CN108191593A - A kind of olefin preparation method and device - Google Patents

A kind of olefin preparation method and device Download PDF

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Publication number
CN108191593A
CN108191593A CN201810016987.4A CN201810016987A CN108191593A CN 108191593 A CN108191593 A CN 108191593A CN 201810016987 A CN201810016987 A CN 201810016987A CN 108191593 A CN108191593 A CN 108191593A
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China
Prior art keywords
alcohol
catalyst
reaction
methanol
olefin preparation
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CN201810016987.4A
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Chinese (zh)
Inventor
王明党
郑红霞
王宝石
岳建伟
席清波
吴辰捷
郭巧玲
唐娉玺
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Sinopec Engineering Group Co Ltd
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Sinopec Engineering Group Co Ltd
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Priority to CN201810016987.4A priority Critical patent/CN108191593A/en
Publication of CN108191593A publication Critical patent/CN108191593A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • C07C4/10—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from acyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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

Abstract

The present invention relates to olefin producing technologies field, more particularly, to a kind of olefin preparation method and device.Olefin preparation method is included to C4‑C8Hydrocarbon raw material and raw polyol are preheated respectively；Make the C after preheating4‑C8Hydro carbons and alcohol jointly with catalyst for cracking under fluidized state haptoreaction, obtain reaction product and carbon deposition catalyst；The reaction product is detached with the carbon deposition catalyst；Isolated ethylene, propylene are carried out to the reaction product.Wherein, the alcohol is methanol either not include the mixed alcohol of methanol or being the mixed alcohol for including methanol.The type of the applicable alcohol of olefin preparation method provided by the invention is more, and selectivity is more, can more be used widely.It can be using the by-product mixed alcohol generated in chemical process as the reaction raw materials of olefin preparation method provided by the invention, so as to which the effective upgrading of by-product low value mixed alcohol be enable to utilize, waste of resource is avoided, is good for the environment, moreover it is possible to which reduction prepares the cost of ethylene, propylene.

Description

A kind of olefin preparation method and device
Technical field
The present invention relates to olefin producing technologies field, more particularly, to a kind of olefin preparation method and device.
Background technology
The low-carbon alkenes such as ethylene, propylene are most important basic chemical raw materials, with the fast development of chemical industry, to low The demand of carbon olefin is also being continuously increased.The industrial method for obtaining the low-carbon alkenes such as ethylene, propylene is mainly using tradition Steam splitting process, in recent years, MTO/MTP techniques and ethane, dehydrogenating propane technique productions olefin product also become low-carbon Effective supplement in alkene source.In order to meet the needs of chemical industry is growing to low-carbon alkene, expand low-carbon alkene production Raw material sources and production ways be always chemical industry pursue target, utilize various light hydrocarbons catalytic pyrolysis low-carbon alkene Hydrocarbon causes the extensive concern of industry.
In the relevant technologies, someone using a kind of coupling petroleum hydrocarbon catalytic pyrolysis preparing low-carbon olefins method, with stone Petroleum hydrocarbon class is raw material with methanol or dimethyl ether, using fluidized-bed reactor, in the effect of solid acid catalyst and high-temperature vapor Under, pass through the cracking catalyst process preparing low-carbon olefins of coupling.The patent is the heat release of methanol decomposition and the suction of hydrocarbon cracking Heat organically combines, and improves the deficiency of heat when hydro carbons individually cracks.
But the problem is that, the above method is suitable for the cracking heat release of methanol, has limitation, then can be suitable for The range that this method crack exothermic substance is small, and selectivity is small.And since methanol is important Elementary Chemical Industry raw material, Price is relatively high, and for coupling cracking with petroleum hydrocarbon, the cost is relatively high.
Invention content
The purpose of the present invention is to provide a kind of olefin preparation method, to solve alkene preparation side in the prior art The technical issues of range of the exothermic substance of cracking that method can use is small.
The present invention provides a kind of olefin preparation method, including：
To C4-C8Hydrocarbon raw material and raw polyol are preheated respectively；
Make the C after preheating4-C8Hydro carbons and alcohol jointly with catalyst for cracking under fluidized state haptoreaction, reacted Product and carbon deposition catalyst；
The reaction product is detached with the carbon deposition catalyst；
Isolated ethylene, propylene are carried out to the reaction product；
Wherein, the alcohol is methanol either not include the mixed alcohol of methanol or being the mixed alcohol for including methanol；
Make the C after preheating4-C8Hydro carbons and alcohol jointly with catalyst for cracking under fluidized state haptoreaction, reacted During product and carbon deposition catalyst, reaction temperature is 400 DEG C -670 DEG C, reaction pressure 0.01MPa-0.30Mpa, reaction weight Amount air speed is 1h-1-10h-1。
Further, the catalyst includes active component and modified component；The active component is less than for silica alumina ratio 160 modified zeolite；The modified component is in phosphorus containg substances, II A groups metal oxide and rare-earth oxide three At least two combination.
Further, the content of the active component in the catalyst is 15%~95%.
Further, the modified zeolite is the ZSM-5 zeolite that silica alumina ratio is 40~100.
Further, C4-C8Hydrocarbon raw material is preheated to 200 DEG C -650 DEG C, and raw polyol preheating temperature is no more than 300 DEG C.
Further, C4-C8The weight ratio of hydro carbons and alcohol is 0-4:1.
Further, C4-C8The weight ratio of hydro carbons and alcohol is 0.5-2:1.
Further, the reaction weight space velocity is 2-1-5h-1。
Further, it after carrying out separating step to the reaction product and the carbon deposition catalyst, further includes, carbon distribution is urged Agent is regenerated.
The present invention also provides a kind of alkene preparation facilities, connect including fluidized-bed reactor and respectively with fluidized-bed reactor Logical C4-C8Hydrocarbon raw material storage tank and raw polyol storage tank.
Olefin preparation method provided by the invention passes through to C4-C8Hydro carbons carries out copyrolysis with alcohol, makes the anti-of alcohol cracking release The C that hot should be absorbed heat4-C8Hydrocarbon cracking is absorbed and utilized, and is realized that the optimization of energy is complementary, is solved when the two is individually reacted because needing Remove or additional heat and caused by complexity in engineering, so as to simplify engineering, while can avoid caused by afterburning Catalyst hot-spot, the loss and structure for reducing catalyst destroy.
The type of the applicable alcohol of olefin preparation method provided by the invention is more, and selectivity is more, extensively should can more obtain With with more practicability.The mixing that can will be generated in alcohol or other Chemical Manufactures in Fischer-Tropsch synthesis, in methanol production Reaction raw materials of the alcohol as olefin preparation method provided by the invention, so as to which by-product low value mixed alcohol be enable effectively to carry Matter utilizes, and avoids waste of resource, is good for the environment, moreover it is possible to which reduction prepares the cost of ethylene, propylene, and it is vigorous to obtain the market demand Ethylene, propylene, and then the overall economic efficiency of enterprise can be improved.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution of the prior art Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is the flow chart of olefin preparation method provided in an embodiment of the present invention；
Fig. 2 is alkene preparation facilities provided in an embodiment of the present invention；
Fig. 3 is table 1- catalyst physico-chemical properties；
Fig. 4 is formed for table 2- mixing raw polyol；
Fig. 5 is table 3- coker gasoline properties；
Fig. 6 couples lytic effect for table 4- methanol with 1- butylene；
Fig. 7 couples lytic effect for table 5- mixed alcohols with 1- butylene；
Fig. 8 couples lytic effect for table 6- methanol with coker gasoline；
Fig. 9 couples lytic effect for table 7- mixed alcohols with coker gasoline.
Reference numeral：1- oil gas vents；The first cyclone separators of 2-；The close phase reaction device beds of 3-；4- alcohols feedstocks are distributed Pipe；5- hydrocarbon raw material distributor pipes；6- stripped vapor distributor pipes；7- reclaimable catalyst circulation pipes；8- regenerated catalyst circulation pipes；9- Distributor pipe of cardinal wind；10- regenerator beds；The second cyclone separators of 11-；12- exhanst gas outlets.
Specific embodiment
Technical scheme of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation Example is part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill Personnel's all other embodiments obtained without making creative work, shall fall within the protection scope of the present invention.
It should be noted that C4-C8Hydro carbons can be C4To C8Detailed hydrocarbon, or C4To C8The mixing of any combination Hydrocarbon, for example, C4With C5Combination, C3、C6And C7Combination or C4、C5、C6、C7And C8Any combinations such as combination.
Fig. 1 is the flow chart of olefin preparation method provided in an embodiment of the present invention；Fig. 2 is alkene provided in an embodiment of the present invention Hydrocarbon preparation facilities；Fig. 3 is table 1- catalyst physico-chemical properties；Fig. 4 is formed for table 2- mixing raw polyol；Fig. 5 is table 3- coker gasolines Property；Fig. 6 couples lytic effect for table 4- methanol with 1- butylene；Fig. 7 couples lytic effect for table 5- mixed alcohols with 1- butylene；Figure 8 couple lytic effect for table 6- methanol with coker gasoline；Fig. 9 couples lytic effect for table 7- mixed alcohols with coker gasoline.
As shown in Figure 1, the present invention provides a kind of olefin preparation method, including：
To C4-C8Hydrocarbon raw material and raw polyol carry out preheating S1 respectively；
Make the C after preheating4-C8Hydro carbons and alcohol jointly with catalyst for cracking under fluidized state haptoreaction, reacted Product and carbon deposition catalyst S2；
The reaction product is carried out with the carbon deposition catalyst to detach S3；
Isolated ethylene, propylene S4 are carried out to the reaction product.
Wherein, alcohol is methanol either not include the mixed alcohol of methanol or being the mixed alcohol for including methanol；It is described to make C after preheating4-C8Hydro carbons and alcohol obtain reaction product and carbon deposition catalyst process jointly with catalyst for cracking haptoreaction In, reaction temperature is 400 DEG C -670 DEG C, reaction pressure 0.01MPa-0.30Mpa, and the weight space velocity of reaction is 1h-1-10h-1。
Olefin preparation method provided in this embodiment, required response parameter are：Reaction temperature is 400 DEG C -670 DEG C, instead Pressure is answered as 0.01MPa-0.30Mpa, the weight space velocity of the reaction is 1h-1-10h-1, just make C under the above-described reaction conditions4- C8Hydro carbons obtains expected product with alcohol copyrolysis, and above-mentioned reaction condition can ensure being normally carried out for cracking reaction.
Wherein, reaction temperature be 400 DEG C -670 DEG C, that is, reaction temperature can be 400 DEG C, 460 DEG C, 520 DEG C, 580 DEG C or Any value in 670 DEG C of grade sections of person.
Preferably, reaction temperature takes the temperature of 500 DEG C of -610 DEG C of temperature ranges, and the temperature of the range can reach preferable Reaction effect, additionally it is possible to avoid heating temperature high and waste of energy, so as to save production cost.
Reaction pressure is 0.01MPa-0.30Mpa, that is, reaction pressure can be 0.01Mpa, 0.09Mpa, 0.17Mpa, Any value in the sections such as 0.25Mpa or 0.30Mpa.
Preferably, reaction pressure takes 0.1Mpa-0.2Mpa, the section pressure, easy to implement in engineering, and has relatively high Olefins yield.
Reaction velocity is 1h-1-10h-1, that is, reaction velocity can be 1h-1、4h-1、6h-1、8h-1Or 10h-1Deng the section Any value.
Preferably, reaction velocity takes 2h-1-5h-1, which can be such that catalyst is come into full contact with raw material, so as to Promote cracking reaction complete, and can be to avoid air speed is small and influences the treating capacity of raw material.
C4-C8Hydro carbons refers to hydro carbons of the carbon number more than or equal to four or the C rich in alkene obtained by secondary operation4-C8Lightweight Hydrocarbon fraction, the fraction can come from FCC apparatus, coking plant, steam cracking device, MTBE devices, MTO/MTP devices and expense Hold in the palm synthesizer etc..
The mixed alcohol for not including methanol can be ethyl alcohol, propyl alcohol, butanol, sec-butyl alcohol, isobutanol, amylalcohol, n-butanol, isoamyl Two kinds or more of combinations in the alcohol such as alcohol.Mixed alcohol comprising methanol can be ethyl alcohol, propyl alcohol, butanol, sec-butyl alcohol, isobutyl The combination of one or more of alcohol such as alcohol, amylalcohol, n-butanol, isoamyl alcohol and methanol.
Olefin preparation method provided in this embodiment passes through to C4-C8Hydro carbons carries out copyrolysis with alcohol, makes alcohol cracking release The C that reaction heat is absorbed heat4-C8Hydrocarbon cracking is absorbed and utilized, and realizes that the optimization of energy is complementary, when both solving individually reaction because Need to remove or additional heat and caused by complexity in engineering, so as to simplify engineering, while can avoid caused by afterburning Catalyst hot-spot, reduce catalyst loss and structure destroy.
The type of the applicable alcohol of olefin preparation method provided in this embodiment is more, and selectivity is more, can more obtain extensively Using with more practicability.
At present, in F- T synthesis technology while synthetic liquid fuel is obtained, a considerable number of water phase pair is also produced Product, wherein tens kinds of important chemical products such as alcohol, aldehyde, ketone, acid containing low carbon number, will thoroughly detach it, It needs to carry out multitower rectifying, flow is complicated, and energy consumption is higher.The general way of coal liquifaction enterprise is that water-phase product is carried out at present Predistillation concentrate, slough carboxylic acid, obtain the mixed alcohol of a concentration of 10%-20% or so, mainly form for methanol, ethyl alcohol, Propyl alcohol, butanol and a small amount of acetaldehyde and acetone, the part mixed alcohol are handled with low value harmful influence, directly influence the effect of enterprise Benefit.
In addition, normal propyl alcohol, sec-butyl alcohol, isobutanol, amylalcohol, n-butanol, isoamyl can be also generated in the industrial production of methanol The alcohols byproduct such as alcohol in the rectification process for obtaining refined methanol, can obtain mixed alcohol fraction simultaneously, at present, part mixing Alcohol is mainly added in diesel oil as fuel oil, is not effectively used.
It then can be using the mixed alcohol generated in alcohol or other Chemical Manufactures in Fischer-Tropsch synthesis, in methanol production as this The reaction raw materials for the olefin preparation method that embodiment provides, so as to enable the effective upgrading profit of by-product low value mixed alcohol With avoiding waste of resource, be good for the environment, moreover it is possible to which reduction prepares the cost of ethylene, propylene, obtains the vigorous second of the market demand Alkene, propylene, and then the overall economic efficiency of enterprise can be improved.
On above-described embodiment basis, further, C4-C8Hydrocarbon raw material is preheated to 200 DEG C -650 DEG C, that is, C4-C8 Hydrocarbon raw material preheating temperature can be any value in the section such as 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C or 650 DEG C, C4-C8Hydro carbons preheating temperature can be heated to preset temperature during could ensureing reheating in next step in the range, and preheat Temperature is excessively high to influence C4-C8The cracking reaction of hydro carbons, cannot get desired product.Similarly raw polyol preheating temperature is no more than 300 DEG C, it avoids influencing cracking reaction.
C4-C8Hydrocarbon raw material, raw polyol specific preheating temperature needs put down according to the heat of whole system in alkene preparation process It weighs to be calculated.
On above-described embodiment basis, further, the catalyst for cracking includes active component and modified component； The active component is less than 160 modified zeolite for silica alumina ratio；The modified component is phosphorus containg substances, II A group metal oxides And at least two combination in rare-earth oxide three.
Wherein, the active component is less than 160 modified zeolite for silica alumina ratio, and the modified component is phosphorus containg substances, II A Organize at least two combination in metal oxide and rare-earth oxide three.That is, modified component for phosphorus containg substances with And II A group metal oxides the combination either combination of phosphorus containg substances and rare-earth oxide or II A group metal oxygens It the combination of compound and rare-earth oxide or is aoxidized for phosphorus containg substances, II A groups metal oxide and rare earth metal The combination of object.Wherein, phosphorus containg substances refer to P elements or phosphorus compound.This catalyst can effectively facilitate hydro carbons and alcohol Copyrolysis reacts, so as to obtain desired product.
Preferably, the modified zeolite is the ZSM-5 zeolite that silica alumina ratio is 40~100, and the physicochemical property of the catalyst is expired Sufficient circulation conveying requirement.
Preferably, the content of the active component in the catalyst is 15%-95%.Further be conducive to following for catalyst Ring utilizes.
On above-described embodiment basis, further, C4-C8The weight ratio of hydro carbons and alcohol is 0-4:1.That is, reaction is former C4-C8 hydro carbons can be free of in material, it can be using the weight ratio of C4-C8 hydro carbons and alcohol as 1:2、1:1、2:1、3:1 or 4:1 etc. Any proportion in the section meets the C4-C8 hydro carbons weight of the section ratio value and alcohol weight, can the present embodiment provides Reaction condition under abundant cracking reaction, obtain desired product.
Preferably, C4-C8The weight ratio of hydro carbons and alcohol is 0.5-2:1, meet the C4-C8 hydro carbons weights of the section ratio value Amount and alcohol weight, the reaction heat and the C4-C8 hydrocarbon crackings of heat absorption for making alcohol cracking release reach balance, further realize energy Optimization it is complementary.
Specifically, as shown in Fig. 2, the present invention also provides a kind of alkene preparation facilities, including fluidized-bed reactor and divide The C not connected with fluidized-bed reactor4-C8Hydrocarbon raw material storage tank, raw polyol storage tank.
Wherein, fluidized-bed reactor can select riser reactor, dense-phase circulating fluidized bed reactor and riser to add Any one in the combined reactor of bed or the reactor of these three types.
Such as：To C4-C8Hydrocarbon raw material and alcohols feedstock is preheated respectively；C after preheating4-C8Hydrocarbon raw material and Methanol or mixing raw polyol pass through C respectively4-C8Hydrocarbon raw material distributor pipe 5 and alcohols feedstock distributor pipe 4, in close phase reaction device bed 3 Mi Xiangfanyingqu is contacted with catalyst, and cracking reaction is carried out under process conditions provided by the invention.Reaction oil gas and catalysis Agent is detached under the first cyclone separator 2 effect for being located at reactor top, and reaction oil gas is gone from the oil gas vent 1 at top Oil and gas separating system, process gradually products such as isolated ethylene, propylene.Carbon deposition catalyst is through in stripped vapor distributor pipe 6 After steam stripping, regenerator bed 10 is recycled by reclaimable catalyst circulation pipe 7, introducing air by distributor pipe of cardinal wind 9 is burnt Coke regeneration, catalyst and flue gas after regeneration are detached under the second cyclone separator 11 effect for being located at regenerator top Afterwards, regenerated catalyst is recycled back to reactor by regenerated catalyst circulation pipe 8 and continues to participate in reaction, and flue gas is from regenerator overhead flue gas Outlet 12 is gone to carry out heat recovery.
In the present embodiment, catalyst recycles, and can save material, reduce cost, be good for the environment.
Alkene preparation facilities provided in this embodiment can be good at realizing system preparation method provided by the invention, can Using the mixed alcohol generated in alcohol or other Chemical Manufactures in Fischer-Tropsch synthesis, in methanol production as alkene provided by the invention The reaction raw materials of hydrocarbon preparation method so as to which the effective upgrading of by-product low value mixed alcohol be enable to utilize, avoid waste of resource, It is good for the environment, moreover it is possible to which reduction prepares the cost of ethylene, propylene, obtains the vigorous ethylene of the market demand, propylene, and then can carry The overall economic efficiency of high enterprise.
For the effect of more directviewing description olefin preparation method provided by the invention, below with specific experiment result for It is bright.
Each test example is included using the implementation that olefin preparation method provided by the invention carries out ethylene, prepared by propylene Example, further includes comparative example 1 and comparative example 2.
The catalyst that embodiment in each test example is prepared using following methods：Specifically, by modified material phosphorus, lanthanum Wiring solution-forming, then ZSM-5 molecular sieve is immersed in the solution 1 hour, it is then dried at a temperature of 120 DEG C, then at 550 DEG C Under conditions of roasted to get modified zsm-5 zeolite.Then by 30% through phosphorus, the ZSM-5 molecular sieve of lanthanum modification, 20% Kaolin and surplus Aluminum sol and deionized water mix and disperse to be beaten, and obtained slurry is urged on spray-drying installation Agent is molded, and obtains the microspherical catalyst that particle size distribution is 0~200 μ, and fresh catalyst obtained is carried out the old of routine The catalyst of experiment is obtained after changing deactivation.Catalyst physico-chemical property is as shown in the table 1 in Fig. 3.
The feedstock oil used in embodiment has methanol, mixed alcohol, 1- butylene and coker gasoline respectively, and wherein methanol is industry Grade, 1- butene contents 99%, mixed alcohol are the by-products from certain methyl alcohol product installation, concrete composition as shown in table 2 in Fig. 4, The property of coker gasoline is as shown in table 3 in Fig. 5.
The experimental rig used in embodiment is dense-phase fluidized bed, device catalyst inventory 5kg, the close phase section of reactor Reserve 0-1.8kg.
Reaction bed heating output：After fingering material at the reaction temperatures reacting balance when, the output of reaction bed heating furnace Load, the index can intuitively reflect height of the differential responses with respect to fuel factor
First case：
For the present embodiment using 1- butylene and methanol as raw material, the weight ratio of 1- butylene and methanol is 1:2.Comparative example is respectively with 1- Butylene and methanol are raw material, process conditions and result of the test as shown in the table 4 in Fig. 6.Simultaneously by the experiment knot of two comparative examples Fruit is fitted with forming for embodiment raw material, is listed in table, in order to illustrate the effect of patent.By table it can be seen that implementing The cracking result of example is compared with match value, and major product productivity of propylene significantly improves, and ethylene yield also has small size raising.The two During coupling cracking, the heat that methanol decomposition is released is absorbed and utilized by butene cracking, shows in the heating output of reaction bed.Phase For, calorific requirement is larger when butylene individually cracks, thus the output load of bed heating is also high, and when coupling cracks, bed adds The output load of heat is reduced.
Second case：
For the present embodiment using 1- butylene and mixed alcohol as raw material, the weight ratio of 1- butylene and mixed alcohol is 1:2.Comparative example is distinguished Using 1- butylene and mixed alcohol as raw material, process conditions and result of the test are as shown in the table 5 in Fig. 7.Simultaneously by two comparative examples Result of the test is fitted with forming for embodiment raw material, is listed in table, in order to illustrate the effect of patent.It can be seen by table Go out the cracking result of embodiment compared with match value, target product propylene and ethylene yield all increase, reaction bed heating Output is significantly reduced, and is illustrated that mixed alcohol can replace charging of the methanol as coupling cracking, is reached same effect.
Third example：
For the present embodiment using coker gasoline and methanol as raw material, coker gasoline and methanol weight ratio are 1:1, comparative example respectively with Coker gasoline and methanol are raw material, process conditions and result of the test as shown in the table 6 in Fig. 8.Simultaneously by the examination of two comparative examples It tests result to be fitted with forming for embodiment raw material, be listed in table, in order to illustrate the effect of patent.By table it can be seen that Compared with match value, target product propylene and ethylene yield all increase the cracking result of embodiment, and reaction bed heating is defeated Go out to be significantly reduced, fuel factor when coker gasoline individually cracks can be reduced by illustrating the introducing of methanol, promote reaction efficiency.
4th：
For the present embodiment using coker gasoline and mixed alcohol as raw material, coker gasoline and mixed alcohol weight ratio are 1:1, comparative example point Not using coker gasoline and mixed alcohol as raw material, process conditions and result of the test are as shown in the table 7 in Fig. 9.Simultaneously by two comparisons The result of the test of example is fitted with forming for embodiment raw material, is listed in table, in order to illustrate the effect of patent.Embodiment Cracking result compared than match value, target product propylene and ethylene yield all increase, reaction bed heating output it is also bright It is aobvious to reduce, illustrate that mixed alcohol can replace charging of the methanol as coupling cracking, reach same effect.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to Can so modify to the technical solution recorded in foregoing embodiments either to which part or all technical features into Row equivalent replacement；And these modifications or replacement, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (10)

1. a kind of olefin preparation method, which is characterized in that including：
To C4-C8Hydrocarbon raw material and raw polyol are preheated respectively；
Make the C after preheating4-C8Hydro carbons and alcohol jointly with catalyst for cracking under fluidized state haptoreaction, obtain reaction product With carbon deposition catalyst；
The reaction product is detached with the carbon deposition catalyst；
Isolated ethylene, propylene are carried out to the reaction product；
Wherein, the alcohol is methanol either not include the mixed alcohol of methanol or being the mixed alcohol for including methanol；
The C made after preheating4-C8Hydro carbons and alcohol jointly with catalyst for cracking under fluidized state haptoreaction, reacted During product and carbon deposition catalyst, reaction temperature is 400 DEG C -670 DEG C, reaction pressure 0.01MPa-0.30Mpa, reaction weight Amount air speed is 1h-1-10h-1。
2. a kind of olefin preparation method according to claim 1, which is characterized in that the catalyst include active component with And modified component；
The active component is less than 160 modified zeolite for silica alumina ratio；
The modified component is at least two in phosphorus containg substances, II A groups metal oxide and rare-earth oxide three Combination.
3. a kind of olefin preparation method according to claim 2, which is characterized in that the active component is in the catalyst Content is 15%~95%.
4. a kind of olefin preparation method according to claim 2, which is characterized in that the modified zeolite is that silica alumina ratio is 40 ~100 ZSM-5 zeolite.
5. a kind of olefin preparation method according to claim 1, which is characterized in that
C4-C8Hydrocarbon raw material is preheated to 200 DEG C -650 DEG C, and raw polyol preheating temperature is no more than 300 DEG C.
A kind of 6. olefin preparation method according to claim 1, which is characterized in that C4-C8The weight ratio of hydro carbons and alcohol is 0-4:1。
A kind of 7. olefin preparation method according to claim 6, which is characterized in that C4-C8The weight ratio of hydro carbons and alcohol is 0.5-2:1。
8. a kind of olefin preparation method according to claim 1, which is characterized in that the reaction weight space velocity is 2-1-5h-1。
9. a kind of olefin preparation method according to claim 1, which is characterized in that the reaction product and the carbon distribution After catalyst carries out separating step, further include,
Carbon deposition catalyst is regenerated.
10. a kind of alkene preparation facilities, which is characterized in that connected including fluidized-bed reactor and respectively with fluidized-bed reactor C4-C8Hydrocarbon raw material storage tank and raw polyol storage tank.
CN201810016987.4A 2018-01-08 2018-01-08 A kind of olefin preparation method and device Pending CN108191593A (en)

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Publication number Priority date Publication date Assignee Title
CN102050691A (en) * 2009-11-10 2011-05-11 中国石油大学(北京) Method for preparing low carbon olefin by use of coupling between methanol and C4 hydrocarbon
CN102531821A (en) * 2010-12-28 2012-07-04 中国科学院大连化学物理研究所 Method for catalyzing catalytic cracking reaction of methanol coupled with naphtha using modified ZSM-5 molecular sieve based catalyst
CN103012031A (en) * 2012-11-27 2013-04-03 洪仁作 Method for synthesizing propylene by lower alcohols
CN103773440A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Pretreatment method for desulphurization adsorbents and desulphurization method for sulfur-containing hydrocarbon raw materials
CN110871107A (en) * 2019-11-06 2020-03-10 厦门大学 Catalyst for preparing low-carbon olefin by coupling catalytic cracking of low-carbon alcohol and naphtha as well as preparation method and application of catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050691A (en) * 2009-11-10 2011-05-11 中国石油大学(北京) Method for preparing low carbon olefin by use of coupling between methanol and C4 hydrocarbon
CN102531821A (en) * 2010-12-28 2012-07-04 中国科学院大连化学物理研究所 Method for catalyzing catalytic cracking reaction of methanol coupled with naphtha using modified ZSM-5 molecular sieve based catalyst
CN103773440A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Pretreatment method for desulphurization adsorbents and desulphurization method for sulfur-containing hydrocarbon raw materials
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