CN102276399B - Method for producing lower olefins from methanol and naphtha - Google Patents
Method for producing lower olefins from methanol and naphtha Download PDFInfo
- Publication number
- CN102276399B CN102276399B CN2010101999560A CN201010199956A CN102276399B CN 102276399 B CN102276399 B CN 102276399B CN 2010101999560 A CN2010101999560 A CN 2010101999560A CN 201010199956 A CN201010199956 A CN 201010199956A CN 102276399 B CN102276399 B CN 102276399B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- petroleum naphtha
- carbon
- methanol
- ratio
- 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.)
- Active
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
- Y02P20/52—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
- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for producing lower olefins from methanol and naphtha. The method is used for mainly solving the problem of the low yield of the lower olefins in the prior art. The problem is well solved by adopting the technical scheme as follows: the method for producing the lower olefins from the methanol and the naphtha mainly comprises the following steps: (a) a raw material mainly including methanol is in contact with a catalyst in a reactor to generate a product material flow I including the lower olefins and hydrocarbon with more than four carbons and form a carbon deposition catalyst at the same time; (b) the carbon deposition catalyst enters a regenerator to be regenerated through a spent inclined tube so as to form a regeneration catalyst; (c) the regenerationcatalyst is divided into three parts, the first part returns into a methanol reactor, the second part enters the upper section of a naphtha conversion reactor and is in contact with the raw material including the hydrocarbon with more than four carbons, the third part enters the lower section of the naphtha conversion reactor and is in contact with the raw material including the naphtha, and a product material flow II including the lower olefins is generated and enters an assistant sedimentation steam stripper above the regenerator; and (d) the decaying catalyst in the assistant sedimentationsteam stripper returns to the regenerator through a spent vertical tube built-in the regenerator, wherein the ratio of the mass flow of the catalyst in the spent inclined tube to the mass flow of themethanol is 0.4-1.5; the ratio of the mass flow of the catalyst in the spent inclined tube to the mass flow of the catalyst in the spent vertical tube is less than 0.8; and the ratio of the residencetimes of the upper section and the lower section of the naphtha conversion reactor is 1.5-4.0. The method can be applied in the industrial production of the lower olefins.
Description
Technical field
The present invention relates to a kind of method of producing low-carbon alkene by methyl alcohol and petroleum naphtha.
Technical background
Low-carbon alkene, namely 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 by petroleum path, but because limited supply and the higher price of petroleum resources, 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 ethene processed, propylene.Wherein, the important alternative materials that is used for light olefin production of one class is oxygenatedchemicals, such as alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed by coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, such as methyl alcohol, can be made by coal or Sweet natural gas, and technique is very ripe, can realize up to a million tonnes industrial scale.Because the popularity in oxygenatedchemicals source, add and transform the economy that generates light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), particularly the technique by preparing olefin by conversion of methanol (MTO) is subject to increasing attention.
Petroleum naphtha is a kind of light-end products, is cut corresponding cut and is got by crude distillation or oil secondary processing.Its boiling spread is decided according to need, is generally wider boiling range, such as 20～220 ℃.Petroleum naphtha is the pyrolysis in tubular furnace preparing ethylene, and propylene and catalytic reforming are produced the important source material of benzene,toluene,xylene.As cracking stock, require petroleum naphtha form in the content of alkane and naphthenic hydrocarbon be not less than 70% (volume).The naphtha catalytic pyrolysis preparing low-carbon alkene then is under the condition that catalyzer exists, and petroleum hydrocarbon is carried out the production process that cracking obtains low-carbon alkene.Compare with traditional tube furnace steam heat cracking, this process reaction temperature is than approximately low 50～200 ℃ of steam cracking reactions, and energy consumption significantly reduces; Cracking furnace pipe inwall coking rate also can reduce, thereby but prolong operation cycle increases the boiler tube life-span; Simultaneously Carbon emission also can reduce, and has alleviated pollution, and can adjust the product mix flexibly.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene have been announced among the US6166282, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu reaction of gas speed is finished, 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 greatly reduce.But there is the lower problem of yield of light olefins in the method.
The multiple riser reaction unit of having announced among the CN1723262 with central catalyst return is low-carbon alkene technique 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 gas product are separated.But there is the lower problem of yield of light olefins in the method.
Announced a kind of method of methanol production propylene among EP0448000 and the EP0882692, methyl alcohol at first is converted into DME and water, then mixture is transported to the First reactor, and adds steam in this reactor.In the first reactor methyl alcohol with (or) dme or its mixture contact with catalyzer and react, catalyzer adopts the special-purpose ZSM-5 catalyzer that contains ZnO and CdO, 280～570 ℃ of temperature of reaction, pressure 0.01～0.1MPa prepares the product take propylene as main hydro carbons.Heavier product such as C
5 +The hydrocarbon continuation is reacted in second reactor and is converted into take propylene as main hydro carbons, sends separator back to after cooling.Product is compressed, can obtain purity after further refining is 97% chemical grade propylene.But adopt a plurality of fixed-bed reactor in this technique, because the restriction of the activity of catalyzer therefore need frequent blocked operation, and the heat-obtaining problem is also very complicated.
US 20070083071 has announced the processing method that a kind of hydrocarbon catalytic pyrolysis is produced ethene, propylene, hydrocarbon feed is converted into the product that comprises low-carbon alkene in catalytic cracker, then product stream is separated into C2～C3 alkane, C2～C3 alkene, three kinds of logistics of C4+ hydrocarbon by series of process, C2～C3 alkane is returned tube cracking furnace carry out thermo-cracking, the C4+ hydrocarbon returns catalytic cracker and carries out catalytic pyrolysis, finally obtains ethene, the propylene product of higher yields.The method adopts riser reactor, and reactant residence time is shorter, and low-carbon alkene product once through yield is lower.
Although there has been respectively the technology of methanol-to-olefins, petroleum naphtha alkene processed in the prior art, but two kinds of techniques there is no the precedent of coupling operation in the prior art, and how effectively to utilize for the carbon four above high-carbon hydrocarbon by products that produce in the methanol-to-olefins reaction process also be one of difficult problem.Simultaneously, all there is the lower problem of yield of light olefins in prior art.The present invention has solved the problems referred to above targetedly.
Summary of the invention
Technical problem to be solved by this invention is the not high problem of yield of light olefins that exists in the prior art, and a kind of new method by methyl alcohol and petroleum naphtha production low-carbon alkene is provided.The method is used for the production of low-carbon alkene, has advantages of that yield of light olefins is higher.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method of producing low-carbon alkene by methyl alcohol and petroleum naphtha, said method comprising the steps of: the raw material that (a) is mainly methyl alcohol contacts with catalyzer in reactor, generation comprises the product stream I of low-carbon alkene, carbon four above hydrocarbon, forms simultaneously carbon deposition catalyst; (b) carbon deposition catalyst enters revivifier regeneration by inclined tube to be generated, forms regenerated catalyst; (c) regenerated catalyst is divided into three parts, first part returns methanol reactor, second section enters petroleum naphtha conversion reactor epimere, contact with the raw material that comprises carbon four above hydrocarbon, third part enters petroleum naphtha conversion reactor hypomere, contact with the raw material that comprises petroleum naphtha, generate the product stream II that comprises low-carbon alkene, enter the auxiliary sedimentation stripper of revivifier top; (d) decaying catalyst in the auxiliary sedimentation stripper returns revivifier by the regeneration standpipe that is built in the revivifier; Wherein, inclined tube mass flow of catalyst to be generated is 0.4～1.5 with the ratio of the mass rate of methyl alcohol, and the ratio of the mass flow of catalyst in inclined tube to be generated and the regeneration standpipe is less than 0.8, and petroleum naphtha conversion reactor epimere is 1.5～4.0 with the ratio of the hypomere residence time.
In the technique scheme, described molecular sieve comprises ZSM-5; Described methanol conversion is fast fluidized bed; Described petroleum naphtha conversion reactor is the reducing riser tube, and riser tube epimere diameter and hypomere diameter ratio are 1.2～2.5: 1; Described carbon four above hydrocarbon are from carbon four hydrocarbon mixtures of separating in the product stream I, and wherein the alkene mass content is greater than 60%; Described product stream I and product stream II share a cover separation process; Described regenerated catalyst carbon deposition quantity massfraction is less than 0.5%; Described petroleum naphtha boiling range is between 20 ℃～220 ℃; Described regenerated catalyst is divided into three parts, and 20～40% return methanol conversion by regenerator sloped tube, and 20～40% enter petroleum naphtha conversion reactor epimere, and 20～60% enter petroleum naphtha conversion reactor hypomere; Reaction conditions is in the described methanol conversion: temperature of reaction is 400～500 ℃, and the gas phase linear speed is 0.8～2.0 meter per second; Reaction conditions is in the described petroleum naphtha conversion reactor: temperature of reaction is 570～650 ℃, hypomere gas phase linear speed is 5～10 meter per seconds, epimere gas phase linear speed is 1.5～3.0 meter per seconds, and the mass rate of catalyzer is 5.0～8.0 with the ratio of the mass rate of petroleum naphtha in the regeneration standpipe; The silica alumina ratio of described ZSM-5 molecular sieve is 30～100.
Adopt method of the present invention, methanol-to-olefins and two kinds of techniques of producing olefin hydrocarbon by catalytic pyrolysis of naphtha organically are coupled, adopt a kind of catalyzer, reach the purpose of common property low-carbon alkene.The present invention has effectively guaranteed naphtha cracking and the required gas-solid contact time of carbon four above hydrocarbon pyrolysis reactions by adopting lower thin and upper thick reducing riser tube, has improved the yield of alkene.Because naphtha catalytic cracking and carbon four above high-carbon hydrocarbon catalytic cracking reaction types have similarity, the by-product carbon four above high-carbon hydrocarbons that in the method for the invention methanol conversion generated return the epimere of petroleum naphtha conversion reactor, effectively guaranteeing on the basis of catalyst activity and gas-solid contact time increased low carbon olefine output as much as possible.Therefore, adopt method of the present invention, can realize improving the purpose of yield of light olefins.
Adopt technical scheme of the present invention: described molecular sieve comprises ZSM-5; Described methanol conversion is fast fluidized bed; Described petroleum naphtha conversion reactor is the reducing riser tube, and riser tube epimere diameter and hypomere diameter ratio are 1.2～2.5: 1; Described carbon four above hydrocarbon are from carbon four hydrocarbon mixtures of separating in the product stream I, and wherein the alkene mass content is greater than 60%; Described product stream I and product stream II share a cover separation process; Described regenerated catalyst carbon deposition quantity massfraction is less than 0.5%; Described petroleum naphtha boiling range is between 20 ℃～220 ℃; Described regenerated catalyst is divided into three parts, and 20～40% return methanol conversion by regenerator sloped tube, and 20～40% enter petroleum naphtha conversion reactor epimere, and 20～60% enter petroleum naphtha conversion reactor hypomere; Reaction conditions is in the described methanol conversion: temperature of reaction is 400～500 ℃, and the gas phase linear speed is 0.8～2.0 meter per second; Reaction conditions is in the described petroleum naphtha conversion reactor: temperature of reaction is 570～650 ℃, hypomere gas phase linear speed is 5～10 meter per seconds, epimere gas phase linear speed is 1.5～3.0 meter per seconds, and the mass rate of catalyzer is 5.0～8.0 with the ratio of the mass rate of petroleum naphtha in the regeneration standpipe; The silica alumina ratio of described ZSM-5 molecular sieve is 30～100, and the low-carbon alkene carbon base absorption rate of product stream I can reach 60.14% weight, and the low-carbon alkene carbon base absorption rate of product stream II can reach 40.42% weight, has obtained preferably technique effect.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
Among Fig. 1,1 is the charging of methanol conversion raw material; 2 is the methanol conversion reaction zone; 3 are gas-solid sharp separation equipment; 4 is the methanol conversion stripping zone; 5 is methanol conversion reclaimable catalyst circulation inclined tube; 6 is inclined tube to be generated; 7 is the methanol conversion interchanger; 8 is the methanol conversion gas-solid cyclone separator; 9 is the methanol conversion negative area; 10 is the product collection chamber; 11 is product stream I outlet line; 12 is regenerator sloped tube; 13 is plug valve to be generated; 14 is the regenerating medium source line; 15 is regeneration standpipe; 16 is regenerator sloped tube; 17 is the feed naphtha feeding line; 18 is regenerator sloped tube; 19 is pre lift zone; 20 is revivifier; 21 is stripping medium inlet pipeline; 22 is stripping zone; 23 is the revivifier cyclonic separator; 24 is the regenerated flue gas outlet line; 25 are auxiliary sedimentation stripper; 26 is gas-solid cyclone separator; 27 is product stream II outlet line; 28 is the material feeding tube line that comprises carbon four above hydrocarbon; 29 is petroleum naphtha conversion reactor epimere; 30 is petroleum naphtha conversion reactor hypomere.
Methyl alcohol enters in the methanol conversion reaction zone 2 through feeding line 1, contact with molecular sieve catalyst, reaction generates the product that contains low-carbon alkene, carry reclaimable catalyst and enter methanol conversion negative area 9 through gas-solid sharp separation equipment 3, wherein, most of catalyzer that gas-solid sharp separation equipment 3 is separated enters methanol conversion stripping zone 4, and gaseous products and part are not carried out Re-isolation by the catalyzer of gas-solid sharp separation device separates through entering cyclonic separator 8 separation, catalyzer turns back to methanol conversion stripping zone 4 through the dipleg of cyclonic separator 8, and gaseous products enters collection chamber 10 and enters follow-up centrifugal station by outlet line 11.Be divided into two portions by gas-solid sharp separation equipment 3 and cyclonic separator 8 isolated reclaimable catalysts through behind the stripping, turn back to the bottom of methanol conversion reaction zone 2 after 7 heat exchange of part process interchanger by catalyst recirculation inclined tube 5, a part enters coke-burning regeneration in the revivifier 20 through inclined tube 6 to be generated in addition, the flue gas that the coke burning generates enters follow-up energy-recuperation system through behind the cyclonic separator 23 by exhanst gas outlet pipeline 24, a regenerated catalyst part is returned in the methanol conversion reaction zone 2 by regenerator sloped tube 12, a part enters petroleum naphtha conversion reactor hypomere 30 by regenerator sloped tube 16, contact with feed naphtha, the product that generates carries catalyzer and enters petroleum naphtha conversion reactor epimere 29, contact with the regenerated catalyst that from regenerator sloped tube 18, comes with the raw material that comprises carbon four above hydrocarbon, the mixing prod of producing enters auxiliary sedimentation stripper 25, after the gas-solid cyclone separator separation, catalyzer enters stripping zone 22, return revivifier 20 through stripping by regeneration standpipe 15, the product of generation enters centrifugal station through outlet line 27.
The invention will be further elaborated below by embodiment, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
In small-sized fast fluidized bed reaction-regenerative device, type of reactor is with shown in Figure 1, and catalyzer adopts ZSM-5, and silica alumina ratio is 50 (volumes).The reaction of methanol conversion district medial temperature is 440 ℃, and the gas phase linear speed is 1.12 meter per seconds, and purity is 99.5% methanol feeding, and the methyl alcohol weight hourly space velocity is 5.7 hours
-1, inclined tube mass flow of catalyst to be generated is 0.7 with the ratio of methanol feeding mass rate, and the revivifier medial temperature is 675 ℃, and the regenerated catalyst carbon deposition quantity is 0.24% (weight).The ratio of mass flow of catalyst is 0.5 in inclined tube to be generated and the regeneration standpipe.The petroleum naphtha boiling range is at 25～204 ℃, the content of alkane and naphthenic hydrocarbon is 93.5% (weight), and olefin(e) centent is less than 0.2% (weight), and aromaticity content is 6.2% (weight), and add the water vapour of 15% (weight), with the petroleum naphtha parallel feeding.The ratio of petroleum naphtha conversion reactor epimere diameter and hypomere diameter is 2.5: 1, ratio with gas phase residence time of hypomere in the epimere is 2.1, and riser tube hypomere temperature of reaction is 632 ℃, and hypomere gas phase linear speed is 7.3 meter per seconds, the epimere temperature of reaction is 608 ℃, and epimere gas phase linear speed is 2.1 meter per seconds.Section feeding comprises that (wherein olefin(e) centent is 88% for the above hydrocarbon of mixed c 4 of massfraction 60% on the petroleum naphtha conversion reactor, carbon four hydrocarbon total amounts are 91%), 30% petroleum naphtha, 10% water vapour, regenerated catalyst is divided into three parts, 20% returns methanol conversion by regenerator sloped tube, 20% enters petroleum naphtha conversion reactor epimere, and 60% enters petroleum naphtha conversion reactor hypomere.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of product stream I can reach 60.14% weight, and the yield of light olefins of product stream II can reach 36.25% weight.
[embodiment 2]
According to embodiment 1 described condition, catalyzer adopts ZSM-5, and silica alumina ratio is 30 (volumes).The reaction of methanol conversion district medial temperature is 400 ℃, and the gas phase linear speed is 0.8 meter per second, and inclined tube mass flow of catalyst to be generated is 0.4 with the ratio of methanol feeding mass rate, and the revivifier medial temperature is 668 ℃, and the regenerated catalyst carbon deposition quantity is 0.21% (weight).The ratio of mass flow of catalyst is 0.34 in inclined tube to be generated and the regeneration standpipe.Petroleum naphtha conversion reactor epimere is 4.0 with the ratio of the gas phase residence time of hypomere, and riser tube hypomere temperature of reaction is 649 ℃, and hypomere gas phase linear speed is 10 meter per seconds, and the epimere temperature of reaction is 631 ℃, and epimere gas phase linear speed is 1.5 meter per seconds.Section feeding comprises that (wherein olefin(e) centent is 88% for the above hydrocarbon of mixed c 4 of massfraction 75% on the petroleum naphtha conversion reactor, carbon four hydrocarbon total amounts are 91%), 10% petroleum naphtha, 15% water vapour, regenerated catalyst is divided into three parts, 40% returns methanol conversion by regenerator sloped tube, 40% enters petroleum naphtha conversion reactor epimere, and 20% enters petroleum naphtha conversion reactor hypomere.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of product stream I can reach 56.08% weight, and the yield of light olefins of product stream II can reach 39.17% weight.
[embodiment 3]
According to embodiment 1 described condition, catalyzer adopts ZSM-5, and silica alumina ratio is 100 (volumes).The reaction of methanol conversion district medial temperature is 500 ℃, and the gas phase linear speed is 2.0 meter per seconds, and inclined tube mass flow of catalyst to be generated is 1.5 with the ratio of methanol feeding mass rate, and the revivifier medial temperature is 640 ℃, and the regenerated catalyst carbon deposition quantity is 0.47% (weight).The ratio of mass flow of catalyst is 0.8 in inclined tube to be generated and the regeneration standpipe.The ratio of petroleum naphtha conversion reactor epimere diameter and hypomere diameter is 1.2: 1, petroleum naphtha conversion reactor epimere is 1.5 with the ratio of the gas phase residence time of hypomere, riser tube hypomere temperature of reaction is 583 ℃, hypomere gas phase linear speed is 5 meter per seconds, the epimere temperature of reaction is 71 ℃, and epimere gas phase linear speed is 3.0 meter per seconds.Section feeding comprises that (wherein olefin(e) centent is 88% for the above hydrocarbon of mixed c 4 of massfraction 82% on the petroleum naphtha conversion reactor, carbon four hydrocarbon total amounts are 91%), 18% water vapour, the stability that keeps catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, the low-carbon alkene carbon base absorption rate of product stream I can reach 53.69% weight, and the yield of light olefins of product stream II can reach 32.89% weight.
[embodiment 4]
According to embodiment 1 described condition, section feeding comprises that (wherein olefin(e) centent is 88% for the above hydrocarbon of mixed c 4 of massfraction 70% on the petroleum naphtha conversion reactor, carbon four hydrocarbon total amounts are 91%), 30% water vapour, section feeding comprises that (wherein olefin(e) centent is 88% for the above hydrocarbon of mixed c 4 of massfraction 50% under the petroleum naphtha conversion reactor, carbon four hydrocarbon total amounts are 91%), 35% petroleum naphtha, 15% water vapour, the low-carbon alkene carbon base absorption rate of product stream I can reach 59.95% weight, and the yield of light olefins of product stream II can reach 40.42% weight.
[comparative example]
According to embodiment 1 described condition, do not establish the petroleum naphtha conversion reactor, the above hydrocarbon of mixed c 4 in the product stream I does not return yet again and transforms, and regenerated catalyst directly turns back to the bottom of fluidized bed reaction zone, and the low-carbon alkene carbon base absorption rate of product stream I is 57.84% weight.
Obviously, adopt method of the present invention, can reach the purpose that improves yield of light olefins, have larger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (5)
1. method of being produced low-carbon alkene by methyl alcohol and petroleum naphtha said method comprising the steps of:
(a) raw material that is mainly methyl alcohol contacts with molecular sieve catalyst in methanol conversion, generates the product stream I that comprises low-carbon alkene, carbon four above hydrocarbon, forms simultaneously carbon deposition catalyst;
(b) described carbon deposition catalyst enters revivifier regeneration by inclined tube to be generated, forms regenerated catalyst;
(c) described regenerated catalyst is divided into three parts, first part returns methanol conversion by regenerator sloped tube, second section enters petroleum naphtha conversion reactor epimere, contact with the raw material that comprises described carbon four above hydrocarbon, third part enters petroleum naphtha conversion reactor hypomere, contact with the raw material that comprises petroleum naphtha, generate the product stream II that comprises low-carbon alkene, carry catalyzer and enter the auxiliary sedimentation stripper that is positioned at the revivifier top;
(d) decaying catalyst in the auxiliary sedimentation stripper returns revivifier by the regeneration standpipe that is built in the revivifier;
Wherein, inclined tube mass flow of catalyst to be generated is 0.4～1.5 with the ratio of the mass rate of methyl alcohol, the ratio of the mass flow of catalyst in inclined tube to be generated and the regeneration standpipe is less than 0.8, and the ratio of the petroleum naphtha conversion reactor epimere residence time with the hypomere residence time is 1.5～4.0;
Described molecular sieve comprises ZSM-5; Described methanol conversion is fast fluidized bed; Described petroleum naphtha conversion reactor is the reducing riser tube, and riser tube epimere diameter and hypomere diameter ratio are 1.2～2.5: 1; Described regenerated catalyst carbon deposition quantity massfraction is less than 0.5%; Described regenerated catalyst is divided into three parts, and 20～40% return methanol conversion by regenerator sloped tube, and 20～40% enter petroleum naphtha conversion reactor epimere, and 20～60% enter petroleum naphtha conversion reactor hypomere;
Reaction conditions is in the described methanol conversion: temperature of reaction is 400～500 ℃, and the gas phase linear speed is 0.8～2.0 meter per second; Reaction conditions is in the described petroleum naphtha conversion reactor: temperature of reaction is 570～650 ℃, hypomere gas phase linear speed is 5～10 meter per seconds, epimere gas phase linear speed is 1.5～3.0 meter per seconds, and the mass rate of catalyzer is 5.0～8.0 with the ratio of the mass rate of petroleum naphtha in the regeneration standpipe.
2. described method of being produced low-carbon alkene by methyl alcohol and petroleum naphtha according to claim 1 is characterized in that described carbon four above hydrocarbon from carbon four hydrocarbon mixtures of separating among the product stream I, and wherein the alkene mass content is greater than 60%.
3. described method of being produced low-carbon alkene by methyl alcohol and petroleum naphtha according to claim 1 is characterized in that described product stream I and product stream II share a cover separation process.
4. described method of being produced low-carbon alkene by methyl alcohol and petroleum naphtha according to claim 1 is characterized in that described petroleum naphtha boiling range is between 20 ℃～220 ℃.
5. described method of being produced low-carbon alkene by methyl alcohol and petroleum naphtha according to claim 1 is characterized in that the silica alumina ratio of described ZSM-5 molecular sieve is 30～100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101999560A CN102276399B (en) | 2010-06-11 | 2010-06-11 | Method for producing lower olefins from methanol and naphtha |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101999560A CN102276399B (en) | 2010-06-11 | 2010-06-11 | Method for producing lower olefins from methanol and naphtha |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102276399A CN102276399A (en) | 2011-12-14 |
| CN102276399B true CN102276399B (en) | 2013-10-16 |
Family
ID=45102192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101999560A Active CN102276399B (en) | 2010-06-11 | 2010-06-11 | Method for producing lower olefins from methanol and naphtha |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102276399B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336726B (en) * | 2018-11-29 | 2024-05-31 | 北京惠尔三吉绿色化学科技有限公司 | Process for preparing propylene ethylene by coupling catalytic cracking of carbon four, light oil and methanol |
| CN111229135A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Raw material conversion device containing naphtha |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101104576A (en) * | 2006-07-13 | 2008-01-16 | 中国石油化工股份有限公司 | Combination catalysis conversion method for organic oxygen-containing compound and hydrocarbons |
| 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 |
| CN101279875A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for increasing production of ethylene and propone |
| CN101279877A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for increasing yield of ethylene and propone in conversion process of oxocompound |
| WO2009065875A1 (en) * | 2007-11-19 | 2009-05-28 | Shell Internationale Research Maatschappij B.V. | Process for converting an oxygenate into an olefin-containing product, and reactor system |
| CN101633593A (en) * | 2008-07-26 | 2010-01-27 | 中国石化集团洛阳石油化工工程公司 | Conversion method of C4 and heavier components |
-
2010
- 2010-06-11 CN CN2010101999560A patent/CN102276399B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101104576A (en) * | 2006-07-13 | 2008-01-16 | 中国石油化工股份有限公司 | Combination catalysis conversion method for organic oxygen-containing compound and hydrocarbons |
| CN101279875A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for increasing production of ethylene and propone |
| CN101279877A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for increasing yield of ethylene and propone in conversion process of oxocompound |
| WO2009065875A1 (en) * | 2007-11-19 | 2009-05-28 | Shell Internationale Research Maatschappij B.V. | Process for converting an oxygenate into an olefin-containing product, and reactor system |
| 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 |
| CN101633593A (en) * | 2008-07-26 | 2010-01-27 | 中国石化集团洛阳石油化工工程公司 | Conversion method of C4 and heavier components |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102276399A (en) | 2011-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101402538B (en) | Method for improving yield of light olefins | |
| CN101333141B (en) | Reaction device for conversing methanol or dimethyl ether to be low carbon olefin | |
| CN102464524B (en) | Method for producing low-carbon olefins from methanol | |
| CN102276406B (en) | Method for increasing yield of propylene | |
| CN102875285B (en) | Methyl alcohol and light naphthar are catalytically conveted to the method for low-carbon alkene | |
| CN101306969B (en) | Reaction device for preparing low-carbon olefin from oxygen-containing compounds | |
| CN102875289B (en) | Method for preparing low-carbon olefins | |
| CN102276404B (en) | Reaction device for producing lower olefins from methanol | |
| CN102276389B (en) | Reaction and regeneration device for catalyzing and converting methanol and naphtha into lower olefins | |
| CN102276391B (en) | Method for catalyzing and converting methanol and naphtha into low-carbon olefins | |
| CN102276399B (en) | Method for producing lower olefins from methanol and naphtha | |
| CN102875283B (en) | The method of low-carbon alkene is prepared by methyl alcohol and petroleum naphtha | |
| CN102276400B (en) | Low carbon olefin reaction-regeneration device by using methanol | |
| CN102875288B (en) | Method for producing low-carbon olefins | |
| CN102875304B (en) | Method for preparing low carbon olefins from methanol and naphtha | |
| CN102276395B (en) | Method for producing ethylene and propylene | |
| CN102875286B (en) | Method for producing low-carbon olefins from methanol and naphtha | |
| CN102276403B (en) | Method for producing low-carbon olefin | |
| CN102295501B (en) | Method for producing low-carbon olefin | |
| CN103739418A (en) | Method of increasing the yield of low-carbon olefins in process of preparing the low-carbon olefins from methanol | |
| CN102875297B (en) | The method of low-carbon alkene is prepared with methyl alcohol and petroleum naphtha | |
| CN102875284B (en) | The reaction unit of low-carbon alkene is prepared with methyl alcohol and petroleum naphtha | |
| CN102875295A (en) | Production method of low-carbon olefins | |
| CN102274751A (en) | Steam stripping method for spent catalyst in process for preparing olefins by oxygenated chemicals | |
| CN102875279B (en) | Reaction unit for preparing low-carbon 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 |