CN101092322B - Method for converting by-product of MTO reaction to alkane - Google Patents

Method for converting by-product of MTO reaction to alkane Download PDF

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Publication number
CN101092322B
CN101092322B CN200710054769A CN200710054769A CN101092322B CN 101092322 B CN101092322 B CN 101092322B CN 200710054769 A CN200710054769 A CN 200710054769A CN 200710054769 A CN200710054769 A CN 200710054769A CN 101092322 B CN101092322 B CN 101092322B
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logistics
effluent
reaction
mto
alkane
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CN101092322A (en
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王月霞
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China Petrochemical Corp
Sinopec Luoyang Guangzhou Engineering Co Ltd
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Sinopec Luoyang Petrochemical Engineering Corp
China Petrochemical Corp
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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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

This invention discloses a method for converting MTO reaction byproducts into alkanes. The method solves the problem of high apparatus investment faced by the present technique. The method comprises:separating MTO reaction effluent to obtain a first effluent containing ethylene and propylene, and a second effluent containing dimethyl ether, C4+ compounds and oxides, dehydrating the first effluent, separating, mixing the byproducts with the second effluent, separating the C4+-containing effluent, and reacting with H2 in the presence of hydrogenating catalyst to obtain alkanes. The reaction conditions are: H2 partial pressure 0.8-2.0 MPa, temperature 220-300 deg.C, liquid hourly space velocity 0.2-2.0 h-1, and H2/hydrocarbon ratio is 150-1000. The method can convert oxides and an olefin pollutant produced by MTO reaction into alkanes by hydrogenation, and has such advantages as low hydrogenation pressure, low apparatus investment and low operation cost.

Description

A kind of method that the MTO byproduct of reaction is changed into alkane
Technical field
The present invention relates to handle the method for methanol to olefins reaction by product, particularly the methanol to olefins reaction by product is changed into the method for alkane.
Background technology
The method of traditional mode of production alkene is to be that raw material is by catalysis and steam cracking production, particularly steam cracking with the petroleum hydrocarbon.Alkene, particularly ethene and propylene are main industrial chemicals, and supply falls short of demand always for many years, and the approach of exploring raising and production alkene is global pursuit.In recent years, owing to soaring of crude oil price, exploring with non-crude oil was that raw material production alkene becomes a focus.
With oxide compound, particularly methanol conversion became light olefin after deliberation many years, had developed many technology, but the C that in the MTO process, produces 4 +, C 5 +These heavy alkene and oxide compounds, in the MTO effluent, can make the alkene of production not meet the requirement of polymerization-grade alkene, therefore must from alkene, isolate these materials, how handling these materials in addition is the keys that improve the MTO economy, in USP5714662, disclose and a kind of by product has further been separated and carried out respectively the method for etherificate, dimerization, isomerization, hydration and hydrogenation reaction, consequently by product can have been changed into high-octane number component and other value products.And in USP7030284, disclose and a kind ofly will weigh the method that alkene and oxide compound are hydrogenated into alkane, this technology adopts with sulfurized Ni, Co, Mo and Ni, Co, W is that active metal component is that the catalyst towards heavy alkene and the oxide compound of carrier carries out hydrogenation with the aluminum oxide, Ni, Co, Mo and Ni, Co, W is traditional hydrofining active ingredient, these metal general requirements are than higher temperature of reaction and pressure, temperature of reaction is 150～350 ℃, be preferably 180～350 ℃, reaction pressure is greater than 5.0Mpa, be preferably 10.0～20.0MPa, for hydrogenation process, severe reaction conditions, then high more to the requirement of conversion unit, invest also high more.
Summary of the invention
The present invention be directed to the prior art conversion unit and invest high shortcoming, and provide a kind of method of the MTO of processing byproduct of reaction, oxide compound that this method can produce the MTO process and olefin contaminants are through being hydroconverted into alkane, reduce the pressure of MTO by product hydrogenation, thereby reduce facility investment and process cost.
A kind of method of handling the MTO byproduct of reaction provided by the invention the steps include:
1) separate: the reaction effluent acquisition (a) that separates from MTO contains ethene and propylene stream; (b) contain dme, C 4 +Hydrocarbon and oxide compound logistics, logistics (a) is divided into ethene, propylene and by product after dehydration separates, and logistics (b) and by product mix, and separate again, are divided into containing less than C 4Logistics and contain C 4 +Logistics.
2) hydrogenation: being reactive metal, with TiO with W, Ni or W, Mo, Ni 2And Al 2O is under the hydrogenation catalyst effect of carrier, contains C with what step 1) was separated 4 +Logistics mixes with hydrogen and reacts, and generates alkane, and reaction conditions is: hydrogen dividing potential drop 0.8～2.0MPa, 220～300 ℃ of temperature, liquid hourly space velocity 0.2～2.0h -1, hydrogen hydrocarbon volume ratio is 150～1000.
The oxide compound of separating from the MTO reactor effluent of the present invention is one or more a mixture in dme, methyl ethyl ether and the methyl isopropyl ether.
It is carrier that the used hydrogenation catalyst of the present invention adopts titanium dioxide, aluminium sesquioxide, W, Ni or W, Mo, Ni are reactive metal, wherein titanium dioxide accounts for 1～60% of total weight of carrier, aluminium sesquioxide accounts for 40%～99% of total weight of carrier, in support oxide butt gross weight, when adopting W, Ni to be reactive metal, catalyzer consist of WO 3Account for 5～35% of total catalyst weight, NiO accounts for 1～20% of total catalyst weight, and surplus is a carrier; When adopt W, Mo, when Ni is reactive metal, catalyzer consist of WO 3Account for 5～35% of total catalyst weight, NiO accounts for 1～20% of total catalyst weight, MoO 3Account for 1～25% of total catalyst weight, surplus is a carrier.
Dme of the present invention, C 4 +The alkane that changes into behind the compound hydrogenation can be used as various value products or raw material, as C 5 +Alkane can be used as the blend component of gasoline or the raw material of solvent oil or steam cracking, C 4Perhaps less than C 4Component as the raw material or the fuel of steam cracking, as LPG.
Oxide compound that the present invention can produce the MTO process and olefin contaminants reduce the pressure of MTO by product hydrogenation through being hydroconverted into alkane.Compared with prior art, reaction pressure of the present invention is low, and investment and process cost are low, hydrogenation products quality height.
Describe the present invention in detail with the drawings and specific embodiments below, but the drawings and specific embodiments do not limit the scope of the invention.
Description of drawings
Figure is a kind of MTO reactants separate of the present invention and hydrotreatment by product flow process synoptic diagram.
Among the figure: 1-methyl alcohol, 2-oxygen, 3-reaction effluent, 4-contain dme, C 4 +Hydrocarbon and oxide compound logistics, 5-contains ethene and propylene stream, and 7-contains olefin stream, and 8-contains methyl alcohol and hydrocarbon stream, and 9-contains dme, C 4 +Hydrocarbon and methanol stream, 10-hydrogen, 11-contains C 4 +Logistics, 12-alkane, 13-polymer grade ethylene and propylene, 14-contains less than C 4Logistics, 15-methanol oxidation reactor, 16-quench tower, 17-compressor, 18-knockout tower, 19-water trap, 20-separator, 21-hydrogenator.
Embodiment
As shown in the figure, material benzenemethanol 1 carries out oxidizing reaction with oxygen 2 in methanol oxidation reactor 15, and reaction effluent 3 enters quench tower 16 to carry out chilling and be separated into (a) containing ethene and propylene stream 5; (b) contain dme, C 4 +Hydrocarbon and oxide compound logistics 4, after containing ethene and propylene stream 5 and in compressor 17, compressing, in water trap 19, dewater it is separated into and contains olefin stream 7 and contain methyl alcohol and hydrocarbon stream 8, contain olefin stream 7 and in separator 20, further be separated into two kinds of components, a kind of component is polymer grade ethylene and propylene 13, and another kind of component is to contain dme, C 4 +Hydrocarbon and methanol stream 9 contain dme, C 4 +Hydrocarbon and methanol stream 9, contain methyl alcohol and hydrocarbon stream 8, contain dme, C 4 +Hydrocarbon and oxide compound logistics 4 mix the back to knockout tower 18, are separated into to contain less than C 4Logistics 14 with contain C 4 +Logistics 11 contains C then 4 + Logistics 11 is mixed into hydrogenator 21 with hydrogen 10 and carries out hydrogenation reaction, changes into alkane 12, and W, Ni/TiO are housed in the reactor 2-Al 2O 3Or W, Mo, Ni/TiO 2-Al 2O 3Catalyzer, hydrogenation conditions is: hydrogen dividing potential drop 0.8～2.0MPa, 220～300 ℃ of temperature, liquid hourly space velocity 0.2～2.0h -1, hydrogen-hydrocarbon ratio is 150～1000.

Claims (2)

1. one kind changes into the method for alkane with the MTO byproduct of reaction, it is characterized in that comprising the steps:
1) separate: the reaction effluent acquisition (a) that separates from MTO contains ethene and propylene stream; (b) contain dme, C 4 +Hydrocarbon and oxide compound logistics, logistics (a) is divided into ethene, propylene and by product after dehydration separates, and logistics (b) and by product mix, and separate again, are divided into containing less than C 4Logistics and contain C 4 +Logistics;
2) hydrogenation: being reactive metal, with TiO with W, Ni or W, Mo, Ni 2And Al 2O is under the hydrogenation catalyst effect of carrier, contains C with what step 1) was separated 4 +Logistics mixes with hydrogen and reacts, and generates alkane, and reaction conditions is: hydrogen dividing potential drop 0.8～2.0MPa, 220～300 ℃ of temperature, liquid hourly space velocity 0.2～2.0h -1, hydrogen-hydrocarbon ratio is 150～1000.
2. method according to claim 1 is characterized in that: described oxide compound is one or more a mixture in dme, methyl ethyl ether and the methyl isopropyl ether.
CN200710054769A 2007-07-13 2007-07-13 Method for converting by-product of MTO reaction to alkane Active CN101092322B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102190545A (en) * 2010-03-03 2011-09-21 中国石油化工股份有限公司 Method for utilizing byproducts in the process of preparing olefins from methanol
CN103724147B (en) * 2013-12-27 2016-03-09 中国天辰工程有限公司 The removal methods of divinyl in a kind of methanol to olefins reaction product
CN114644541A (en) * 2020-12-18 2022-06-21 中国石油化工股份有限公司 Device and method for preparing low-carbon olefin from alcohol

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5174662A (en) * 1990-11-16 1992-12-29 Lucas Industries Public Limited Company Device for applying braking torque to a shaft
US7030284B2 (en) * 2002-08-20 2006-04-18 Exxonmobil Chemical Patents Inc. Method and reactor system for converting oxygenate contaminants in an MTO reactor system product effluent to hydrocarbons

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5174662A (en) * 1990-11-16 1992-12-29 Lucas Industries Public Limited Company Device for applying braking torque to a shaft
US7030284B2 (en) * 2002-08-20 2006-04-18 Exxonmobil Chemical Patents Inc. Method and reactor system for converting oxygenate contaminants in an MTO reactor system product effluent to hydrocarbons

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Address after: 100029 Beijing City, Chaoyang District Hui Street No. 6

Co-patentee after: Luoyang Petrochemical Engineering Corporation /SINOPEC

Patentee after: China Petrochemical Group Corp.

Address before: 100029 Beijing City, Chaoyang District Hui Street No. 6

Co-patentee before: Luoyang Petrochemical Engineering Co., China Petrochemical Group

Patentee before: China Petrochemical Group Corp.