CN102372541A - Method for raising yield of low-carbon olefins - Google Patents

Method for raising yield of low-carbon olefins Download PDF

Info

Publication number
CN102372541A
CN102372541A CN2010102620104A CN201010262010A CN102372541A CN 102372541 A CN102372541 A CN 102372541A CN 2010102620104 A CN2010102620104 A CN 2010102620104A CN 201010262010 A CN201010262010 A CN 201010262010A CN 102372541 A CN102372541 A CN 102372541A
Authority
CN
China
Prior art keywords
peclet number
action
zone
low
yield
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010102620104A
Other languages
Chinese (zh)
Other versions
CN102372541B (en
Inventor
齐国祯
陈伟
俞志楠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201010262010.4A priority Critical patent/CN102372541B/en
Publication of CN102372541A publication Critical patent/CN102372541A/en
Application granted granted Critical
Publication of CN102372541B publication Critical patent/CN102372541B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02P20/584—Recycling of 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

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for raising the yield of low-carbon olefins, mainly solving the problem of low yield of medium and low carbon olefins in the prior art. The method comprises the following steps: putting the raw material containing methanol in a precontact zone with the axial Peclet number of less than 15, letting the raw material contact with spent catalyst and regenerated catalyst, letting the liquid phase flow and catalyst in the precontact zone enter in a main contact zone with an axial Peclet number which is at least 20 % larger than the axial Peclet number of the precontact zone to generate a product containing low-carbon olefins. The invention can be applied in the industrial production of low-carbon olefins.

Description

Improve the method for yield of light olefins
Technical field
The present invention relates to a kind of method that improves yield of light olefins.
Technical background
Low-carbon alkene, promptly ethene and propylene are two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are to produce through petroleum path, but because limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms system ethene, propylene.Wherein, One type of important alternative materials that is used for low-carbon alkene production is an oxygenatedchemicals; For example alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed through coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, like methyl alcohol, can be made by coal or Sweet natural gas, and technology is very ripe, can realize up to a million tonnes industrial scale.Because the popularity in oxygenatedchemicals source is added and is transformed the economy that generates low-carbon alkene technology, so by the technology of oxygen-containing compound conversion to produce olefine (OTO), particularly the technology by methanol conversion system alkene (MTO) receives increasing attention.
In the US4499327 patent silicoaluminophosphamolecular molecular sieves catalyst applications is studied in great detail in methanol conversion system olefin process, think that SAPO-34 is the first-selected catalyzer of MTO technology.The SAPO-34 catalyzer has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction times of low-carbon alkene 10 seconds, more even reach in the reaction time range of riser tube.
Announced among the US6166282 that a kind of methanol conversion is the technology and the reactor drum of low-carbon alkene; Adopt fast fluidized bed reactor; Gas phase is after the lower Mi Xiangfanyingqu reaction of gas speed is accomplished; After rising to the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Because reaction after product gas and catalyzer sharp separation have effectively prevented the generation of secondary reaction.Through analog calculation, to compare with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all significantly reduce.But there is the lower problem of yield of light olefins in this method.
Announced among the CN1723262 that it is low-carbon alkene technology that the multiple riser reaction unit that has central catalyst return is used for oxygenate conversion; This covering device comprises a plurality of riser reactors, gas solid separation district, a plurality of offset components etc.; Each riser reactor has the port of injecting catalyst separately; Be pooled to the disengaging zone of setting, catalyzer and product gas are separated.There is the lower problem of yield of light olefins equally in this method.
It is the method for alkene with oxygenate in the reactor drum of baffle plate that CN 200680018303 has announced a kind of, in this method reactive moieties is divided into three zones, and one is initial conduit; One is the contact conduit; One is linking conduit, wherein in the contact conduit, baffle plate is set, and the gas phase linear speed is greater than 1.52 meter per seconds; But this method exists methanol conversion and the lower shortcoming of selectivity of light olefin; Methanol conversion is up to 98%, and selectivity of light olefin is up to 76.3%, makes yield of light olefins be merely 74.8%.
All there is the lower problem of yield of light olefins in prior art, and the present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the lower problem of yield of light olefins that exists in the prior art, and a kind of method of new raising yield of light olefins is provided.This method is used for the production of low-carbon alkene, has the yield of light olefins advantage of higher.
For addressing the above problem; The technical scheme that the present invention adopts is following: a kind of method that improves yield of light olefins; Comprise that the raw material that contains methyl alcohol gets into axial Peclet number less than 15 preparatory zone of action; Contact with regenerated catalyst with reclaimable catalyst, the gaseous stream of zone of action and catalyzer get into the main reaction region of axial Peclet number than the axial Peclet number big at least 20% of preparatory zone of action in advance, generate the product that comprises low-carbon alkene.
In the technique scheme, said catalyzer is selected from SAPO-34; The axial Peclet number of said preparatory zone of action is less than 6; The axial Peclet number of said main reaction region is than the axial Peclet number of preparatory zone of action greatly at least 40%; The temperature of reaction of said preparatory zone of action is 380～450 ℃, and the average carbon deposition quantity massfraction of catalyzer is 1.0～4.0%; The temperature of reaction of said main reaction region is 400～485 ℃, and the gas phase linear speed is 0.8～3.0 meter per second.
Axially the Peclet number is a non-dimensional number; It is the situation that departs from that characterizes gas phase piston flow when gas stream is crossed beds in the reactor drum; Axially the Peclet number is big more; Gas phase flows and to approach piston flow more, infinitely-great Peclet number reflection be ideal piston flow situation, and general Peclet number 4 below can be thought mixing complete mixing flow gas-solid flow flowing mode comparatively completely.The method of calculation of Peclet number are among the present invention:
Peclet number=μ g* H/D g, wherein, μ gBe gas phase linear speed, meter per second; H is the reactor beds layer height, rice; D gBe the axial gas spread coefficient, rice 2/ second.Known in the field, the axial gas diffusion coefficient D gCan adopt tracing method to measure.
Adopt method of the present invention; The bigger preparatory zone of action of back-mixing is set; Regenerated catalyst and reclaimable catalyst are mixed; And conversion methyl alcohol is low-carbon alkene under lower temperature, then at the production low-carbon alkene of the less main reaction region highly selective of back-mixing, reaches the purpose that improves yield of light olefins.
Adopt technical scheme of the present invention: said catalyzer is selected from SAPO-34; The axial Peclet number of said preparatory zone of action is less than 6; The axial Peclet number of said main reaction region is than the axial Peclet number of preparatory zone of action greatly at least 40%; The temperature of reaction of said preparatory zone of action is 380～450 ℃, and the average carbon deposition quantity massfraction of catalyzer is 1.0～4.0%; The temperature of reaction of said main reaction region is 400～485 ℃, and the gas phase linear speed is 0.8～3.0 meter per second, and low-carbon alkene carbon back yield reaches 83.17% (weight), and is higher at least more than 3% than yield of light olefins of the prior art, obtained better technical effect.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
Among Fig. 1,1 is the methyl alcohol bottom feed; 2 is main reaction region; 3 is stripping zone; 4 is heat production coil pipe; 5 are gas-solid sharp separation equipment; 6 is gas-solid cyclone separator; 7 is reactor drum; 8 is the products export pipeline; 9 is inclined tube to be generated; 10 is the reclaimable catalyst circulation tube; 11 is regenerator sloped tube; 12 is preparatory zone of action; 13 is the reclaimable catalyst circulation tube; 14 is heat collector.
Methyl alcohol gets into preparatory zone of action 12 from feeding line 1, and contacts from the catalyzer of reclaimable catalyst circulation tube 10 with regenerator sloped tube 11, then gaseous stream and catalyzer entering main reaction region 2; Generation comprises the product of low-carbon alkene; Get in the gas-solid sharp separation equipment 5, isolated gaseous products is separated through cyclonic separator 6 once more after pipeline 8 gets into centrifugal station, the reclaimable catalyst that cyclonic separator is told; Behind stripping zone 3 strippings; A part is gone revivifier regeneration through inclined tube 9 to be generated, and a part is returned preparatory zone of action 12 through catalyst recirculation pipe 10, and a part is returned in the main reaction region 2 through catalyst recirculation pipe 13.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
On reaction unit as shown in Figure 1, pure methanol feeding, catalyzer adopts SAPO-34; The zone of action temperature of reaction is 405 ℃ in advance, and the average carbon deposition quantity massfraction of catalyzer is 2.8%, and axially the Peclet number is 10; The main reaction region temperature of reaction is 467 ℃, and the gas phase linear speed is 1.25 meter per seconds, and axially the Peclet number is bigger by 150% than the axial Peclet number of preparatory zone of action; Catalyzer 65% through behind the stripping returns preparatory zone of action through the catalyst recirculation pipe, and 25% goes revivifier regeneration, and 10% returns main reaction region through the catalyst recirculation pipe; Reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon back yield of reactor outlet is 82.49% (weight).
[embodiment 2]
According to embodiment 1 described condition and step, changing preparatory zone of action temperature of reaction is 380 ℃, and the average carbon deposition quantity massfraction of catalyzer is 1.1%; Axially the Peclet number is 15, and the main reaction region temperature of reaction is 400 ℃, and the gas phase linear speed is 0.8 meter per second; Axially the Peclet number is bigger by 20% than the axial Peclet number of preparatory zone of action; Catalyzer 55% through behind the stripping returns preparatory zone of action through the catalyst recirculation pipe, and 35% goes revivifier regeneration, and 10% returns main reaction region through the catalyst recirculation pipe; Reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon back yield of reactor outlet is 79.85% (weight).
[embodiment 3]
According to embodiment 1 described condition and step, changing preparatory zone of action temperature of reaction is 450 ℃, and the average carbon deposition quantity massfraction of catalyzer is 3.97%; Axially the Peclet number is 15; The main reaction region temperature of reaction is 485 ℃, and the gas phase linear speed is 3.0 meter per seconds, and axially the Peclet number is bigger by 300% than the axial Peclet number of preparatory zone of action; Catalyzer 75% through behind the stripping returns preparatory zone of action through the catalyst recirculation pipe; 25% goes revivifier regeneration, and reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon back yield of reactor outlet is 81.95% (weight).
[embodiment 4]
According to embodiment 1 described condition and step, changing preparatory zone of action temperature of reaction is 420 ℃, and the average carbon deposition quantity massfraction of catalyzer is 2.5%; Axially the Peclet number is 6, and the main reaction region temperature of reaction is 470 ℃, and the gas phase linear speed is 1.5 meter per seconds; Axially the Peclet number is bigger by 180% than the axial Peclet number of preparatory zone of action; Catalyzer 55% through behind the stripping returns preparatory zone of action through the catalyst recirculation pipe, and 35% goes revivifier regeneration, and 10% returns main reaction region through the catalyst recirculation pipe; Reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon back yield of reactor outlet is 83.17% (weight).
[embodiment 5]
According to embodiment 3 described condition and steps; Changing the average carbon deposition quantity massfraction of catalyzer is 2.5%; Main reaction region gas phase linear speed is 0.9 meter per second, and axially the Peclet number is bigger by 40% than the axial Peclet number of preparatory zone of action, and the low-carbon alkene carbon back yield of reactor outlet is 82.88% (weight).
[comparative example 1]
According to embodiment 4 described condition and steps; Preparatory zone of action is not set, and 75% reclaimable catalyst is back to the main reaction region bottom, and 25% reclaimable catalyst goes regeneration; Regenerated catalyst is back to the main reaction region bottom, and the diene carbon back yield of reactor outlet is 80.5% (weight).
Obviously, adopt method of the present invention, can reach the purpose that improves yield of light olefins, have bigger technical superiority, can be used in the industrial production of low-carbon alkene.

Claims (6)

1. method that improves yield of light olefins; Comprise that the raw material that contains methyl alcohol gets into axial Peclet number less than 15 preparatory zone of action; Contact with regenerated catalyst with reclaimable catalyst; The gaseous stream of zone of action and catalyzer get into the main reaction region of axial Peclet number than the axial Peclet number big at least 20% of preparatory zone of action in advance, generate the product that comprises low-carbon alkene.
2. according to the method for the said raising yield of light olefins of claim 1, it is characterized in that said catalyzer is selected from SAPO-34.
3. according to the method for the said raising yield of light olefins of claim 1, the axial Peclet number that it is characterized in that said preparatory zone of action is less than 6.
4. according to the method for the said raising yield of light olefins of claim 1, the axial Peclet number that it is characterized in that said main reaction region is than the axial Peclet number of preparatory zone of action greatly at least 40%.
5. according to the method for the said raising yield of light olefins of claim 1, the temperature of reaction that it is characterized in that said preparatory zone of action is 380～450 ℃, and the average carbon deposition quantity massfraction of catalyzer is 1.0～4.0%.
6. according to the method for the said raising yield of light olefins of claim 1, the temperature of reaction that it is characterized in that said main reaction region is 400～485 ℃, and the gas phase linear speed is 0.8～3.0 meter per second.
CN201010262010.4A 2010-08-23 2010-08-23 Improve the method for yield of light olefins Active CN102372541B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201010262010.4A CN102372541B (en) 2010-08-23 2010-08-23 Improve the method for yield of light olefins

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201010262010.4A CN102372541B (en) 2010-08-23 2010-08-23 Improve the method for yield of light olefins

Publications (2)

Publication Number Publication Date
CN102372541A true CN102372541A (en) 2012-03-14
CN102372541B CN102372541B (en) 2016-04-13

Family

ID=45791831

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010262010.4A Active CN102372541B (en) 2010-08-23 2010-08-23 Improve the method for yield of light olefins

Country Status (1)

Country Link
CN (1) CN102372541B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101184709A (en) * 2005-05-27 2008-05-21 埃克森美孚化学专利公司 Oxygenate-to-olefin conversions in a baffled reactor
CN101270023A (en) * 2008-04-11 2008-09-24 中国石油化工股份有限公司 Method for improving selectivity of light olefin hydrocarbon
CN101402538A (en) * 2008-11-21 2009-04-08 中国石油化工股份有限公司 Method for improving yield of light olefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101184709A (en) * 2005-05-27 2008-05-21 埃克森美孚化学专利公司 Oxygenate-to-olefin conversions in a baffled reactor
CN101270023A (en) * 2008-04-11 2008-09-24 中国石油化工股份有限公司 Method for improving selectivity of light olefin hydrocarbon
CN101402538A (en) * 2008-11-21 2009-04-08 中国石油化工股份有限公司 Method for improving yield of light olefins

Also Published As

Publication number Publication date
CN102372541B (en) 2016-04-13

Similar Documents

Publication Publication Date Title
CN101333141B (en) Reaction device for conversing methanol or dimethyl ether to be low carbon olefin
CN101402538A (en) Method for improving yield of light olefins
CN101357874B (en) Method for producing low carbon olefinic hydrocarbon from methanol or dimethyl ether
CN102372569B (en) Method for preparing light olefin with methanol
CN102875289B (en) Method for preparing low-carbon olefins
CN102295505B (en) Reaction device for preparing low-carbon olefin from methanol
CN102464535B (en) Method for producing low carbon olefin from methanol or dimethyl ether
CN102464524A (en) Method for producing low-carbon olefins from methanol
CN102276390A (en) Method for adjusting product proportion in process of preparing olefin from methanol
CN102463074B (en) Reaction device for producing low-carbon olefin from methanol or dimethyl ether
CN102372542A (en) Method for improving yield of ethylene and propylene
CN102372540A (en) Method for conversing methanol to light olefin
CN102372570B (en) Method for producing low-carbon olefin by using methanol
CN102463080A (en) Reaction device for producing low-carbon olefin by using methanol as raw materials
CN102276395B (en) Method for producing ethylene and propylene
CN102464528A (en) Method for increasing yields of ethylene and propylene
CN102464534B (en) Method for producing low-carbon olefins from methanol
CN102372541B (en) Improve the method for yield of light olefins
CN103739418A (en) Method of increasing the yield of low-carbon olefins in process of preparing the low-carbon olefins from methanol
CN102295501B (en) Method for producing low-carbon olefin
CN102463083B (en) Reaction device for producing low-carbon olefin
CN102875282A (en) Reaction unit for preparing low-carbon olefins from methanol
CN102875288A (en) Method for producing low-carbon olefins
CN102276403B (en) Method for producing low-carbon olefin
CN102276399B (en) Method for producing lower olefins from methanol and naphtha

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant