CN102344328A - Semi-continuous method for converting methyl alcohol into propylene by using moving bed technology - Google Patents
Semi-continuous method for converting methyl alcohol into propylene by using moving bed technology Download PDFInfo
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- CN102344328A CN102344328A CN2011102086342A CN201110208634A CN102344328A CN 102344328 A CN102344328 A CN 102344328A CN 2011102086342 A CN2011102086342 A CN 2011102086342A CN 201110208634 A CN201110208634 A CN 201110208634A CN 102344328 A CN102344328 A CN 102344328A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention discloses a semi-continuous method for converting methyl alcohol into propylene by using a moving bed technology, which comprises the following steps: mixing a molecular sieve based catalyst with a diluent, and then, introducing into a first reaction zone; introducing a methyl alcohol raw material into the first reaction zone to generate contact reaction with the molecular sieve based catalyst to generate a first material flow; introducing the first material flow into a second reaction zone to generate the contact reaction with the molecular sieve based catalyst to generate a second material flow; after the second material flow and the methyl alcohol raw material exchange heat and after dehydration and oxide removing are carried out, carrying out separation to obtain a second reaction zone return, a second reaction zone discharge and a third reaction zone feed, and merging the second reaction zone return into the first material flow; introducing the third reaction zone feed into a third reaction zone to be contacted with the molecular sieve based catalyst to generate a third material flow; and conveying the molecular sieve based catalyst into a regenerating unit at regular intervals by adopting a catalyst collector for regeneration, and intermittently merging into the molecular sieve based catalyst for circulation. Three stages of reaction of the methyl alcohol into the propylene are realized only by one molecular sieve based catalyst, thereby, the propylene yield is improved.
Description
Technical field
The present invention relates to use moving bed technique to prepare the field of propylene, be specifically related to a kind of moving bed technique that uses the semicontinuous method of methanol conversion as propylene.
Background technology
Propylene is a kind of important basic chemical industry raw material in the modern chemistry industry, is second largest chemical of present global demand amount.Along with the development of countries in the world industrial economy, the propylene demand is with increasing.The traditional production route of propylene is the catalytic pyrolysis of petroleum.Because the world oil total amount is limited, International Crude Oil rises steadily, and causing with the oil is that the cost of raw material production propylene constantly raises, thereby has caused the research boom with comparatively cheap methanol production propylene technology (MTP).Under and the situation that also will be difficult to from now on descend very high in current crude oil price, for the China of oil starvation, weak breath, rich coal, methanol production propylene Technology highlights stronger competitive power and far-reaching strategic importance more.
At present, the methanol-to-olefins technology of comparative maturity mainly contains the methanol-to-olefins technology (MTO) of American UOP company and the fixed bed preparing propylene from methanol technology (MTP) of German Lurgi company in the world.The fluidized-bed preparing propylene from methanol technology (FMTP) that the domestic preparing light olefins from methanol technology (DMTO) that Dalian Chemiclophysics Inst., Chinese Academy of Sciences exploitation then arranged and Tsing-Hua University research and develop.MTO technology is mainly used in preparation ethene and propylene, and MTP technology then is mainly used in the preparation propylene.
Fixed bed preparing propylene from methanol technology is mainly accomplished by the exploitation of German Lurgi company and is formed patented technology, and European patent EP 0448000B1, Chinese patent CN1431982A etc. all discloses this process method and employed catalyzer.The modified zsm-5 zeolite catalyzer that this process method provides based on the southern chemical company of Germany adopts single-stage and multistage insulation fix bed reactor, has higher propene yield, simultaneously by-product small amount of ethylene, gasoline and LPG liquefied petroleum gas (LPG).Because catalyzer need carry out the original position super regeneration in the fixed bed; Therefore; Usually employing is provided with a plurality of fixed-bed reactor and (opens one fully as two; Promptly use two fixed-bed reactor, subsequent use fixed-bed reactor) switch to address the above problem, the system device requirement is high, the problem of complicated operation but this design exists.
Fluidization is researched and developed successfully by Uop Inc. at first, in addition, and the domestic exploitation that also has the Dalian Chemistry and Physics Institute, Tsing-Hua University to be engaged in this technology at present.Fluidization mainly adopts the SAPO-34 catalyzer, and it has very high selectivity to low-carbon alkene, but not high to the one way selectivity of propylene, and the serious wear of SAPO-34 catalyzer in fluidized-bed, and this is the difficult problem that need capture of its industrial applications from now on.
Moving bed technique is because little, the reaction of solid back-mixing is near piston flow in the bed, thereby feed stock conversion is high, and the bed inner catalyst constantly moves (regeneration) thereby can keep good catalytic performance, more and more receives researchist's attention.Publication number is that the one Chinese patent application of CN1803738A discloses a kind of moving-bed preparing propylene from methanol technology; Through adopting the bifunctional molecule sieve catalyst; Utilize reaction-regenerated method to realize the circulation of catalyzer, the circulation of introducing by product simultaneously transforms, thereby improves the selectivity of propylene.ZSM-5 is a kind of sieve catalyst with mesopore character, has medium coke deposit rate.Moving bed technique is a kind of successive reaction regenerating technique, is particularly useful for having the catalyzer of medium coke deposit rate.It both can not need catalyzer to have very high wear resistance again simultaneously as the regeneration of circulating fluidized bed successive reaction.
Granted publication number discloses the successive reaction-regenerating unit that contains four reaction areas for the Chinese patent of CN1152944C; Publication number is that the one Chinese patent application of CN 101367701A discloses a kind of employing two-stage reaction district; Oxygen-containing compound material is generated product at first section reaction zone; Again the above component of the C5 in the product is fed second reaction zone and carry out the preparatory carbon deposit of catalyzer; Catalyzer with the preparatory carbon deposit of second reaction zone is used for the reaction of first reaction zone again, at last catalyzer is fed revivifier.The process method of this reaction cyclic regeneration that utilizes successive reaction-regenerating unit and catalyzer is transported to first reaction zone from second reaction zone; All need increase catalyst transport that special air-lift device comes out reactor stream between the reactive system and between reactive system and the regenerating unit to regenerating unit regeneration; This needs very big transmitting power, exists the technological deficiency that energy consumption is too high, economic benefit is not good enough.
Summary of the invention
The invention provides a kind of moving bed technique that uses with the semicontinuous method of methanol conversion as propylene, only realized promptly that with a kind of sieve catalyst methyl alcohol is to three sections reactions of propylene in the moving-bed, final realization improves the purpose of propene yield.
A kind of moving bed technique that uses may further comprise the steps the semicontinuous method of methanol conversion as propylene:
1) sieve catalyst is mixed the back with catalyst diluent and feed first reaction zone continuously; Methanol feedstock is fed first reaction zone to be contacted with sieve catalyst; Under 240 ℃～300 ℃, 0.1MPa～1MPa condition; Sieve catalyst stops 30h～100h in first reaction zone, produce first burst of logistics;
Described first burst of logistics comprises methyl alcohol, dme and water;
Described first reaction zone comprises a moving-burden bed reactor at least;
2) enter into second reaction zone through the sieve catalyst behind first reaction zone; The first burst of logistics that obtains in the step 1) fed second reaction zone to be contacted with sieve catalyst; Under 430 ℃～530 ℃, 0.1MPa～0.8MPa condition; Sieve catalyst stops 30h～100h in second reaction zone, produce second burst of logistics;
Described second burst of logistics comprises ethene, propylene, butylene, C
1～C
4Alkane and C
5Above component;
Described second reaction zone comprises a moving-burden bed reactor at least;
3) with step 2) in after the second burst of logistics and the methanol feedstock heat exchange in the step 1) that produce; Through separating (separating after promptly after gas-liquid separation and rectifying, removing water and oxide compounds such as unconverted methyl alcohol and dme) behind dehydration and the oxide removal; Obtain the second reaction zone returns, the second reaction zone discharging and the 3rd reaction zone feeds, the second reaction zone returns are incorporated first burst of logistics into and are circulated to step 2);
The described second reaction zone returns comprise ethene, butylene and C
2～C
4Alkane, the described second reaction zone discharging comprises C
1Alkane and propylene, described the 3rd reaction zone feeds comprises C
5Above component;
4) enter into the 3rd reaction zone through the sieve catalyst behind second reaction zone; The 3rd reaction zone feeds that obtains in the step 3) is fed the 3rd reaction zone to be contacted with sieve catalyst; Under 465 ℃～540 ℃, 0.1MPa～0.5MPa condition; Sieve catalyst stops 30h～100h at the 3rd reaction zone, produces the 3rd burst of logistics;
Described the 3rd burst of logistics comprises propylene, ethene, butylene, C
1～C
4Alkane and C
5Above hydrocarbon;
Described the 3rd reaction zone comprises a moving-burden bed reactor at least;
Sieve catalyst be transported to first reaction zone continuously after catalyst diluent is mixed; Sieve catalyst slowly moves continuously; Flow through successively first reaction zone, second reaction zone, the 3rd reaction zone; Regularly regenerating after collecting through the sieve catalyst behind the 3rd reaction zone obtains regenerated catalyst, and regenerated catalyst is incorporated into off and on and is circulated to step 1) in the sieve catalyst.
In order better to be invented effect, below as of the present invention further preferred:
The described moving bed technique that uses also comprises the semicontinuous method of methanol conversion as propylene: 5) with the 3rd burst of logistics that obtains in the step 4) with separate after second reaction zone feeds is carried out heat exchange, separate obtaining ethene, butylene and C
2～C
4Alkane is incorporated first burst of logistics into and is circulated to step 2).The increase of step 5) makes the present invention use moving bed technique that methanol conversion is further improved as capacity usage ratio in the propylene and utilization of materials, has better economic benefit.
Moving-burden bed reactor can specifically be selected existing moving-burden bed reactor for use; Like application number is that 201010175837.1 one Chinese patent application disclosed a kind of being used for the oxygenatedchemicals is the tube-type moving-bed reactor of raw material production propylene; Application number is that 200810120839.3 one Chinese patent application disclosed a kind of being used for the oxygenatedchemicals is the radially moving bed reactor of raw material production propylene, and application number is that 200810120838.9 one Chinese patent application disclosed a kind of being used for the oxygenatedchemicals is the horizontal moving bed reactor of raw material production propylene.
The catalyzer of described three reaction zones is with a kind of sieve catalyst; Described sieve catalyst is preferably the ZSM-5 molecular sieve; The ZSM-5 molecular sieve is a kind of sieve catalyst with mesopore character, has medium coke deposit rate, and the wearability in moving-bed is better.Because the preparing propylene from methanol reaction is strong exothermal reaction,, prevent hot localised points so need to add the solids dilute catalyst of inertia, big specific heat capacity.Described catalyst diluent is ceramic particle or quartz sand particle, generally selects for use to have the measure-alike catalyst diluent of bigger specific heat capacity, particle size and molecular sieve.The mass ratio of described sieve catalyst and catalyst diluent is 1: 1～20.Methanol feedstock can be different industrial raw material, as adopting the mixture of methyl alcohol or methyl alcohol and water, can comprise a spot of impurity in the methanol feedstock.
Because the reaction heat that adopts the dme of first burst of logistics in the step 1) to generate propylene and other alkene is that propylene is much lower than directly from methanol conversion; The present invention is that propylene was divided into for three steps with methanol conversion; Wherein the first step mainly is to be dme (first reaction zone) with methanol conversion; Second step mainly was to be propylene (second reaction zone) with dimethyl ether conversion, and the 3rd step was that the high-carbon hydrocarbon cracking is converted into propylene (the 3rd reaction zone).Thereby with methanol conversion is the reaction heat separated into two parts of propylene, and two portions reaction heat is released in first and second reaction zones respectively.Because coke forms the reaction acceleration under the comparatively high temps, simultaneously, the sieve catalyst dealumination reaction quickens; Therefore; The present invention is the reaction heat separated into two parts of propylene with methanol conversion, thereby to avoid methanol conversion be that temperature raises too fastly in the process of propylene, not only can suppress the formation of coke; And can suppress the dealuminzation of catalyzer, make catalyzer keep high reactivity.
Described step 2), add in first burst of logistics and feed second reaction zone behind the water vapour and contact with sieve catalyst.Water vapour can specifically be selected general facilities water vapour for use.The increase of water vapour can obviously reduce the carbon deposit of sieve catalyst, within the long period, makes the activity of sieve catalyst remain on the certain limit value.The mol ratio of preferred first burst of logistics and water vapour is controlled at 0.25～4: 1.
The temperature of reaction of described second reaction zone is selected 430 ℃～530 ℃; Oxygenatedchemicals can effectively be converted into alkene under this TR; The lesser temps of this scope helps the generation of propylene; And comparatively high temps helps the generation of ethene, and in order to make propylene conversion improve, temperature of reaction is preferably 450 ℃～500 ℃.
Reaction raw materials stream in described first reaction zone, second reaction zone and the 3rd reaction zone flows with sieve catalyst and is adverse current.Wherein, reaction raw materials is flowed the bottom of introducing reaction zone, and shift out from reaction zone top, sieve catalyst moves down under action of gravity, thereby presents adverse current.When the flow velocity of reaction raw materials stream is higher; Occur in the starting stage of conversion, reaction raw materials stream is to contact with the sieve catalyst of part inactivation, and when the flow velocity of reaction raw materials stream hangs down; Occur in going deep into the stage subsequently of conversion; Reaction raw materials stream is contact with the higher sieve catalyst of activity, and therefore, methanol feedstock and sieve catalyst be mobile to be adverse current and can effectively to have kept the selectivity of catalyzer to low-carbon alkene.
Catalyzer is that propylene conversion and distribution of reaction products have remarkable influence in the residence time of reaction zone (being the duration of contact of reactant and catalyzer) to methanol conversion.The residence time is short, and raw material contacts insufficient with catalyzer, and reaction conversion ratio is low, and the residence time is oversize, causes by products such as alkane such as methane in the product, propane, butane, aromatic hydrocarbons to increase easily.Usually represent with weight hourly space velocity (WHSV) duration of contact of reactant and catalyzer; WHSV refers to the ratio of the quality and the catalyst in reactor quality of reaction raw materials in the per hour charging; WHSV numerical value is big more represents the residence time short more, all preferred 0.1～20hr of the WHSV of the present invention's first reaction zone, second reaction zone and the 3rd reaction zone
-1
The residence time of described sieve catalyst in reaction zone is preferably 90～300h.Sieve catalyst or incorporate sieve catalyst after the regenerated catalyst into and get into the moving-burden bed reactor of first reaction zone from feed entrance after; In moving-burden bed reactor, slowly move; Move through the moving-burden bed reactor of second reaction zone, the moving-burden bed reactor of the 3rd reaction zone then continuously, after 90～300 hours, shift out moving-burden bed reactor entering catalyzer scoop.
In the step 4); Adopt the catalyzer scoop through the sieve catalyst behind the 3rd reaction zone (being the sieve catalyst of carbon deposit); The sieve catalyst of collecting regularly is transported in the regenerating unit regeneration obtains regenerated catalyst, regenerated catalyst is incorporated into and is circulated to step 1) in the sieve catalyst.The mass ratio of the sieve catalyst (being fresh sieve catalyst) that described regenerated catalyst is preceding with not incorporating regenerated catalyst into is 0～3: 7.Reactive system is independent mutually with catalyst regeneration device, and promptly catalyzer runs up to a certain amount of sent for regeneration device regeneration of concentrating afterwards, not only can save the conveying cost, has also reduced the complicacy of device.
A kind of is the device of propylene with methanol conversion, comprises placed in-line successively catalyzer feed pot, catalyzer feed regulator, first reaction zone, second reaction zone, the 3rd reaction zone, catalyzer discharging surge tank, catalyzer discharging unit and catalyzer scoop.Wherein, described first reaction zone, second reaction zone and the 3rd reaction zone comprise a moving-burden bed reactor respectively at least.Each moving-burden bed reactor places the different horizontal height; Between the adjacent moving-burden bed reactor; The bottom of moving-burden bed reactor is communicated with the top of next moving-burden bed reactor; For example, can be through pipeline or moving-bed eclipsed form serial connection, two ends were connected with catalyzer feed regulator, catalyzer discharging surge tank respectively after each moving-burden bed reactor connected.Each moving-burden bed reactor that connects in this way can guarantee that catalyzer relies on self gravitation to move from top to bottom, and successively through each moving-burden bed reactor, material benzenemethanol and catalyzer form cross-flow, and capable of reducing energy consumption from top to bottom.
Described catalyzer feed regulator is that catalyzer is by the no valvegear of low pressure to high-pressure delivery.This no valvegear is controlled particle by low pressure flowing and end to high pressure section through low pressure epimere, transition interlude, high reduction section and the tremie pipe, butterfly gate and the accessory throttling set that are communicated with the adjacent both ends zone.
Described catalyzer discharging unit is no block of valve pressure device.When the pressure in the reactor drum is higher than external atmospheric pressure; For catalyzer is transported to reaction zone from hopper; The pressure that must improve catalyst feeds perhaps reduces the pressure of first reaction zone, for achieving this end, at catalyst inlet a no block of valve is set and presses e Foerderanlage; No block of valve pressure device can realize that granules of catalyst is by the conveying of high pressure to low pressure; And do not reveal the pressure in the moving-burden bed reactor, realize a lock compression functions and the blanking speed of this lock pressure device may command catalyzer and can reduce the wear phenomenon of catalyzer in the blanking flow process greatly.
This methanol conversion is that the device of propylene also comprises regenerating unit, and the way of the sieve catalyst employing artificial conveyance in the catalyzer scoop is regularly delivered in the regenerating unit and regenerated, and joins off and in the catalyzer feed pot afterwards.
Be equipped with heat-exchanger rig in described first reaction zone, second reaction zone, the 3rd reaction zone.Described heat-exchanger rig is in moving-burden bed reactor and/or between each moving-burden bed reactor.Heat-exchanger rig is set between moving-burden bed reactor; Not only can remove the reaction heat that produces in the reaction process; Be convenient to the temperature of reaction of the per step reaction of better control; And the heat that exchanges out can preheating the material of each reaction zone inlet, the input of having saved the general facilities heat has reached the purpose of utilization system heat energy.When thermal discharge is excessive, the chilling device that set up this moment between moving-burden bed reactor, chilling device specifically can be selected interchanger; Can effectively remove unnecessary reaction heat; After second burst of logistics in the step 3) and methanol feedstock heat exchange, the Quench liquid in the chilling device specifically adopts methanol feedstock, and methanol feedstock specifically can be selected the mixture of methyl alcohol or methyl alcohol and water for use; When adopting methanol feedstock, can improve the treatment capacity of methanol feedstock.
Compared with prior art, the present invention has the following advantages:
1) regenerated catalyst of the present invention is incorporated sieve catalyst (being fresh sieve catalyst) off and on into; Successive is through the moving bed reaction district; The carbon deposited catalyst centralized collection, regularly the method for sent for regeneration uses a kind of sieve catalyst promptly to accomplish preparing dimethyl ether from methanol, dme system propylene and three sections reactions of high-carbon hydrocarbon cracked; Interior material of reactor drum and sieve catalyst reaction have been realized continuously; The outer sieve catalyst of reactor drum is reinforced and collect semi-continuous moving bed process, has increased the independence of reactive system and regenerating unit, has reduced the complicacy of whole plant.
2) the present invention uses moving bed technique that methanol conversion has been divided into three sections as the semicontinuous method of propylene with reaction to react; Use same sieve catalyst for three sections; Not only can improve the transformation efficiency that methyl alcohol generates the dme conversion zone, reduce the content of methyl alcohol in the final isolated waste water, and C
2～C
4The cracking of the freshening of lower carbon number hydrocarbons and the above higher olefins of C5 has improved the selectivity of final purpose product propylene, has avoided operation to go up different catalysts simultaneously and need draw the regenerated complicacy in batches.
3) the present invention is that the reaction heat of propylene reaction process is divided into two sections with methanol conversion; The reaction heat preheating that utilizes the etherification reaction of first reaction zone to emit gets into the reaction raw materials of second reaction zone; Average temperature rising in the propylene building-up reactions district can effectively be controlled; Thereby reduced the carbon distribution and the dealuminzation phenomenon of catalyzer, kept the high reactivity of catalyzer.
4) the present invention has solved catalyst charge and the discharging problem that influences to the reaction unit stopping property through setting up catalyzer feed regulator and catalyzer discharging unit; Adopt the carbon deposited catalyst centralized collection; Regularly the method for sent for regeneration has been simplified the Design of device complicacy.
5) the present invention has set up heat-exchanger rig between the moving-bed of each reaction zone, and the reaction heat that system is unnecessary is used to heat the inlet stream of high temperature section reaction zone, has fully utilized the heat energy that reaction feed and product go out the materials flow thigh.
6) the present invention adopts the multi-reaction-area arranged superposed, and catalyzer continuous flow has realized reacting secular and carried out continuously.The present invention adopts second reaction zone freshening portion of product (ethene, butylene and the C
2～C
4Alkane), improved the propylene selectivity.The present invention adopts the hydro carbons of the 3rd reaction zone cracking number of carbons, and the freshening portion of product (C after will separating
2～C
4Alkane, ethene and butylene) turn back to second reaction zone reaction, reduced content of by-products, improved the yield of propylene.
Description of drawings
Fig. 1 is the structural representation of the device of propylene with methanol conversion for the present invention.
Embodiment
As shown in Figure 1; For being the device of propylene, comprise placed in-line successively catalyzer feed pot ST1, catalyzer feed regulator F1 (catalyzer is by the no valvegear of low pressure to high-pressure delivery), the first reaction zone D1, the second reaction zone D2, the 3rd reaction zone D3, catalyzer discharging surge tank B, catalyzer discharging unit F2 and catalyzer scoop ST2 (no block of valve pressure device) with methanol conversion.The first reaction zone D1, the second reaction zone D2 and the 3rd reaction zone D3 comprise a moving-burden bed reactor respectively at least.Each moving-burden bed reactor places the different horizontal height; Between the adjacent moving-burden bed reactor; The bottom of moving-burden bed reactor is communicated with the top of next moving-burden bed reactor; For example, can be through pipeline or moving-bed eclipsed form serial connection, each moving-burden bed reactor is connected with catalyzer feed regulator F1, catalyzer discharging surge tank B after connecting again.This methanol conversion is that the device of propylene also comprises regenerating unit R, and the way of the sieve catalyst employing artificial conveyance among the catalyzer scoop ST2 is regularly delivered among the regenerating unit R and regenerated, and joins off and on afterwards among the catalyzer feed pot ST1.Be respectively equipped with heat-exchanger rig H1, H2, H3, E1 and E2 among the first reaction zone D1, the second reaction zone D2, the 3rd reaction zone D3.Heat-exchanger rig H1, H2, H3 are used for the material of each reaction zone inlet of accurately preheating in moving-burden bed reactor and/or between each moving-burden bed reactor.Heat-exchanger rig E1 and E2 are used to utilize the material of each reaction zone inlet of heat preheating of reaction zone discharging.Methanol conversion of the present invention is that the device of propylene also comprises disengaging zone sep1, sep2.
The present invention uses moving bed technique with the semicontinuous method of methanol conversion as propylene, may further comprise the steps:
1) sieve catalyst and catalyst diluent are continuously joined first reaction zone D1 through catalyzer feed regulator F1 from the first reaction zone D1 top by catalyzer feed pot ST1, control the speed of charging through the throttling set of regulating feed regulator F1 lower end; Being passed into the first reaction zone D1 from first reaction zone D1 bottom behind the methanol feedstock s process heat-exchanger rig H1 contacts with sieve catalyst; Under 240 ℃～300 ℃, 0.1MPa～1MPa reaction conditions; Sieve catalyst stops 30h～100h at the first reaction zone D1, and the outlet at the first reaction zone D1 top produces first gang of logistics a;
Described first gang of logistics a comprises methyl alcohol, dme and water;
The described first reaction zone D1 comprises a moving-burden bed reactor at least;
2) enter into the second reaction zone D2 through the sieve catalyst behind the first reaction zone D1 from the second reaction zone D2 top; Contact with sieve catalyst feeding the second reaction zone D2 from second reaction zone D2 bottom behind the first gang of logistics a process heat-exchanger rig H2 that obtains in the step 1); Under 430 ℃～530 ℃, 0.1MPa～0.8MPa condition; Sieve catalyst stops 30h～100h at the second reaction zone D2, produces second gang of logistics c and flows out from the outlet at the second reaction zone D2 top;
Described second gang of logistics c comprises ethene, propylene, butylene, C
1～C
4Alkane and C
5Above component;
The described second reaction zone D2 comprises a moving-burden bed reactor at least;
3) with step 2) in second gang of logistics c and step 1) in methanol feedstock s after heat-exchanger rig E1 heat exchange; Through the dehydration with oxide removal after the entering disengaging zone sep1 separate; Obtain the second reaction zone returns d, the second reaction zone discharging p1 and the 3rd reaction zone feeds e, the second reaction zone returns d incorporates first gang of logistics a into and forms the second reaction zone feeds b and be circulated to step 2);
The described second reaction zone returns d comprises ethene, butylene and C
2～C
4Alkane, the described second reaction zone discharging p1 comprises C
1Alkane and propylene, described the 3rd reaction zone feeds e comprises C
5Above component;
The second reaction zone discharging p1 further separation obtains comprising C
1Alkane (fuel gas), propylene;
4) enter into the 3rd reaction zone D3 through the sieve catalyst behind the second reaction zone D2 from the 3rd reaction zone D3 top; Contact with sieve catalyst feeding the 3rd reaction zone D3 from the 3rd reaction zone D3 bottom behind the 3rd reaction zone feeds e process heat-exchanger rig H3 that obtains in the step 3); Under 465 ℃～540 ℃, 0.1MPa～0.5MPa condition; Sieve catalyst stops 30h～100h at the 3rd reaction zone D3, produces the 3rd gang of logistics f and flows out from the outlet at the 3rd reaction zone D3 top;
Described the 3rd gang of logistics f comprises propylene, ethene, butylene, C
1～C
4Alkane and C
5Above hydrocarbon;
Described the 3rd reaction zone D3 comprises a moving-burden bed reactor at least;
5) the 3rd gang of logistics f that obtains in the step 4) got into disengaging zone sep2 with second reaction zone feeds after heat-exchanger rig E2 heat exchange and separate, separate obtaining ethene, butylene and C
2～C
4Alkane is incorporated first gang of logistics a into and is circulated to step 2), obtain comprising C final the separation
1Alkane (fuel gas comprises small amount of ethylene), propylene, C
5Above hydrocarbon (gasoline);
Sieve catalyst be transported to the first reaction zone D1 continuously after catalyst diluent is mixed; Sieve catalyst slowly moves continuously; The first reaction zone D1, the second reaction zone D2, the 3rd reaction zone D3 successively flow through; Through the sieve catalyst behind the 3rd reaction zone D3, pass through sieve catalyst discharging surge tank B and catalyzer discharging unit F2 again after, the speed of sieve catalyst blanking is controlled by the catalyzer discharging unit F2 (no block of valve pressure device) under the surge tank B.Collect at catalyzer scoop ST2, manual regular is transported to regenerate among the regenerating unit R and obtains regenerated catalyst.Regenerated catalyst is incorporated into off and on and is circulated to step 1) in the sieve catalyst, and described regenerated catalyst is 0～3: 7 with the mass ratio of not incorporating the sieve catalyst (being fresh sieve catalyst) before the regenerated catalyst into.
But the separating process that separation method referenced patent 200580025151.1 and the patent 01810472.x of disengaging zone sep1 and sep2 are introduced.
In the step 1), described sieve catalyst is the ZSM-5 molecular sieve.Described catalyst diluent is pottery or quartz sand particle.The mass ratio of described sieve catalyst and catalyst diluent is 1: 1～20.
Step 2) in, feeds the second reaction zone D2 behind the adding material thinner among described first gang of logistics a and contact with sieve catalyst.Described material thinner is a water vapour.Water vapour can specifically be selected general facilities water vapour for use.
Reaction raw materials stream among the first reaction zone D1, the second reaction zone D2 and the 3rd reaction zone D3 flows with sieve catalyst and is adverse current.The WHSV of the first reaction zone D1, the second reaction zone D2 and the 3rd reaction zone D3 is 0.1～20hr
-1
The methanol conversion of present embodiment 1～3 is that the structure of the device of propylene can adopt structure as shown in Figure 1.
Embodiment 1
1) sieve catalyst is mixed the back with catalyst diluent and feed first reaction zone continuously; The temperature in of methanol feedstock is 240 ℃, methanol feedstock is fed first reaction zone contact with sieve catalyst, under 240 ℃～280 ℃, 0.2MPa～0.3MPa condition; Sieve catalyst stops 30h at first reaction zone;, producing first burst of logistics, the temperature out of first burst of logistics is 280 ℃;
First reaction zone is a moving-burden bed reactor;
2) enter into second reaction zone through the sieve catalyst behind first reaction zone; Feed second reaction zone behind the general facilities water vapour and contact with sieve catalyst adding in the first burst of logistics that obtains in the step 1), the mol ratio of first burst of logistics and water vapour is 1: 1, and the inlet temperature of first burst of logistics is 450 ℃; Under 450 ℃～500 ℃, 0.15MPa～0.2MPa condition; Sieve catalyst stops 30h at second reaction zone, produces second burst of logistics, and temperature out is 500 ℃;
Second burst of logistics comprises ethene, propylene, butylene, C
1～C
4Alkane and C
5Above component;
Second reaction zone is a moving-burden bed reactor;
3) with step 2) in second burst of logistics and step 1) in after the methanol feedstock heat exchange; Behind dehydration and oxide removal, obtain comprising the water of micro oxygen containing compound; Separate again; Obtain the second reaction zone returns, the second reaction zone discharging and the 3rd reaction zone feeds, the second reaction zone returns are incorporated first burst of logistics into and are circulated to step 2);
The second reaction zone returns comprise ethene, butylene and C
2～C
4Alkane, the second reaction zone discharging comprises C
1Alkane and propylene, the 3rd reaction zone feeds comprises C
5Above component;
The second reaction zone discharging further separation obtains comprising C
1Alkane (fuel gas), propylene;
4) enter into the 3rd reaction zone through the sieve catalyst behind second reaction zone; The 3rd reaction zone feeds that obtains in the step 3) is fed the 3rd reaction zone to be contacted with sieve catalyst; The inlet temperature of the 3rd reaction zone feeds is 520 ℃, and under 470 ℃～520 ℃, 0.1MPa～0.15MPa condition, sieve catalyst stops 30h at the 3rd reaction zone; Produce the 3rd burst of logistics, temperature out is 470 ℃;
Described the 3rd burst of logistics comprises propylene, ethene, butylene, C
1～C
4Alkane, C
5Above hydrocarbon;
Described the 3rd reaction zone is a moving-burden bed reactor;
5) with the 3rd burst of logistics that obtains in the step 4) with separate after second reaction zone feeds is carried out heat exchange, separate obtaining ethene, butylene and C
2～C
4Alkane is incorporated first burst of logistics into and is circulated to step 2), obtain comprising C final the separation
1Mixture (fuel gas), propylene, a spot of C that alkane and small amount of ethylene are formed
3～C
4Hydro carbons (because in suitability for industrialized production, fail the whole C in the 3rd burst of logistics
3～C
4Alkane, propylene and butylene all separate, and in last discharging, still comprise a spot of C
3～C
4Hydro carbons, as LPG liquefied petroleum gas), C
5Above hydrocarbon (gasoline).
It is the ZSM-5 molecular sieve of 1.5～2mm that sieve catalyst is selected particle diameter for use.Catalyst diluent is the ceramic particle identical with the sieve catalyst general size, and the mass ratio of sieve catalyst and catalyst diluent is 1: 3.
The residence time of sieve catalyst (carbon deposition catalyst) in bed of shifting out from the bed bottom of the moving-burden bed reactor of the 3rd reaction zone is 90 hours; Coke content is less than 3%; It is collected in the catalyzer scoop regularly to concentrate to deliver in the revivifier regenerates; Obtain regenerated catalyst, the coke content of regenerated catalyst is lower than 0.5% (sedimentary carbon deposit quality on coke content=unit weight catalyzer).Regenerated catalyst is incorporated into off and on and is circulated to step 1) in the sieve catalyst, and the mass ratio of regenerated catalyst and fresh sieve catalyst is 1: 7.
The WHSV of described first reaction zone, second reaction zone and the 3rd reaction zone is respectively 10hr
-1, 15hr
-1, 20hr
-1
Table 1 has been listed the material balance under the above-mentioned condition, and this material balance is based on experimental data and is enlarged into the annual treatment capacity acquisition of 1,000,000 tons of methyl alcohol through computer simulation.Can know that from table 1 the methanol feeding amount is 207383kg/h, the propylene amount that is generated is 66275kg/h, and methanol conversion is greater than 98%.
Table 1 material balance
| Material | Mass flow |
| Methyl alcohol | 207383kg/h |
| Propylene | 62275kg/h |
| LPG liquefied petroleum gas (LPG) | 4032kg/h |
| Gasoline | 17905kg/h |
| Water (comprising micro oxygen containing compound) | 118076kg/h |
| Fuel gas # | 1466kg/h |
| Coke * | 82kg/h |
In the table 1, # representes to comprise small amount of ethylene, and * representes to comprise the loss in the material circulation; Wherein LPG is C
3～C
4Hydro carbons, be mainly alkane, comprise small amounts of olefins; Gasoline is C
5Above hydrocarbon comprises a spot of C
4Hydrocarbon mainly is the above heavy constituent of C7; Water is the product of methanol dehydration, comprises the micro oxygen containing compound such as dme, aldehydes of not reacted Trace Methanol and generation; Fuel gas mainly is a small amount of C
1～C
2Hydrocarbon component (is mainly C
1Alkane contains small amount of ethylene), coke is the carbon laydown on the catalyzer, down together.
Each product is converted into the butt percentage composition beyond dewatering, has listed products distribution with respect to material benzenemethanol, as shown in table 2.
Table 2 products distribution
| Product | The butt percentage |
| Propylene | 72.62％ |
| LPG liquefied petroleum gas (LPG) | 4.70％ |
| Gasoline | 20.88％ |
| Fuel gas | 1.71％ |
| Coke | 0.10％ |
1) sieve catalyst is mixed the back with catalyst diluent and feed first reaction zone continuously; The temperature in of methanol feedstock is 260 ℃, methanol feedstock is fed first reaction zone contact with sieve catalyst, under 260 ℃～300 ℃, 0.4MPa～0.6MPa condition; Sieve catalyst stops 50h at first reaction zone;, producing first burst of logistics, the temperature out of first burst of logistics is 300 ℃;
First reaction zone is a moving-burden bed reactor;
2) enter into second reaction zone through the sieve catalyst behind first reaction zone; Feed second reaction zone behind the general facilities water vapour and contact with sieve catalyst adding in the first burst of logistics that obtains in the step 1), the mol ratio of first burst of logistics and water vapour is 4: 1, and the inlet temperature of first burst of logistics is 470 ℃; Under 470 ℃～520 ℃, 0.2MPa～0.4MPa condition; Sieve catalyst stops 50h at second reaction zone, produces second burst of logistics, and temperature out is 520 ℃;
Second burst of logistics comprises ethene, propylene, butylene, C
1～C
4Alkane and C
5Above component;
Second reaction zone is a moving-burden bed reactor;
3) with step 2) in second burst of logistics and step 1) in after the methanol feedstock heat exchange; Behind dehydration and oxide removal, obtain comprising the water of micro oxygen containing compound; Separate again; Obtain the second reaction zone returns, the second reaction zone discharging and the 3rd reaction zone feeds, the second reaction zone returns are incorporated first burst of logistics into and are circulated to step 2);
The second reaction zone returns comprise ethene, butylene and C
2～C
4Alkane, the second reaction zone discharging comprises C
1Alkane and propylene, the 3rd reaction zone feeds comprises C
5Above component;
The second reaction zone discharging further separation obtains comprising C
1The mixture of alkane and small amount of ethylene (fuel gas), propylene;
4) enter into the 3rd reaction zone through the sieve catalyst behind second reaction zone; The 3rd reaction zone feeds that obtains in the step 3) is fed the 3rd reaction zone to be contacted with sieve catalyst; The inlet temperature of the 3rd reaction zone feeds is 530 ℃, and under 480 ℃～530 ℃, 0.1MPa～0.2MPa condition, sieve catalyst stops 50h at the 3rd reaction zone; Produce the 3rd burst of logistics, temperature out is 480 ℃;
Described the 3rd burst of logistics comprises propylene, ethene, butylene, C
1～C
4Alkane, C
5Above hydrocarbon;
Described the 3rd reaction zone is a moving-burden bed reactor;
5) with the 3rd burst of logistics that obtains in the step 4) with separate after second reaction zone feeds is carried out heat exchange, separate obtaining ethene, butylene and C
2～C
4Alkane is incorporated first burst of logistics into and is circulated to step 2), obtain comprising C final the separation
1Mixture (fuel gas), propylene, a spot of C that alkane and small amount of ethylene are formed
3～C
4Hydro carbons (because in suitability for industrialized production, fail the whole C in the 3rd burst of logistics
3～C
4Alkane, propylene and butylene all separate, and in last discharging, still comprise a spot of C
3～C
4Hydro carbons, as LPG liquefied petroleum gas), C
5Above hydrocarbon (gasoline).
It is the ZSM-5 molecular sieve of 1.5～2mm that sieve catalyst is selected particle diameter for use.Catalyst diluent is the quartz sand particle identical with the sieve catalyst general size, and the mass ratio of sieve catalyst and catalyst diluent is 1: 5.
The residence time of sieve catalyst (carbon deposition catalyst) in bed of shifting out from the bed bottom of the moving-burden bed reactor of the 3rd reaction zone is 150 hours; Coke content is less than 3%; It is collected in the catalyzer scoop regularly to concentrate to deliver in the revivifier regenerates; Obtain regenerated catalyst, the coke content of regenerated catalyst is lower than 0.5% (sedimentary carbon deposit quality on coke content=unit weight catalyzer).Regenerated catalyst is incorporated into off and on and is circulated to step 1) in the sieve catalyst, and the mass ratio of regenerated catalyst and fresh sieve catalyst is 3: 7.
The WHSV of described first reaction zone, second reaction zone and the 3rd reaction zone is respectively 12hr
-1, 15hr
-1, 18hr
-1
Table 3 has been listed the material balance under the above-mentioned condition, and this material balance is based on experimental data and is enlarged into the annual treatment capacity acquisition of 1,000,000 tons of methyl alcohol through computer simulation.Can know that from table 3 the methanol feeding amount is 207383kg/h, the propylene amount that is generated is 64451kg/h, and methanol conversion is greater than 99%.
Table 3 material balance
| Material | Mass flow |
| Methyl alcohol | 207383kg/h |
| Propylene | 64451kg/h |
| LPG liquefied petroleum gas (LPG) | 4309kg/h |
| Gasoline | 17768kg/h |
| Water (comprising micro oxygen containing compound) | 118736kg/h |
| Fuel gas # | 1588kg/h |
| Coke * | 83kg/h |
In the table 3, # representes to comprise small amount of ethylene, and * representes to comprise the loss in the material circulation;
Each product is converted into the butt percentage composition beyond dewatering, has listed products distribution with respect to material benzenemethanol, as shown in table 4.
Table 4 products distribution
| Product | The butt percentage |
| Propylene | 73.07％ |
| LPG liquefied petroleum gas (LPG) | 4.89％ |
| Gasoline | 20.15％ |
| Fuel gas | 1.80％ |
| Coke | 0.09％ |
Embodiment 3
1) sieve catalyst is mixed the back with catalyst diluent and feed first reaction zone continuously; The temperature in of methanol feedstock is 280 ℃; Methanol feedstock is fed first reaction zone contact with sieve catalyst, under 280 ℃～320 ℃, 0.8MPa～1MPa condition, sieve catalyst stops 100h at first reaction zone; Produce first burst of logistics, the temperature out of first burst of logistics is 320 ℃;
First reaction zone is a moving-burden bed reactor;
2) enter into second reaction zone through the sieve catalyst behind first reaction zone; Feed second reaction zone behind the general facilities water vapour and contact with sieve catalyst adding in the first burst of logistics that obtains in the step 1), the mol ratio of first burst of logistics and water vapour is 1: 4, and the inlet temperature of first burst of logistics is 480 ℃; Under 480 ℃～530 ℃, 0.3MPa～0.5MPa condition; Sieve catalyst stops 100h at second reaction zone, produces second burst of logistics, and temperature out is 530 ℃;
Second burst of logistics comprises ethene, propylene, butylene, C
1～C
4Alkane and C
5Above component;
Second reaction zone is a moving-burden bed reactor;
3) with step 2) in second burst of logistics and step 1) in after the methanol feedstock heat exchange; Behind dehydration and oxide removal, obtain comprising the water of micro oxygen containing compound; Separate again; Obtain the second reaction zone returns, the second reaction zone discharging and the 3rd reaction zone feeds, the second reaction zone returns are incorporated first burst of logistics into and are circulated to step 2);
The second reaction zone returns comprise ethene, butylene and C
2～C
4Alkane, the second reaction zone discharging comprises C
1Alkane and propylene, the 3rd reaction zone feeds comprises C
5Above component;
The second reaction zone discharging further separation obtains comprising C
1The mixture of alkane and small amount of ethylene (fuel gas), propylene;
4) enter into the 3rd reaction zone through the sieve catalyst behind second reaction zone; The 3rd reaction zone feeds that obtains in the step 3) is fed the 3rd reaction zone to be contacted with sieve catalyst; The inlet temperature of the 3rd reaction zone feeds is 540 ℃, and under 490 ℃～540 ℃, 0.1MPa～0.3MPa condition, sieve catalyst stops 100h at the 3rd reaction zone; Produce the 3rd burst of logistics, temperature out is 490 ℃;
Described the 3rd burst of logistics comprises propylene, ethene, butylene, C
1～C
4Alkane, C
5Above hydrocarbon;
Described the 3rd reaction zone is a moving-burden bed reactor;
5) with the 3rd burst of logistics that obtains in the step 4) with separate after second reaction zone feeds is carried out heat exchange, separate obtaining ethene, butylene and C
2～C
4Alkane is incorporated first burst of logistics into and is circulated to step 2), obtain comprising C final the separation
1Mixture (fuel gas), propylene, a spot of C that alkane and small amount of ethylene are formed
3～C
4Hydro carbons (because in suitability for industrialized production, fail the whole C in the 3rd burst of logistics
3～C
4Alkane, propylene and butylene all separate, and in last discharging, still comprise a spot of C
3～C
4Hydro carbons, as LPG liquefied petroleum gas), C
5Above hydrocarbon (gasoline).
It is the ZSM-5 molecular sieve of 1.5～2mm that sieve catalyst is selected particle diameter for use.Catalyst diluent is the ceramic particle identical with the sieve catalyst general size, and the mass ratio of sieve catalyst and catalyst diluent is 1: 8.
The residence time of sieve catalyst (carbon deposition catalyst) in bed of shifting out from the bed bottom of the moving-burden bed reactor of the 3rd reaction zone is 300 hours; Coke content is less than 3%; It is collected in the catalyzer scoop regularly to concentrate to deliver in the revivifier regenerates; Obtain regenerated catalyst, the coke content of regenerated catalyst is lower than 0.5% (sedimentary carbon deposit quality on coke content=unit weight catalyzer).Regenerated catalyst is incorporated into off and on and is circulated to step 1) in the sieve catalyst, and the mass ratio of regenerated catalyst and fresh sieve catalyst is 2: 7.
The WHSV of described first reaction zone, second reaction zone and the 3rd reaction zone is respectively 8hr
-1, 12hr
-1, 16hr
-1
Table 5 has been listed the material balance under the above-mentioned condition, and this material balance is based on experimental data and is enlarged into the annual treatment capacity acquisition of 1,000,000 tons of methyl alcohol through computer simulation.Can know that from table 5 the methanol feeding amount is 207383kg/h, the propylene amount that is generated is 69380kg/h, methanol conversion 100%.
Table 5 material balance
| Material | Mass flow |
| Methyl alcohol | 207383kg/h |
| Propylene | 69380kg/h |
| LPG liquefied petroleum gas (LPG) | 5703kg/h |
| Gasoline | 15656kg/h |
| Water (comprising micro oxygen containing compound) | 115063kg/h |
| Fuel gas # | 1487kg/h |
| Coke * | 94kg/h |
In the table 5, # representes to comprise small amount of ethylene, and * representes to comprise the loss in the material circulation;
Each product is converted into the butt percentage composition beyond dewatering, has listed products distribution with respect to material benzenemethanol, as shown in table 6.
Table 6 products distribution
| Product | The butt percentage |
| Propylene | 75.15％ |
| LPG liquefied petroleum gas (LPG) | 6.18％ |
| Gasoline | 16.96％ |
| Fuel gas | 1.61％ |
| Coke | 0.10％ |
Find out from above-mentioned three embodiment,, can obtain temperature control preferably and online reaction times of catalyzer and higher propylene selectivity according to process method disclosed by the invention.In addition, in scope disclosed by the invention, operate, the product selectivity rangeability is less.
Claims (10)
1. one kind is used moving bed technique with the semicontinuous method of methanol conversion as propylene, may further comprise the steps:
1) sieve catalyst is mixed the back with catalyst diluent and feed first reaction zone continuously; Methanol feedstock is fed first reaction zone to be contacted with sieve catalyst; Under 240 ℃～300 ℃, 0.1MPa～1MPa condition; Sieve catalyst stops 30h～100h at first reaction zone, produces first burst of logistics;
Described first burst of logistics comprises methyl alcohol, dme and water;
Described first reaction zone comprises a moving-burden bed reactor at least;
2) enter into second reaction zone through the sieve catalyst behind first reaction zone; The first burst of logistics that obtains in the step 1) fed second reaction zone to be contacted with sieve catalyst; Under 430 ℃～530 ℃, 0.1MPa～0.8MPa condition; Sieve catalyst stops 30h～100h at second reaction zone, produces second burst of logistics;
Described second burst of logistics comprises ethene, propylene, butylene, C
1～C
4Alkane and C
5Above component;
Described second reaction zone comprises a moving-burden bed reactor at least;
3) with step 2) in after the second burst of logistics and the methanol feedstock heat exchange in the step 1) that produce; Through the dehydration with oxide removal after separate; Obtain the second reaction zone returns, the second reaction zone discharging and the 3rd reaction zone feeds, the second reaction zone returns are incorporated first burst of logistics into and are circulated to step 2);
The described second reaction zone returns comprise ethene, butylene and C
2～C
4Alkane, the described second reaction zone discharging comprises C
1Alkane and propylene, described the 3rd reaction zone feeds comprises C
5Above component;
4) enter into the 3rd reaction zone through the sieve catalyst behind second reaction zone; The 3rd reaction zone feeds that obtains in the step 3) is fed the 3rd reaction zone to be contacted with sieve catalyst; Under 465 ℃～540 ℃, 0.1MPa～0.5MPa condition; Sieve catalyst stops 30h～100h at the 3rd reaction zone, produces the 3rd burst of logistics;
Described the 3rd burst of logistics comprises propylene, ethene, butylene, C
1～C
4Alkane and C
5Above hydrocarbon;
Described the 3rd reaction zone comprises a moving-burden bed reactor at least;
Sieve catalyst be transported to first reaction zone continuously after catalyst diluent is mixed; Sieve catalyst slowly moves continuously; Flow through successively first reaction zone, second reaction zone, the 3rd reaction zone; Regularly regenerating after collecting through the sieve catalyst behind the 3rd reaction zone obtains regenerated catalyst, and regenerated catalyst is incorporated into off and on and is circulated to step 1) in the sieve catalyst.
2. the moving bed technique that uses according to claim 1 is with the semicontinuous method of methanol conversion as propylene; It is characterized in that; Comprise: 5) with the 3rd burst of logistics that obtains in the step 4) with separate after second reaction zone feeds is carried out heat exchange, separate obtaining ethene, butylene and C
2～C
4Alkane is incorporated first burst of logistics into and is circulated to step 2).
3. the moving bed technique that uses according to claim 1 is characterized in that the semicontinuous method of methanol conversion as propylene in the step 1), described sieve catalyst is the ZSM-5 molecular sieve.
4. the moving bed technique that uses according to claim 1 is characterized in that the semicontinuous method of methanol conversion as propylene in the step 1), described catalyst diluent is ceramic particle or quartz sand particle.
5. the moving bed technique that uses according to claim 1 is characterized in that the semicontinuous method of methanol conversion as propylene in the step 1), the mass ratio of described sieve catalyst and catalyst diluent is 1: 1～20.
6. the moving bed technique that uses according to claim 1 is characterized in that step 2 with the semicontinuous method of methanol conversion as propylene) in, feed second reaction zone behind the adding material thinner in described first burst of logistics and contact with sieve catalyst.
7. the moving bed technique that uses according to claim 6 is characterized in that with the semicontinuous method of methanol conversion as propylene described material thinner is a water vapour.
8. the moving bed technique that uses according to claim 1 is characterized in that the semicontinuous method of methanol conversion as propylene the mass ratio of the sieve catalyst that described regenerated catalyst is preceding with not incorporating regenerated catalyst into is 0～3: 7.
9. the moving bed technique that uses according to claim 1 is characterized in that the semicontinuous method of methanol conversion as propylene the reaction raw materials stream in described first reaction zone, second reaction zone and the 3rd reaction zone flows with sieve catalyst and is adverse current.
10. the moving bed technique that uses according to claim 1 is characterized in that with the semicontinuous method of methanol conversion as propylene the WHSV of described first reaction zone, second reaction zone and the 3rd reaction zone is 0.1～20hr
-1
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924214A (en) * | 2012-10-30 | 2013-02-13 | 浙江大学 | Production technique of propylene |
| CN102942435A (en) * | 2012-11-06 | 2013-02-27 | 浙江大学 | Reaction technology using moving bed technique to convert methanol into propylene |
| CN103333040A (en) * | 2013-06-21 | 2013-10-02 | 浙江大学 | Low energy consumption propylene production technology |
| CN105983376A (en) * | 2015-02-02 | 2016-10-05 | 中石化广州工程有限公司 | Quenching method of moving bed reactor |
Citations (5)
| 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 |
| CN1646221A (en) * | 2002-02-28 | 2005-07-27 | 埃克森美孚化学专利公司 | Molecular sieve compositions, catalyst thereof, their making and use in conversion processes |
| CN101121146A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Method for preserving oxygen-containing compound conversion to produce olefine microshpere catalyst |
| CN101830769A (en) * | 2010-05-12 | 2010-09-15 | 浙江大学 | Method for converting methanol into propylene |
| CN101941876A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Method for increasing production of light olefin |
-
2011
- 2011-07-25 CN CN201110208634.2A patent/CN102344328B/en not_active Expired - Fee Related
Patent Citations (5)
| 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 |
| CN1646221A (en) * | 2002-02-28 | 2005-07-27 | 埃克森美孚化学专利公司 | Molecular sieve compositions, catalyst thereof, their making and use in conversion processes |
| CN101121146A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Method for preserving oxygen-containing compound conversion to produce olefine microshpere catalyst |
| CN101941876A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Method for increasing production of light olefin |
| CN101830769A (en) * | 2010-05-12 | 2010-09-15 | 浙江大学 | Method for converting methanol into propylene |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924214A (en) * | 2012-10-30 | 2013-02-13 | 浙江大学 | Production technique of propylene |
| CN102924214B (en) * | 2012-10-30 | 2015-02-25 | 浙江大学 | Production technique of propylene |
| CN102942435A (en) * | 2012-11-06 | 2013-02-27 | 浙江大学 | Reaction technology using moving bed technique to convert methanol into propylene |
| CN103333040A (en) * | 2013-06-21 | 2013-10-02 | 浙江大学 | Low energy consumption propylene production technology |
| CN105983376A (en) * | 2015-02-02 | 2016-10-05 | 中石化广州工程有限公司 | Quenching method of moving bed reactor |
| CN105983376B (en) * | 2015-02-02 | 2018-08-24 | 中石化广州工程有限公司 | A kind of quick cooling method for moving-burden bed reactor |
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|---|---|
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