, and the tower still is unreacted lighter hydrocarbons, extract wherein a part of backflow out as catalytic distillation tower, turn back in the catalytic distillation tower, the raw material that another part can be used as product or Chemical Manufacture goes out still.
The present invention is suitable for containing the lighter hydrocarbons fraction and the Fatty Alcohol(C12-C14 and C12-C18) reaction production ether product of tertiary olefin, is particularly suitable for C 4~C 8Tertiary olefin and C 1~C 4Fatty Alcohol(C12-C14 and C12-C18) reaction produce corresponding ether product, as methyl tertiary butyl ether (MTBE), Ethyl Tertisry Butyl Ether (ETBE), tertiary amyl ethyl ether (TAEE), methyl-tert hexyl ether (TH xME) and ethyl uncle hexyl ether (TH xThe production of ether product such as EE).
The present invention compared with prior art can more effectively reclaim unreacted alcohol, especially is fit to C 2~C 4Fatty Alcohol(C12-C14 and C12-C18) and the synthetic ether product of tertiary olefin reaction.C in the cat head unreacting hydrocarbon under the operational condition of catalytic distillation tower or product separation tower 2~C 4Fatty Alcohol(C12-C14 and C12-C18) content lower, conventional operating process be with this cat head discharging as backflow owing to contain alcohol in the phegma, the alcohol excess that reaction process requires can not all be carried into cat head, makes in the tower still product and contains alcohol; And with the backflow of the unreacted lighter hydrocarbons that do not contain alcohol at the bottom of the pure recovery tower as catalytic distillation tower or product separation tower, the unreacting hydrocarbon that has increased catalytic distillation tower or product separation tower carries pure ability, make in the tower still product ether content of alcohol lower, what also do not need to increase in addition alcohol carries agent or entrainer.But the save operation expense, shortened process reduces investment.
Fig. 1 is methyltertiarvbutyl ether reactor of the present invention and the placed in-line process flow diagram of product separation tower
Fig. 2 is pre-methyltertiarvbutyl ether reactor of the present invention and the placed in-line process flow diagram of catalytic distillation tower
Below in conjunction with accompanying drawing, ether product production technique of the present invention is described further:
The fixed bed etherification reactor (1) of Fig. 1 of the present invention can adopt tubulation fixed-bed reactor, adiabatic outer circulation reactor, expanded bed reactor or mixed phase bed bioreactor, preferably mixed phase bed bioreactor.Through the pure charging of pipeline (4) and lighter hydrocarbons charging through pipeline (5), recycle alcohol azeotrope charging through pipeline (18) enters reactor (1), and the mol ratio that makes the alcohol that enters in the reactor (1) and tertiary olefin is greater than 1.0, alcohol charging and lighter hydrocarbons charging can be pre-mixed and be preheating to and can enter pre-reactor again after the temperature of initiation reaction, react under the catalyst action in reactor, reaction heat raises the temperature of reactant feed gradually, when temperature is elevated to the bubble point temperature of reaction mass under the working pressure, reaction heat is absorbed by the partial material vaporization, and makes temperature of reaction stable.The working pressure of fixed bed etherification reactor is 0.4~1.0MPa, and temperature is 25~80 ℃, and air speed is 0.5~10h -1After the transformation efficiency of the tertiary olefin in the reactor (1) reaches certain value, enter into product separation tower (2) product separation ether through pipeline (6), the product separation tower is common distillation tower or azeotropic distillation column, its working pressure is 0.4~1.0MPa, tower top temperature is 50~100 ℃, and tower still temperature is 110~160 ℃.The ether product that generates flows out through pipeline (11) from the tower still, wherein a part through reboiler (12) vaporization after at the bottom of pipeline (13) returned tower, another part went out device as product through pipeline (14).Unreacted lighter hydrocarbons flow out from the product separation cat head with alcohol, after pipeline (7), condenser (8) condensation, enter recovery alcohol in the pure recovery tower (3) through pipeline (10), the alcohol recovery tower is the such conventional rectification tower of tray column or packing tower, its working pressure is 1.0~3.0MPa, tower top temperature is 60~140 ℃, and tower still temperature is 65~150 ℃.Unreacted alcohol and part lighter hydrocarbons flow out from cat head with the form of azeotrope in pure recovery tower (3), and after pipeline (15), condenser (16) condensation, a part of phlegma is back to cat head through pipeline (17); Another part phlegma is circulated to the inlet of fixed bed etherification reactor (1) through pipeline (18), and Fatty Alcohol(C12-C14 and C12-C18) is wherein recycled.Most of unreacted lighter hydrocarbons go out from tower bottom flow after separating, a part is returned as the phegma of product separation tower (2), another part is after pipeline (19), reboiler (20) vaporization, at the bottom of returning tower by pipeline (21), a remaining part goes out device as product or other industrial chemicals through pipeline (22).
When the transformation efficiency of tertiary olefin is had relatively high expectations, can adopt second kind of embodiment of the present invention, promptly adopt shown in Figure 2 with pre-methyltertiarvbutyl ether reactor and the placed in-line etherification reaction technology of catalytic distillation tower, at this moment tower (2) is a catalytic distillation tower among Fig. 2, its operational condition is that pressure is 0.5~1.0MPa, tower top temperature is 55~85 ℃, and tower still temperature is 120~160 ℃; Unreacted alcohol and part lighter hydrocarbons flow out from cat head with the form of azeotrope in pure recovery tower (3), after pipeline (15), condenser (16) condensation, part phlegma is back to cat head through pipeline (17), another part phlegma both can be circulated to the inlet of pre-methyltertiarvbutyl ether reactor (1) through pipeline (18), can be circulated to the conversion zone of catalytic distillation tower (2) again through pipeline (23), Fatty Alcohol(C12-C14 and C12-C18) is wherein recycled.Other processing step and operational condition are with the description to Fig. 1.
The catalyzer that uses in fixed bed etherification reactor and the catalytic distillation tower is acidic ion exchange resin catalyst, particularly macropore sulfate resin catalyzer.
With embodiment the present invention is described below, but the present invention is not limited to embodiment:
Embodiment 1
Adopt the ether product production technique of Fig. 1 of the present invention, produce methyl tertiary butyl ether (MTBE) with iso-butylene in the mixed c 4 and methyl alcohol reaction, conversion for isobutene reaches 91.6% in the methyltertiarvbutyl ether reactor, and the unreacted carbon four of pure recovery tower still can be used for the raw material that alkylate oil is produced.
Operational condition and result:
Iso-butylene content in the carbon four, % (m/m), 21.2%
The mol ratio of methyl alcohol and iso-butylene, 1.0: 1.0
The methyltertiarvbutyl ether reactor top hole pressure, MPa, 0.7
The methyltertiarvbutyl ether reactor temperature out, ℃, 63
The reactor air speed, h -1, 2.5
Product separation column overhead pressure, MPa, 0.6
Product separation Tata bottom pressure, MPa, 0.65
Product separation column overhead temperature, ℃, 53.6
Product separation tower still temperature, ℃, 125.8
Iso-butylene in the product separation column overhead unreacted carbon four, % (m/m), 1.78%
MTBE product purity % (m/m) at the bottom of the product separation Tata, 98.4%
Conversion for isobutene, % (m/m), 91.6%
Alcohol recovery tower tower top pressure, MPa, 2.0
Alcohol recovery tower tower bottom pressure, MPa, 2.05
Alcohol recovery tower tower top temperature, ℃, 95.18
Alcohol reclaims Tata still temperature, ℃, 102.4
Alcohol recovery tower cat head is formed % (m/m) methyl alcohol, 8.47; Trimethylmethane, 91.53
Alcohol is formed % (m/m) methyl alcohol, 0.005 at the bottom of reclaiming Tata; Unreacted carbon four, 99.995
Embodiment 2
Adopt the ether product production technique of Fig. 2 of the present invention, produce methyl tertiary butyl ether (MTBE) with iso-butylene in the mixed c 4 and methyl alcohol reaction, the isobutene conversion in pre-methyltertiarvbutyl ether reactor reaches after 90%, and material enters in the catalytic distillation tower.Unreacted iso-butylene and methyl alcohol continue reaction in catalytic distillation tower, separate the MTBE that generates simultaneously, make the total conversion rate of iso-butylene reach 99.8%.The methanol distillation column still is unreacted carbon four, and wherein methanol content is 0.005%, can be used as the raw material of producing 1-butylene or other Chemicals.
Operational condition and result:
Iso-butylene content in the carbon four, % (m/m), 22.5%
The mol ratio of methyl alcohol and iso-butylene, 1.1: 1.0
Pre-methyltertiarvbutyl ether reactor top hole pressure, MPa, 0.9
Pre-methyltertiarvbutyl ether reactor temperature out, ℃, 69.5
Pre-methyltertiarvbutyl ether reactor air speed, h -1, 2.5
The catalytic distillation tower tower top pressure, MPa, 0.8
The catalytic distillation tower tower bottom pressure, MPa, 0.85
The catalytic distillation tower tower top temperature, ℃, 62.9
Catalytic distillation Tata still temperature, ℃, 139.6
Iso-butylene in the catalytic distillation column overhead unreacted carbon four, % (m/m), 0.08%
MTBE product purity % (m/m) at the bottom of the catalytic distillation Tata, 98.5%
Conversion for isobutene, % (m/m), 99.8% pure recovery tower tower top pressure, MPa, 2.5 pure recovery tower tower bottom pressures, MPa, 2.55 pure recovery tower tower top temperatures, ℃, 104.7 alcohol reclaim Tata still temperature, ℃, 114.6 pure recovery tower cats head are formed % (m/m) methyl alcohol, 9.7; Trimethylmethane, 90.3 alcohol are formed % (m/m) methyl alcohol, 0.005 at the bottom of reclaiming Tata; Not anti-carbon four, 99.995

Claims (9)

1. method of producing ether product with lighter hydrocarbons that contain the tertiary olefin component and alcohol reaction, it is characterized in that: the lighter hydrocarbons and the alcohol that contain tertiary olefin enter fixed-bed reactor, under the effect of catalyzer, carry out etherification reaction, the cut that comes out from fixed-bed reactor enters into the product separation tower to be separated, or enter into catalytic distillation tower, further carry out etherification reaction and carry out product separation, at the bottom of product separation tower or catalytic distillation Tata, isolate the product ethers, and enter the pure recovery tower from the logistics that contains unreacted lighter hydrocarbons and alcohol that cat head comes out, alcohol and light constituent in the lighter hydrocarbons are flowed out from cat head with the form of azeotrope, turn back to fixed-bed reactor then or catalytic distillation tower recycles, and unreacted lighter hydrocarbons flow out from the tower still of pure recovery tower, and wherein a part is returned as the backflow of product separation tower or catalytic distillation tower.
2. in accordance with the method for claim 1, fixed-bed reactor wherein are mixed phase bed bioreactor, insulation fix bed reactor, calandria type fixed bed reactor or expanded bed reactor.
3. in accordance with the method for claim 2, fixed-bed reactor wherein are mixed phase bed bioreactors.
4. according to claim 1,2 or 3 described methods, the working pressure of fixed-bed reactor wherein is 0.4~1.0MPa, and temperature is 25~80 ℃, and air speed is 0.5~10h -1
5. in accordance with the method for claim 1, wherein the working pressure of product separation tower is 0.4~1.0MPa, and tower top temperature is 50~100 ℃, and tower still temperature is 110~160 ℃.
6. in accordance with the method for claim 1, wherein the working pressure of catalytic distillation tower is 0.5~1.0MPa, and tower top temperature is 55~85 ℃, and tower still temperature is 120~160 ℃.
7. in accordance with the method for claim 1, pure recovery tower wherein is the such conventional rectification tower of tray column or packing tower.
8. according to claim 1 or 7 described methods, wherein the working pressure of pure recovery tower is 1.0~3.0MPa, and tower top temperature is 60~140 ℃, and tower still temperature is 65~150 ℃.
9. in accordance with the method for claim 1, wherein contain the lighter hydrocarbons of tertiary olefin component for containing C 4~C 8The lighter hydrocarbons of tertiary olefin, alcohol is C 1~C 4Fatty Alcohol(C12-C14 and C12-C18).
CNB001239570A 2000-10-18 2000-10-18 Ether product producing process Expired - Fee Related CN1202060C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102351661A (en) * 2011-09-30 2012-02-15 胡先念 Method for preparing methyl tertiary butyl ether (MTBE)
CN107382681A (en) * 2017-08-01 2017-11-24 山东滨庆新能源开发有限公司 After the washing of MTBE devices methanol after ether carbon four into azeotropy rectification column reflux technique
CN110305702A (en) * 2019-08-06 2019-10-08 凯瑞环保科技股份有限公司 A kind of device and method with industrial waste production methanol gasoline blend component
CN110499179A (en) * 2019-08-30 2019-11-26 北京东方红升新能源应用技术研究院有限公司 The methods and applications of formaldehyde and isoamyl alkene reaction synthetic gasoline component
CN114395415A (en) * 2021-12-29 2022-04-26 江苏新海石化有限公司 Light gasoline etherification system

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102351661A (en) * 2011-09-30 2012-02-15 胡先念 Method for preparing methyl tertiary butyl ether (MTBE)
CN102351661B (en) * 2011-09-30 2014-04-02 惠州中创化工有限责任公司 Method for preparing methyl tertiary butyl ether (MTBE)
CN107382681A (en) * 2017-08-01 2017-11-24 山东滨庆新能源开发有限公司 After the washing of MTBE devices methanol after ether carbon four into azeotropy rectification column reflux technique
CN110305702A (en) * 2019-08-06 2019-10-08 凯瑞环保科技股份有限公司 A kind of device and method with industrial waste production methanol gasoline blend component
CN110499179A (en) * 2019-08-30 2019-11-26 北京东方红升新能源应用技术研究院有限公司 The methods and applications of formaldehyde and isoamyl alkene reaction synthetic gasoline component
CN114395415A (en) * 2021-12-29 2022-04-26 江苏新海石化有限公司 Light gasoline etherification system

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