CN102649664A - Method for producing ethylene through ethanol dehydration - Google Patents

Method for producing ethylene through ethanol dehydration Download PDF

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Publication number
CN102649664A
CN102649664A CN201110045561XA CN201110045561A CN102649664A CN 102649664 A CN102649664 A CN 102649664A CN 201110045561X A CN201110045561X A CN 201110045561XA CN 201110045561 A CN201110045561 A CN 201110045561A CN 102649664 A CN102649664 A CN 102649664A
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reaction
ethanol
ethylene
zsm
raw material
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刘俊涛
王万民
李蕾
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a method for producing ethylene through ethanol dehydration, and mainly solves the technical problem of low reaction space velocity in the prior art. Through the adoption of the technical scheme that ethanol is taken as a raw material, and under the conditions that the reaction temperature is 200 to 380 DEG C, the reaction pressure measured by gauge pressure is 0 to 2 MPa, and the reaction space velocity is 0.1 to 8 hours <-1>, the raw material is in contact with a binderless ZSM-5 molecular sieve taken as a catalyst to generate an ethylene-contained substance separated to obtain ethylene products. Therefore, the invention solves the problem well, and can be used in the industrial production of ethylene.

Description

The method of producing ethylene by ethanol dehydration
Technical field
The present invention relates to a kind of method of producing ethylene by ethanol dehydration, particularly about adopting the method for ZSM-5 molecular sieve catalytic producing ethylene by ethanol dehydration.
Background technology
Ethene is a kind of very important basic Organic Chemicals, and ethylene industry is the basis of petrochemical industry, in national economy, occupies very consequence.In recent years, along with increasing rapidly of verivate demands such as Vilaterm, the demand of ethene was all increased year by year.At present, ethene is raw material through Sweet natural gas or low-density oil cut mainly, adopts steam cracking process to make, but along with Sweet natural gas and low-density oil cut price continue highly, the method for some other approach increasing output of ethylene becomes the focus of concern.Especially along with the fast development of biotechnology, biological legal system alcoholic acid technology is constantly perfect, and the source of raw material is extensive day by day, and the cost of raw material also more becomes rationally, makes the producing ethylene from dehydration of ethanol technology enjoy attention.The producing ethylene from dehydration of ethanol technology has that flow process is short, equipment is few, investment is little, instant effect and characteristics such as stronger supporting flexibility and market handiness.Producing ethylene from dehydration of ethanol technology involved in the present invention is a kind of competitive Technology.
The main reaction of producing ethylene from dehydration of ethanol is:
CH 3CH 2OH→CH 2＝CH 2+H 2O
Be that the reaction of a part alcohol catalysis obtains a part ethene and a part water.Some side reactions also unavoidably can take place in the catalytic dehydration of ethanol process certainly as generating ether, acetaldehyde, carbon monoxide, carbonic acid gas, higher olefins etc.
1993 the 1st phases of document " Speciality Petrochemicals ", introduced a kind of employing for 35～37 pages
Figure BSA00000439717100011
Sieve catalyst is to the research of low-concentration ethanol system ethene, and the result shows, when temperature of reaction is that 250～280 ℃, liquid air speed are 0.5～0.8 hour -1, when the feed ethanol mass concentration was 10% left and right sides, ethanol conversion was up to 99%, and ethylene selectivity can reach 97～99%.But the liquid air speed is lower.
Document " chemical industry and engineering " the 16th the 2nd phase of volume of nineteen ninety-five, introduced the development of NC1301 type catalyst for ethanol delydration to ethylene, this catalyzer main active component is γ-Al 2O 3, 350～440 ℃ of temperature of reaction, reaction pressure≤0.3MPa (absolute pressure), weight space velocity 0.3～0.6 hour -1, ethylene content 97.5～98.8%, transformation efficiency is higher, and by product is less.But there is the lower shortcoming of air speed equally.
USP423475 has reported the producing ethylene from dehydration of ethanol technology, and it adopts oxide catalyst, 320～450 ℃ of temperature of reaction, and air speed 0.4～0.6 hour -1Realize higher ethanol conversion under the condition.
The subject matter that the related technology of above-mentioned document exists is that the catalyst reaction air speed is low, the inefficient technical problem of catalyzer.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past the low technical problem of reaction velocity in the technology, and a kind of method of new producing ethylene by ethanol dehydration is provided.This method has the high advantage of reaction velocity.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of method of producing ethylene by ethanol dehydration is a raw material with ethanol, is 200～380 ℃ in temperature of reaction, is 0～2MPa in the gauge pressure reaction pressure, and reaction velocity is 0.1～8 hour -1Under the condition, raw material contacts the logistics that generates ethene with the adhesiveless ZSM-5 sieve catalyst, obtains ethylene product through separating.
ZSM-5 sieve catalyst silica alumina ratio preferable range is SiO in the technique scheme 2/ Al 2O 3Be 20～600; Silica alumina ratio more preferably scope is SiO 2/ Al 2O 3Be 40～400.The temperature of reaction preferable range is 230～320 ℃, and reaction weight space velocity preferable range is 0.5～5 hour -1, be 0.1～1MPa in gauge pressure reaction pressure preferable range.
In the catalytic dehydration of ethanol reaction increasing output of ethylene process, one of optimal principal reaction route is to realize that at low temperatures the reaction of 1 molecules of ethanol obtains 1 molecule ethene and 1 molecular water.This can cut down the consumption of energy on the one hand, the competitive power that develops skill, and simultaneously, lower temperature of reaction is for avoiding in the catalytic dehydration of ethanol process more contingent side reactions as generating ether, acetaldehyde, carbon monoxide, carbonic acid gas, higher olefins etc.
Catalyzer employing adhesiveless ZSM-5 molecular sieve is a catalyzer in the present technique scheme; Reaction can be carried out under 250 ℃; Need for react more than 360 ℃ with respect to aluminium oxide catalyst, temperature of reaction has reduced more than 100 ℃, and the reduction of temperature obviously can reduce operation energy consumption greatly; In addition, be catalyzer owing to adopt the binderless ZSM-5 molecular sieve, catalytic efficiency (improves, and reaction can be carried out under the high-speed condition, has improved the throughput of unit device greatly.
Adopting technical scheme of the present invention, is catalyzer with the binderless ZSM-5 molecular sieve, and temperature of reaction is 230～320 ℃, and the reaction weight space velocity is 0.5～5 hour -1, be under 0.1～1MPa condition in the gauge pressure reaction pressure, ethanol conversion can reach 100%, and ethylene selectivity can reach more than 95%, has obtained better technical effect.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
Preparation of Catalyst: take by weighing 100 gram silica alumina ratio SiO 2/ Al 2O 3Be 60 ZSM-5 molecular sieve, add after 40 gram 40% (weight) silicon sol mix that extrusion moulding through 120 ℃ of oven dry, obtains sample A.
The tetrapropyl amine bromide, 10 grams 1 that add 5 grams in the reaction kettle in advance, the mixture of 6-hexanediamine and 30 gram zero(ppm) water places sealing back, the online side of reaction kettle Porous Stainless Steel under 180 ℃, to carry out gas-solid 10 gram sample A and handled mutually 100 hours.Product takes out the back and use distilled water wash, dry back in air atmosphere in 600 ℃ of roastings 2 hours, obtain adhesiveless ZSM-5 sieve catalyst sample.
It is 18 millimeters fixed-bed reactor that the adhesiveless ZSM-5 sieve catalyst sample that makes 3 gram is put into internal diameter; Logical nitrogen is cooled to temperature of reaction 550 ℃ of activation after 2 hours before the experiment; The raw material that uses in the experiment is absolute ethyl alcohol, is 250 ℃ in temperature of reaction, air speed 1.2 hours -1, under gauge pressure reaction pressure 0.02MPa condition, ethanol conversion is 99.8%, ethylene selectivity 94.3%.
[embodiment 2]
According to each step and the operational condition of embodiment 1, just change ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2O 3Be 100, make the ZSM-5 sieve catalyst of corresponding binder free.The raw material that uses in the experiment is absolute ethyl alcohol still, is 230 ℃ in temperature of reaction, air speed 0.5 hour -1, under gauge pressure reaction pressure 0.2MPa condition, ethanol conversion is 95.1%, ethylene selectivity 90.5%.
[embodiment 3]
According to each step and the operational condition of embodiment 1, just change ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2O 3Be 180, make the ZSM-5 sieve catalyst of corresponding binder free, and the iron of load 0.5%.Water and ethanol mass ratio are 0.5: 1 in the raw material that uses in the experiment, are 275 ℃ in temperature of reaction, air speed 0.8 hour -1, under gauge pressure reaction pressure 0.05MPa condition, ethanol conversion is 100%, ethylene selectivity 97.6%.
[embodiment 4]
According to each step and the operational condition of embodiment 1, just change ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2O 3Be 300, make the ZSM-5 sieve catalyst of corresponding binder free.The raw material that uses in the experiment is absolute ethyl alcohol, is 360 ℃ in temperature of reaction, air speed 1.2 hours -1, under gauge pressure reaction pressure 0.78MPa condition, ethanol conversion is 98.1%, ethylene selectivity 95.7%.
[embodiment 5]
According to each step and the operational condition of embodiment 1, just change ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2O 3Be 80, make the ZSM-5 sieve catalyst of corresponding binder free.The raw material that uses in the experiment is absolute ethyl alcohol, is 350 ℃ in temperature of reaction, air speed 2 hours -1, under gauge pressure reaction pressure 0.6MPa condition, ethanol conversion is 99.7%, ethylene selectivity 92.6%.
[embodiment 6]
According to each step and the operational condition of embodiment 1, just change ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2O 3Be 500, make the ZSM-5 sieve catalyst of corresponding binder free.The raw material that uses in the experiment is absolute ethyl alcohol, is 280 ℃ in temperature of reaction, air speed 6 hours -1, under gauge pressure reaction pressure 0.05MPa condition, ethanol conversion is 90.8%, ethylene selectivity 95.4%.
[embodiment 7]
According to each step and the operational condition of embodiment 1, just change ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2O 3Be 100, make the ZSM-5 sieve catalyst of corresponding binder free.The raw material that uses in the experiment is absolute ethyl alcohol, is 260 ℃ in temperature of reaction, air speed 0.9 hour -1, under gauge pressure reaction pressure 0.04MPa condition, ethanol conversion is 100%, ethylene selectivity 99.6%.
[embodiment 8]
According to each step and the operational condition of embodiment 1, just change ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2O 3Be 150, make the ZSM-5 sieve catalyst of corresponding binder free.The raw material that uses in the experiment is absolute ethyl alcohol, is 260 ℃ in temperature of reaction, air speed 1.8 hours -1, under gauge pressure reaction pressure 0.1MPa condition, ethanol conversion is 99.3%, ethylene selectivity 96.5%.
[Comparative Examples 1]
According to each step and the operational condition of embodiment 8, just change and contain 10% alumina binder in the ZSM-5 sieve catalyst.Its reaction result is that ethanol conversion is 90.3%, ethylene selectivity 87.5%.

Claims (4)

1. the method for a producing ethylene by ethanol dehydration is a raw material with ethanol, is 200～380 ℃ in temperature of reaction, is 0～2MPa in the gauge pressure reaction pressure, and reaction velocity is 0.1～8 hour -1Under the condition, raw material contacts the logistics that generates ethene with the adhesiveless ZSM-5 sieve catalyst, obtains ethylene product through separating.
2. according to the method for the said producing ethylene by ethanol dehydration of claim 1, it is characterized in that ZSM-5 sieve catalyst silica alumina ratio SiO 2/ Al 2O 3Be 20～600.
3. according to the method for the said producing ethylene by ethanol dehydration of claim 2, it is characterized in that ZSM-5 sieve catalyst silica alumina ratio SiO 2/ Al 2O 3Be 40～400.
4. according to the method for the said producing ethylene by ethanol dehydration of claim 1, it is characterized in that temperature of reaction is 230～320 ℃, the reaction weight space velocity is 0.5～5 hour -1, be 0.1～1MPa in the gauge pressure reaction pressure.
CN201110045561XA 2011-02-25 2011-02-25 Method for producing ethylene through ethanol dehydration Pending CN102649664A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121624A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Method for preparing ethylene by ethanol dehydration

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121624A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Method for preparing ethylene by ethanol dehydration

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Application publication date: 20120829