CN102344328B - 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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- CN102344328B CN102344328B CN201110208634.2A CN201110208634A CN102344328B CN 102344328 B CN102344328 B CN 102344328B CN 201110208634 A CN201110208634 A CN 201110208634A CN 102344328 B CN102344328 B CN 102344328B
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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 semicontinuous method that moving bed technique is propylene by methanol conversion that uses.
Background technology
Propylene is a kind of important basic chemical industry raw material in modern chemistry industry, is second largest chemical of current global demand amount.Along with the development of countries in the world industrial economy, propylene demand is by increasing.The traditional production line of propylene is the catalytic pyrolysis of petroleum.Because world oil total amount is limited, International Crude Oil rises steadily, and causes take the cost that oil is raw material production propylene constantly to raise, thereby has caused the research boom with comparatively cheap methanol production propylene technology (MTP).Very high and be also difficult to from now on decline in the situation that, for the China of oil starvation, weak breath, rich coal, methanol production propylene Technology highlights stronger competitive power and far-reaching strategic importance more in current crude oil price.
At present, the MTO technology of comparative maturity mainly contains the MTO technology (MTO) of American UOP company and the fixed bed process for preparing propylene from methanol (MTP) of German Lurgi company in the world.The fluidized-bed process for preparing propylene from methanol (FMTP) that the preparing light olefins from methanol technique (DMTO) of domestic Ze You Dalian Chemiclophysics Inst., Chinese Academy of Sciences exploitation and Tsing-Hua University research and develop.MTO technique is mainly for the preparation of ethene and propylene, and MTP technique is mainly for the preparation of propylene.
Patented technology has been developed and formed to fixed bed process for preparing propylene from methanol mainly, the catalyzer that European patent EP 0448000B1, Chinese patent CN1431982A etc. all discloses this processing method and used by German Lurgi company.The ZSM-5 Type Zeolites agent that this processing method provides based on the southern chemical company of Germany, adopts single-stage and multistage insulation fix bed reactor, has higher propene yield, simultaneously a small amount of ethene of by-product, gasoline and liquefied petroleum gas (LPG) (LPG).Because catalyzer in fixed bed need carry out original position super regeneration, therefore, conventionally adopt arrange a plurality of fixed-bed reactor (as two open one standby, use two fixed-bed reactor, standby fixed-bed reactor) switch to address the above problem, but this design exists, system device requirement is high, the problem of complicated operation.
Fluidization is researched and developed successfully by Uop Inc. at first, and in addition, the current domestic Ye You Dalian Chemistry and Physics Institute, Tsing-Hua University are engaged in the exploitation of this technique.Fluidization mainly adopts 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 its industrial applications need to be captured from now on.
Moving bed technique because solid back-mixing in bed is little, reaction approaches piston flow, thereby feed stock conversion is high, and a bed inner catalyst constantly moves (regeneration) thereby can keep good catalytic performance, is more and more subject to researchist's attention.Publication number is that the Chinese patent application of CN1803738A discloses a kind of moving-bed preparing propylene from methanol technology, by adopting bifunctional molecule sieve catalyst, utilize reaction-method of regenerating to realize the circulation of catalyzer, the circulation of simultaneously introducing by product transforms, thereby improves the selectivity of propylene.ZSM-5 is a kind of molecular sieve catalyst with Mesoporous property, has medium coke deposit rate.Moving bed technique is a kind of technology of successive reaction regeneration, is particularly useful for having the catalyzer of medium coke deposit rate.It both can successive reaction regenerate as circulating fluidized bed, did not need again catalyzer to have very high wear resistance simultaneously.
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 Chinese patent application of CN 101367701A discloses a kind of employing two-stage reaction district, oxygen-containing compound material is generated to product in first paragraph reaction zone, again the above component of the C5 in product is passed into second reaction zone and carry out the pre-carbon deposit of catalyzer, again the catalyzer of the pre-carbon deposit in second reaction zone is reacted for the first reaction zone, finally catalyzer is passed into revivifier.The processing method of this reaction cyclic regeneration that utilizes successive reaction-regenerating unit and catalyzer is transported to the first reaction zone from second reaction zone, all need between reactive system and between reactive system and regenerating unit, increase special air-lift device by reactor stream catalyst transport out to regenerating unit regeneration, this needs very large 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 semicontinuous method that moving bed technique is propylene by methanol conversion that uses, only with a kind of molecular sieve catalyst, realized methyl alcohol in moving-bed and, to three sections of reactions of propylene, finally realized the object that improves propene yield.
Use the semicontinuous method that moving bed technique is propylene by methanol conversion, comprise the following steps:
1) after being mixed with catalyst diluent, molecular sieve catalyst passes into continuously the first reaction zone, methanol feedstock is passed into the first reaction zone to be contacted with molecular sieve catalyst, under 240 ℃～300 ℃, 0.1MPa～1MPa condition, molecular sieve catalyst stops 30h～100h in the first reaction zone, produces first burst of logistics;
First burst of described logistics comprises methyl alcohol, dme and water;
The first described reaction zone at least comprises a moving-burden bed reactor;
2) molecular sieve catalyst behind the first reaction zone enters into second reaction zone, by step 1) in first burst of logistics obtaining pass into second reaction zone and contact with molecular sieve catalyst, under 430 ℃～530 ℃, 0.1MPa～0.8MPa condition, molecular sieve catalyst stops 30h～100h in second reaction zone, produces second burst of logistics;
Second burst of described logistics comprises ethene, propylene, butylene, C
1～C
4alkane and C
5above component;
Described second reaction zone at least comprises a moving-burden bed reactor;
3) by step 2) in second burst of logistics and step 1 producing) in methanol feedstock heat exchange after, through dehydration, carry out separated (after removing afterwards the oxide compounds such as water and unconverted methyl alcohol and dme through gas-liquid separation and rectifying, carrying out separated) with oxide removal after, obtain second reaction zone returns, second reaction zone discharging and the 3rd reaction zone feeds, second reaction zone returns are incorporated to first burst of logistics and are circulated to step 2);
Described second reaction zone returns comprise ethene, butylene and C
2～C
4alkane, described second reaction zone discharging comprises C
1alkane and propylene, the 3rd described reaction zone feeds comprises C
5above component;
4) molecular sieve catalyst behind second reaction zone enters into the 3rd reaction zone, by step 3) in the 3rd reaction zone feeds that obtains pass into the 3rd reaction zone and contact with molecular sieve catalyst, under 465 ℃～540 ℃, 0.1MPa～0.5MPa condition, molecular sieve catalyst stops 30h～100h in the 3rd reaction zone, produces the 3rd burst of logistics;
The 3rd burst of described logistics comprises propylene, ethene, butylene, C
1～C
4alkane and C
5above hydrocarbon;
The 3rd described reaction zone at least comprises a moving-burden bed reactor;
Molecular sieve catalyst is transported to the first reaction zone continuously after mixing with catalyst diluent, the slow continuous moving of molecular sieve catalyst, flow through successively the first reaction zone, second reaction zone, the 3rd reaction zone, molecular sieve catalyst behind the 3rd reaction zone is regularly regenerated and is obtained regenerated catalyst after collecting, and regenerated catalyst is incorporated to off and on and in molecular sieve catalyst, is circulated to step 1).
In order to obtain better invention effect, below as of the present invention further preferably:
The semicontinuous method that described use moving bed technique is propylene by methanol conversion, also comprises: 5) by step 4) in the 3rd burst of logistics obtaining carry out after carrying out heat exchange with second reaction zone charging separatedly, separation obtains ethene, butylene and C
2～C
4alkane is incorporated to first burst of logistics and is circulated to step 2).Step 5) increase, make the present invention use moving bed technique by methanol conversion for capacity usage ratio in propylene and utilization of materials further improve, there is better economic benefit.
Moving-burden bed reactor can specifically be selected existing moving-burden bed reactor, as disclosed a kind of for take the tube-type moving-bed reactor of oxygenatedchemicals as raw material production propylene in the Chinese patent application that application number is 201010175837.1, application number is that 200810120839.3 Chinese patent application is disclosed a kind of for take the radially moving bed reactor that oxygenatedchemicals is raw material production propylene, and the Chinese patent application that application number is 200810120838.9 is disclosed a kind of for take the horizontal moving bed reactor of oxygenatedchemicals as raw material production propylene.
The catalyzer of three described reaction zones is same molecular sieve catalyst, described molecular sieve catalyst is preferably ZSM-5 molecular sieve, ZSM-5 molecular sieve is a kind of molecular sieve catalyst with Mesoporous property, has medium coke deposit rate, and the wearability in moving-bed is better.Because preparing propylene from methanol reaction is strong exothermal reaction, therefore need to add the solids dilute catalyst of inertia, large specific heat capacity, prevent hot localised points.Described catalyst diluent is ceramic particle or quartz sand particle, generally selects and has the measure-alike catalyst diluent of larger specific heat capacity, particle size and molecular sieve.Described molecular sieve catalyst and the mass ratio of catalyst diluent are 1: 1～20.Methanol feedstock can be different industrial raw material, as adopted the mixture of methyl alcohol or methyl alcohol and water, in methanol feedstock, can comprise a small amount of impurity.
Owing to adopting step 1) in the dme of the first burst of logistics reaction heat that generates propylene and other alkene than directly, from methanol conversion, be that propylene is much lower, the present invention is that propylene is divided into three steps by methanol conversion, wherein the first step is to be mainly dme (the first reaction zone) by methanol conversion, second step is to be mainly propylene (second reaction zone) by dimethyl ether conversion, and the 3rd step is that high-carbon hydrocarbon cracking is converted into propylene (the 3rd reaction zone).Thereby the reaction heat that is propylene by methanol conversion is divided into two portions, two portions reaction heat is released in respectively the first and second reaction zones.Because forming reaction, coke under comparatively high temps accelerates, simultaneously, molecular sieve catalyst dealumination reaction accelerates, therefore, the reaction heat that the present invention is propylene by methanol conversion is divided into two portions, thereby in the process that to avoid methanol conversion be propylene, temperature raises too fastly, not only can suppress the formation of coke, and can suppress the dealuminzation of catalyzer, make catalyzer keep high reactivity.
Described step 2), in first burst of logistics, add and pass into second reaction zone after water vapour and contact with molecular sieve catalyst.Water vapour can specifically be selected general facilities water vapour.The increase of water vapour can obviously reduce the carbon deposit of molecular sieve catalyst, makes the activity keeping of molecular sieve catalyst in certain limit value within the long period.Preferably the mol ratio of 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 ℃, under this temperature range, oxygenatedchemicals can effectively be converted into alkene, the lesser temps of this scope is conducive to the generation of propylene, and comparatively high temps is conducive to the generation of ethene, for the transformation efficiency of propylene is improved, temperature of reaction is preferably 450 ℃～500 ℃.
Reaction raw materials stream in the first described reaction zone, second reaction zone and the 3rd reaction zone flows and is adverse current with molecular sieve catalyst.Wherein, reaction raw materials stream is introduced to the top, ，Bing Cong reaction zone, bottom of reaction zone and shifted out, molecular sieve catalyst, under action of gravity, moves down, 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 molecular sieve catalyst of part inactivation, and when the flow velocity of reaction raw materials stream is lower, occur in going deep into the stage subsequently of conversion, reaction raw materials stream is that the molecular sieve catalyst higher with activity contacts, and therefore, methanol feedstock and molecular sieve catalyst flow and to be adverse current and can effectively to have kept the selectivity of catalyzer to low-carbon alkene.
Transformation efficiency and distribution of reaction products that catalyzer is propylene in the residence time of reaction zone (being the duration of contact of reactant and catalyzer) on methanol conversion have significant impact.The residence time is short, and raw material contacts insufficient with catalyzer, and reaction conversion ratio is low, and the residence time is oversize, easily causes the by products such as the alkane such as methane in product, propane, butane, aromatic hydrocarbons to increase.Conventionally by weight hourly space velocity (WHSV), represent the duration of contact of reactant and catalyzer, WHSV refers to the ratio of quality and the catalyst in reactor quality of reaction raw materials in charging per hour, WHSV numerical value is larger represents that the residence time is shorter, and the WHSV of the present invention the first reaction zone, second reaction zone and the 3rd reaction zone is preferred 0.1～20hr
-1.
The residence time of described molecular sieve catalyst in reaction zone is preferably 90～300h.Molecular sieve catalyst or the molecular sieve catalyst being incorporated to after regenerated catalyst enter after the moving-burden bed reactor of the first reaction zone from feed entrance, in moving-burden bed reactor, slowly move, then continuous moving, by the moving-burden bed reactor of second reaction zone, the moving-burden bed reactor of the 3rd reaction zone, shifted out moving-burden bed reactor and enters catalyzer collector after 90～300 hours.
Step 4) in, molecular sieve catalyst behind the 3rd reaction zone (being the molecular sieve catalyst of carbon deposit) adopts catalyzer collector, the molecular sieve catalyst of collecting is regularly transported in regenerating unit to regeneration and obtains regenerated catalyst, regenerated catalyst is incorporated to and in molecular sieve catalyst, is circulated to step 1).Described regenerated catalyst is 0～3: 7 with the mass ratio that is not incorporated to molecular sieve catalyst before regenerated catalyst (be fresh molecular sieve catalyst).Reactive system and catalyst regeneration device is independent mutually, and catalyzer runs up to a certain amount of sent for regeneration device regeneration of concentrating afterwards, not only can save conveying cost, has also reduced the complicacy of device.
A device that is propylene by methanol conversion, comprises catalyzer feed pot, catalyzer feed regulator, the first reaction zone, second reaction zone, the 3rd reaction zone, catalyzer discharging surge tank, catalyzer discharging controller and the catalyzer collector of connecting successively.Wherein, the first described reaction zone, second reaction zone and the 3rd reaction zone at least comprise respectively a moving-burden bed reactor.Each moving-burden bed reactor is placed in different level heights, between 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 connected in series by pipeline or moving-bed eclipsed form, after each moving-burden bed reactor connects, two ends are connected with catalyzer feed regulator, catalyzer discharging surge tank respectively.Each moving-burden bed reactor connecting in this way can guarantee that catalyzer relies on self gravitation to move from top to bottom, and successively by 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 be catalyzer by low pressure to high-pressure delivery without valvegear.This controls particle mobile and cut-off to high pressure section by low pressure without valvegear by tremie pipe, butterfly gate and the attached throttling set in low pressure epimere, transition interlude, high reduction section and connection adjacent both ends region.
Described catalyzer discharging controller is without block of valve pressure device.Pressure in reactor is during higher than external atmospheric pressure, for catalyzer being transported to from hopper to reaction zone, must improve the pressure of catalyst feeds or reduce the pressure of the first reaction zone, for achieving this end, at catalyst inlet, arrange one and press e Foerderanlage without the block of valve, without block of valve pressure device, can realize granules of catalyst conveying to low pressure by high pressure, and do not reveal the pressure in moving-burden bed reactor, realize a lock compression functions, and the blanking speed of the controlled controlling catalyst of this lock pressure device and can greatly reduce the wear phenomenon of catalyzer in blanking flow process.
This methanol conversion is that the device of propylene also comprises regenerating unit, and the molecular sieve catalyst in catalyzer collector adopts the way of artificial conveyance regularly to deliver in regenerating unit and regenerate, and joins off and in catalyzer feed pot afterwards.
In the first described reaction zone, second reaction zone, the 3rd reaction zone, be equipped with heat-exchanger rig.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 producing in reaction process, be convenient to better control the temperature of reaction of every step reaction, and the heat being swapped out can each reaction zone entrance of preheating material, save the input of general facilities heat, reached the object of utilization system heat energy.When thermal discharge is excessive, the chilling device of now setting up between moving-burden bed reactor, chilling device specifically can be selected interchanger, can effectively remove unnecessary reaction heat, as step 3) in after second burst of logistics and methanol feedstock heat exchange, the Quench liquid in chilling device specifically adopts methanol feedstock, methanol feedstock specifically can be selected the mixture of methyl alcohol or methyl alcohol and water, 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 to molecular sieve catalyst (being fresh molecular sieve catalyst) off and on, the continuous moving bed reaction district that passes through, carbon deposited catalyst centralized collection, the method of regular sent for regeneration, use a kind of molecular sieve catalyst to complete preparing dimethyl ether from methanol, three sections of reactions of dme propylene processed and high-carbon hydrocarbon cracking, realized material in reactor and reacted continuous with molecular sieve catalyst, the outer molecular sieve catalyst of reactor feeds in raw material and collects semi-continuous moving bed process, increased the independence of reactive system and regenerating unit, reduced the complicacy of whole plant.
2) the present invention uses semicontinuous method that moving bed technique is propylene by methanol conversion that reaction has been divided into three sections to react, use same molecular sieve catalyst for three sections, not only can improve the transformation efficiency that methyl alcohol generates dme conversion zone, reduce the content of methyl alcohol in 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 the upper different catalysts of operation need to draw the complicacy of regeneration simultaneously in batches.
3) reaction heat that the present invention is propylene reaction process by methanol conversion is divided into two sections, utilize reaction heat preheating that the etherification reaction of the first reaction zone is emitted to enter the reaction raw materials of second reaction zone, average temperature rising in propylene building-up reactions district can effectively be controlled, thereby reduced carbon distribution and the dealuminzation phenomenon of catalyzer, kept the high reactivity of catalyzer.
4) the present invention has solved catalyst charge and the affect problem of discharging on reaction unit stopping property by setting up catalyzer feed regulator and catalyzer discharging controller, adopt carbon deposited catalyst centralized collection, regularly the method for sent for regeneration, has simplified the design complexity installing.
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 for heating the inlet stream of high temperature section reaction zone, has fully utilized the heat energy of reaction feed and product discharging stream thigh.
6) the present invention adopts multi-reaction-area arranged superposed, and catalyzer continuous flow has realized and reacted long-term carrying out continuously.The present invention adopts second reaction zone freshening portion of product (ethene, butylene and C
2～C
4alkane), improved Propylene Selectivity.The present invention adopts the hydro carbons of the high carbon number of the 3rd reaction zone cracking, and by the freshening portion of product (C after separation
2～C
4alkane, ethene and butylene) turn back to second reaction zone reaction, reduced the content of by product, improved the yield of propylene.
Accompanying drawing explanation
Fig. 1 is the structural representation of the present invention's device that is propylene by methanol conversion.
Embodiment
As shown in Figure 1, for the device that is propylene by methanol conversion, comprise successively series connection catalyzer feed pot ST1, catalyzer feed regulator F1 (catalyzer by low pressure to high-pressure delivery without valvegear), the first D1, second reaction zone, reaction zone D2, the 3rd reaction zone D3, catalyzer discharging surge tank B, catalyzer discharging controller F2 and catalyzer collector ST2 (without block of valve pressure device).The first reaction zone D1, second reaction zone D2 and the 3rd reaction zone D3 at least comprise respectively a moving-burden bed reactor.Each moving-burden bed reactor is placed in different level heights, between 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 connected in series by pipeline or moving-bed eclipsed form, 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 molecular sieve catalyst employing artificial conveyance in catalyzer collector ST2 is regularly delivered in regenerating unit R and regenerated, and joins off and on afterwards in catalyzer feed pot ST1.In the first D1, second reaction zone, reaction zone D2, the 3rd reaction zone D3, be respectively equipped with heat-exchanger rig H1, H2, H3, E1 and E2.Heat-exchanger rig H1, H2, H3 are in moving-burden bed reactor and/or between each moving-burden bed reactor, for the material of each reaction zone entrance of more accurate preheating.Heat-exchanger rig E1 and E2 are for utilizing the material of each reaction zone entrance 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 the semicontinuous method that moving bed technique is propylene by methanol conversion, comprises the following steps:
1) molecular sieve catalyst and catalyst diluent are continuously joined to first reaction zone D1 by catalyzer feed regulator F1 from the first D1 top, reaction zone by catalyzer feed pot ST1, by regulating the throttling set of feed regulator F1 lower end to control the speed of charging; Methanol feedstock s is passed into the first reaction zone D1 from the first reaction zone D1 bottom and contacts with molecular sieve catalyst after heat-exchanger rig H1, under 240 ℃～300 ℃, 0.1MPa～1MPa reaction conditions, molecular sieve catalyst stops 30h～100h at the first reaction zone D1, and the outlet at the first D1 top, reaction zone produces first gang of logistics a;
First gang of described logistics a comprises methyl alcohol, dme and water;
The first described reaction zone D1 at least comprises a moving-burden bed reactor;
2) molecular sieve catalyst after the first reaction zone D1 enters into second reaction zone D2 from D2 top, second reaction zone, by step 1) in first gang of logistics a obtaining after heat-exchanger rig H2, from second reaction zone D2 bottom, pass into second reaction zone D2 and contact with molecular sieve catalyst, under 430 ℃～530 ℃, 0.1MPa～0.8MPa condition, molecular sieve catalyst stops 30h～100h at second reaction zone D2, produces second gang of logistics c and flows out from the outlet at D2 top, second reaction zone;
Second gang of described logistics c comprises ethene, propylene, butylene, C
1～C
4alkane and C
5above component;
Described second reaction zone D2 at least comprises a moving-burden bed reactor;
3) by step 2) in second gang of logistics c and step 1) in methanol feedstock s after heat-exchanger rig E1 heat exchange, through dehydration, enter disengaging zone sep1 after oxide removal separated, obtain second reaction zone returns d, second reaction zone discharging p1 and the 3rd reaction zone feeds e, second reaction zone returns d is incorporated to first gang of logistics a formation second reaction zone charging b and is circulated to step 2);
Described second reaction zone returns d comprises ethene, butylene and C
2～C
4alkane, described second reaction zone discharging p1 comprises C
1alkane and propylene, the 3rd described reaction zone feeds e comprises C
5above component;
The second reaction zone further separation of discharging p1 obtains comprising C
1alkane (fuel gas), propylene;
4) molecular sieve catalyst after the D2 of second reaction zone enters into the 3rd reaction zone D3 from the 3rd D3 top, reaction zone, by step 3) in the 3rd reaction zone feeds e that obtains after heat-exchanger rig H3, from the 3rd reaction zone D3 bottom, pass into the 3rd reaction zone D3 and contact with molecular sieve catalyst, under 465 ℃～540 ℃, 0.1MPa～0.5MPa condition, molecular 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 D3 top, reaction zone;
The 3rd gang of described logistics f comprises propylene, ethene, butylene, C
1～C
4alkane and C
5above hydrocarbon;
The 3rd described reaction zone D3 at least comprises a moving-burden bed reactor;
5) by step 4) in the 3rd gang of logistics f obtaining and second reaction zone charging after heat-exchanger rig E2 heat exchange, to enter disengaging zone sep2 separated, separation obtains ethene, butylene and C
2～C
4alkane is incorporated to first gang of logistics a and is circulated to step 2), final separation obtains comprising C
1alkane (fuel gas comprises a small amount of ethene), propylene, C
5above hydrocarbon (gasoline);
Molecular sieve catalyst is transported to the first reaction zone D1 continuously after mixing with catalyst diluent, the slow continuous moving of molecular sieve catalyst, the first D1, second reaction zone, reaction zone D2, the 3rd reaction zone D3 successively flow through, molecular sieve catalyst after the 3rd reaction zone D3, after molecular sieve catalyst discharging surge tank B and catalyzer discharging controller F2, the speed of molecular sieve catalyst blanking is controlled by the catalyzer discharging controller F2 (without block of valve pressure device) under surge tank B again.At catalyzer collector ST2, collect, be manually regularly transported to regeneration in regenerating unit R and obtain regenerated catalyst.Regenerated catalyst is incorporated to off and on and in molecular sieve catalyst, is circulated to step 1), described regenerated catalyst is 0～3: 7 with the mass ratio that is not incorporated to molecular sieve catalyst before regenerated catalyst (be fresh molecular sieve catalyst).
The separation method of disengaging zone sep1 and sep2 can referenced patent 200580025151.1 and the separating process introduced of patent 01810472.x.
Step 1), in, described molecular sieve catalyst is ZSM-5 molecular sieve.Described catalyst diluent is pottery or quartz sand particle.Described molecular sieve catalyst and the mass ratio of catalyst diluent are 1: 1～20.
Step 2), in, in first gang of described logistics a, add to pass into second reaction zone D2 after material thinner and contact with molecular sieve catalyst.Described material thinner is water vapour.Water vapour can specifically be selected general facilities water vapour.
Reaction raw materials stream in the first reaction zone D1, second reaction zone D2 and the 3rd reaction zone D3 flows and is adverse current with molecular sieve catalyst.The WHSV of the first reaction zone D1, second reaction zone D2 and the 3rd reaction zone D3 is 0.1～20hr
-1.
The methanol conversion of the present embodiment 1～3 is that the structure of the device of propylene can adopt structure as shown in Figure 1.
Embodiment 1
1) after being mixed with catalyst diluent, molecular sieve catalyst passes into continuously the first reaction zone, the temperature in of methanol feedstock is 240 ℃, methanol feedstock is passed into the first reaction zone to be contacted with molecular sieve catalyst, under 240 ℃～280 ℃, 0.2MPa～0.3MPa condition, molecular sieve catalyst stops 30h in the first reaction zone,, producing first burst of logistics, the temperature out of first burst of logistics is 280 ℃;
The first reaction zone is a moving-burden bed reactor;
2) molecular sieve catalyst behind the first reaction zone enters into second reaction zone, by step 1) in add in first burst of logistics obtaining and pass into second reaction zone after general facilities water vapour and contact with molecular sieve catalyst, the mol ratio of first burst of logistics and water vapour is 1: 1, the inlet temperature of first burst of logistics is 450 ℃, under 450 ℃～500 ℃, 0.15MPa～0.2MPa condition, molecular sieve catalyst stops 30h in 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) by step 2) in second burst of logistics and step 1) in after methanol feedstock heat exchange, after dehydration and oxide removal, obtain comprising the water of micro oxygen containing compound, carry out again separation, obtain second reaction zone returns, second reaction zone discharging and the 3rd reaction zone feeds, second reaction zone returns are incorporated to first burst of logistics and are circulated to step 2);
Second reaction zone returns comprise ethene, butylene and C
2～C
4alkane, second reaction zone discharging comprises C
1alkane and propylene, the 3rd reaction zone feeds comprises C
5above component;
Discharging further separation in second reaction zone obtains comprising C
1alkane (fuel gas), propylene;
4) molecular sieve catalyst behind second reaction zone enters into the 3rd reaction zone, by step 3) in the 3rd reaction zone feeds that obtains pass into the 3rd reaction zone and contact with molecular sieve catalyst, the inlet temperature of the 3rd reaction zone feeds is 520 ℃, under 470 ℃～520 ℃, 0.1MPa～0.15MPa condition, molecular sieve catalyst stops 30h in the 3rd reaction zone, produce the 3rd burst of logistics, temperature out is 470 ℃;
The 3rd burst of described logistics comprises propylene, ethene, butylene, C
1～C
4alkane, C
5above hydrocarbon;
The 3rd described reaction zone is a moving-burden bed reactor;
5) by step 4) in the 3rd burst of logistics obtaining carry out after carrying out heat exchange with second reaction zone charging separatedly, separation obtains ethene, butylene and C
2～C
4alkane is incorporated to first burst of logistics and is circulated to step 2), final separation obtains comprising C
1the mixture (fuel gas) that alkane and a small amount of ethene form, propylene, a small amount of C
3～C
4hydro carbons (due in suitability for industrialized production, fail the whole C in the 3rd burst of logistics
3～C
4alkane, propylene and butylene are all separated, in last discharging, still comprise a small amount of C
3～C
4hydro carbons, as liquefied petroleum gas (LPG)), C
5above hydrocarbon (gasoline).
It is the ZSM-5 molecular sieve of 1.5～2mm that molecular sieve catalyst is selected particle diameter.Catalyst diluent is the ceramic particle roughly the same with molecular sieve catalyst size, and the mass ratio of molecular sieve catalyst and catalyst diluent is 1: 3.
The residence time of the molecular sieve catalyst (carbon deposition catalyst) shifting out from the bed bottom of the moving-burden bed reactor of the 3rd reaction zone in bed is 90 hours, coke content is less than 3%, being collected in regular concentrated delivering in revivifier in catalyzer collector regenerates, obtain regenerated catalyst, the coke content of regenerated catalyst is lower than 0.5% (the carbon deposit quality depositing on coke content=unit weight catalyzer).Regenerated catalyst is incorporated to off and on and in molecular sieve catalyst, is circulated to step 1), the mass ratio of regenerated catalyst and fresh molecular sieve catalyst is 1: 7.
The WHSV of the first described 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 above-mentioned condition, and this material balance is based on experimental data, by computer simulation, to be enlarged into 1,000,000 tons of annual treatment capacities of methyl alcohol to obtain.As can be known from Table 1, methanol feeding amount is 207383kg/h, and the propylene amount generating is 66275kg/h, and methanol conversion is greater than 98%.
Table 1 material balance
| Material | Mass flow |
| Methyl alcohol | 207383kg/h |
| Propylene | 62275kg/h |
| Liquefied petroleum gas (LPG) (LPG) | 4032kg/h |
| Gasoline | 17905kg/h |
| Water (comprising micro oxygen containing compound) | 118076kg/h |
| Fuel gas # | 1466kg/h |
| Coke * | 82kg/h |
In table 1, # represents to comprise a small amount of ethene, and * represents to comprise the loss in Matter Transfer; Wherein LPG is C
3～C
4hydro carbons, be mainly alkane, comprise a small amount of alkene; Gasoline is C
5above hydrocarbon, comprises a small amount of C
4hydrocarbon is mainly 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 is mainly a small amount of C
1～C
2hydrocarbon component (is mainly C
1alkane, contains a small amount of ethene), coke is the carbon laydown on catalyzer, lower same.
Each product is converted into the butt percentage composition beyond dewatering, has listed the products distribution with respect to material benzenemethanol, as shown in table 2.
Table 2 products distribution
| Product | Butt percentage |
| Propylene | 72.62％ |
| Liquefied petroleum gas (LPG) (LPG) | 4.70％ |
| Gasoline | 20.88％ |
| Fuel gas | 1.71％ |
| Coke | 0.10％ |
Embodiment 2
1) after being mixed with catalyst diluent, molecular sieve catalyst passes into continuously the first reaction zone, the temperature in of methanol feedstock is 260 ℃, methanol feedstock is passed into the first reaction zone to be contacted with molecular sieve catalyst, under 260 ℃～300 ℃, 0.4MPa～0.6MPa condition, molecular sieve catalyst stops 50h in the first reaction zone,, producing first burst of logistics, the temperature out of first burst of logistics is 300 ℃;
The first reaction zone is a moving-burden bed reactor;
2) molecular sieve catalyst behind the first reaction zone enters into second reaction zone, by step 1) in add in first burst of logistics obtaining and pass into second reaction zone after general facilities water vapour and contact with molecular sieve catalyst, the mol ratio of first burst of logistics and water vapour is 4: 1, the inlet temperature of first burst of logistics is 470 ℃, under 470 ℃～520 ℃, 0.2MPa～0.4MPa condition, molecular sieve catalyst stops 50h in 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) by step 2) in second burst of logistics and step 1) in after methanol feedstock heat exchange, after dehydration and oxide removal, obtain comprising the water of micro oxygen containing compound, carry out again separation, obtain second reaction zone returns, second reaction zone discharging and the 3rd reaction zone feeds, second reaction zone returns are incorporated to first burst of logistics and are circulated to step 2);
Second reaction zone returns comprise ethene, butylene and C
2～C
4alkane, second reaction zone discharging comprises C
1alkane and propylene, the 3rd reaction zone feeds comprises C
5above component;
Discharging further separation in second reaction zone obtains comprising C
1mixture (fuel gas), the propylene of alkane and a small amount of ethene;
4) molecular sieve catalyst behind second reaction zone enters into the 3rd reaction zone, by step 3) in the 3rd reaction zone feeds that obtains pass into the 3rd reaction zone and contact with molecular sieve catalyst, the inlet temperature of the 3rd reaction zone feeds is 530 ℃, under 480 ℃～530 ℃, 0.1MPa～0.2MPa condition, molecular sieve catalyst stops 50h in the 3rd reaction zone, produce the 3rd burst of logistics, temperature out is 480 ℃;
The 3rd burst of described logistics comprises propylene, ethene, butylene, C
1～C
4alkane, C
5above hydrocarbon;
The 3rd described reaction zone is a moving-burden bed reactor;
5) by step 4) in the 3rd burst of logistics obtaining carry out after carrying out heat exchange with second reaction zone charging separatedly, separation obtains ethene, butylene and C
2～C
4alkane is incorporated to first burst of logistics and is circulated to step 2), final separation obtains comprising C
1the mixture (fuel gas) that alkane and a small amount of ethene form, propylene, a small amount of C
3～C
4hydro carbons (due in suitability for industrialized production, fail the whole C in the 3rd burst of logistics
3～C
4alkane, propylene and butylene are all separated, in last discharging, still comprise a small amount of C
3～C
4hydro carbons, as liquefied petroleum gas (LPG)), C
5above hydrocarbon (gasoline).
It is the ZSM-5 molecular sieve of 1.5～2mm that molecular sieve catalyst is selected particle diameter.Catalyst diluent is the quartz sand particle roughly the same with molecular sieve catalyst size, and the mass ratio of molecular sieve catalyst and catalyst diluent is 1: 5.
The residence time of the molecular sieve catalyst (carbon deposition catalyst) shifting out from the bed bottom of the moving-burden bed reactor of the 3rd reaction zone in bed is 150 hours, coke content is less than 3%, being collected in regular concentrated delivering in revivifier in catalyzer collector regenerates, obtain regenerated catalyst, the coke content of regenerated catalyst is lower than 0.5% (the carbon deposit quality depositing on coke content=unit weight catalyzer).Regenerated catalyst is incorporated to off and on and in molecular sieve catalyst, is circulated to step 1), the mass ratio of regenerated catalyst and fresh molecular sieve catalyst is 3: 7.
The WHSV of the first described 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 above-mentioned condition, and this material balance is based on experimental data, by computer simulation, to be enlarged into 1,000,000 tons of annual treatment capacities of methyl alcohol to obtain.As can be known from Table 3, methanol feeding amount is 207383kg/h, and the propylene amount generating is 64451kg/h, and methanol conversion is greater than 99%.
Table 3 material balance
| Material | Mass flow |
| Methyl alcohol | 207383kg/h |
| Propylene | 64451kg/h |
| Liquefied petroleum gas (LPG) (LPG) | 4309kg/h |
| Gasoline | 17768kg/h |
| Water (comprising micro oxygen containing compound) | 118736kg/h |
| Fuel gas # | 1588kg/h |
| Coke * | 83kg/h |
In table 3, # represents to comprise a small amount of ethene, and * represents to comprise the loss in Matter Transfer;
Each product is converted into the butt percentage composition beyond dewatering, has listed the products distribution with respect to material benzenemethanol, as shown in table 4.
Table 4 products distribution
| Product | Butt percentage |
| Propylene | 73.07％ |
| Liquefied petroleum gas (LPG) (LPG) | 4.89％ |
| Gasoline | 20.15％ |
| Fuel gas | 1.80％ |
| Coke | 0.09％ |
Embodiment 3
1) after being mixed with catalyst diluent, molecular sieve catalyst passes into continuously the first reaction zone, the temperature in of methanol feedstock is 280 ℃, methanol feedstock is passed into the first reaction zone to be contacted with molecular sieve catalyst, under 280 ℃～320 ℃, 0.8MPa～1MPa condition, molecular sieve catalyst stops 100h in the first reaction zone, produce first burst of logistics, the temperature out of first burst of logistics is 320 ℃;
The first reaction zone is a moving-burden bed reactor;
2) molecular sieve catalyst behind the first reaction zone enters into second reaction zone, by step 1) in add in first burst of logistics obtaining and pass into second reaction zone after general facilities water vapour and contact with molecular sieve catalyst, the mol ratio of first burst of logistics and water vapour is 1: 4, the inlet temperature of first burst of logistics is 480 ℃, under 480 ℃～530 ℃, 0.3MPa～0.5MPa condition, molecular sieve catalyst stops 100h in 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) by step 2) in second burst of logistics and step 1) in after methanol feedstock heat exchange, after dehydration and oxide removal, obtain comprising the water of micro oxygen containing compound, carry out again separation, obtain second reaction zone returns, second reaction zone discharging and the 3rd reaction zone feeds, second reaction zone returns are incorporated to first burst of logistics and are circulated to step 2);
Second reaction zone returns comprise ethene, butylene and C
2～C
4alkane, second reaction zone discharging comprises C
1alkane and propylene, the 3rd reaction zone feeds comprises C
5above component;
Discharging further separation in second reaction zone obtains comprising C
1mixture (fuel gas), the propylene of alkane and a small amount of ethene;
4) molecular sieve catalyst behind second reaction zone enters into the 3rd reaction zone, by step 3) in the 3rd reaction zone feeds that obtains pass into the 3rd reaction zone and contact with molecular sieve catalyst, the inlet temperature of the 3rd reaction zone feeds is 540 ℃, under 490 ℃～540 ℃, 0.1MPa～0.3MPa condition, molecular sieve catalyst stops 100h in the 3rd reaction zone, produce the 3rd burst of logistics, temperature out is 490 ℃;
The 3rd burst of described logistics comprises propylene, ethene, butylene, C
1～C
4alkane, C
5above hydrocarbon;
The 3rd described reaction zone is a moving-burden bed reactor;
5) by step 4) in the 3rd burst of logistics obtaining carry out after carrying out heat exchange with second reaction zone charging separatedly, separation obtains ethene, butylene and C
2～C
4alkane is incorporated to first burst of logistics and is circulated to step 2), final separation obtains comprising C
1the mixture (fuel gas) that alkane and a small amount of ethene form, propylene, a small amount of C
3～C
4hydro carbons (due in suitability for industrialized production, fail the whole C in the 3rd burst of logistics
3～C
4alkane, propylene and butylene are all separated, in last discharging, still comprise a small amount of C
3～C
4hydro carbons, as liquefied petroleum gas (LPG)), C
5above hydrocarbon (gasoline).
It is the ZSM-5 molecular sieve of 1.5～2mm that molecular sieve catalyst is selected particle diameter.Catalyst diluent is the ceramic particle roughly the same with molecular sieve catalyst size, and the mass ratio of molecular sieve catalyst and catalyst diluent is 1: 8.
The residence time of the molecular sieve catalyst (carbon deposition catalyst) shifting out from the bed bottom of the moving-burden bed reactor of the 3rd reaction zone in bed is 300 hours, coke content is less than 3%, being collected in regular concentrated delivering in revivifier in catalyzer collector regenerates, obtain regenerated catalyst, the coke content of regenerated catalyst is lower than 0.5% (the carbon deposit quality depositing on coke content=unit weight catalyzer).Regenerated catalyst is incorporated to off and on and in molecular sieve catalyst, is circulated to step 1), the mass ratio of regenerated catalyst and fresh molecular sieve catalyst is 2: 7.
The WHSV of the first described 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 above-mentioned condition, and this material balance is based on experimental data, by computer simulation, to be enlarged into 1,000,000 tons of annual treatment capacities of methyl alcohol to obtain.As can be known from Table 5, methanol feeding amount is 207383kg/h, and the propylene amount generating is 69380kg/h, methanol conversion 100%.
Table 5 material balance
| Material | Mass flow |
| Methyl alcohol | 207383kg/h |
| Propylene | 69380kg/h |
| Liquefied petroleum gas (LPG) (LPG) | 5703kg/h |
| Gasoline | 15656kg/h |
| Water (comprising micro oxygen containing compound) | 115063kg/h |
| Fuel gas # | 1487kg/h |
| Coke * | 94kg/h |
In table 5, # represents to comprise a small amount of ethene, and * represents to comprise the loss in Matter Transfer;
Each product is converted into the butt percentage composition beyond dewatering, has listed the products distribution with respect to material benzenemethanol, as shown in table 6.
Table 6 products distribution
| Product | Butt percentage |
| Propylene | 75.15％ |
| Liquefied petroleum gas (LPG) (LPG) | 6.18％ |
| Gasoline | 16.96％ |
| Fuel gas | 1.61％ |
| Coke | 0.10％ |
From above-mentioned three embodiment, find out, according to processing method disclosed by the invention, can obtain good temperature control and online reaction times of catalyzer and higher Propylene Selectivity.In addition, in scope disclosed by the invention, operate, the selectivity rangeability of product is less.
Claims (3)
1. use the semicontinuous method that moving bed technique is propylene by methanol conversion, comprise the following steps:
1) after being mixed with catalyst diluent, molecular sieve catalyst passes into continuously the first reaction zone, methanol feedstock is passed into the first reaction zone to be contacted with molecular sieve catalyst, under 240 ℃～300 ℃, 0.1MPa～1MPa condition, molecular sieve catalyst stops 30h～100h in the first reaction zone, produces first burst of logistics;
First burst of described logistics comprises methyl alcohol, dme and water;
The first described reaction zone at least comprises a moving-burden bed reactor;
Described molecular sieve catalyst is ZSM-5 molecular sieve;
Described catalyst diluent is ceramic particle or quartz sand particle;
Described molecular sieve catalyst and the mass ratio of catalyst diluent are 1:1～20;
2) molecular sieve catalyst behind the first reaction zone enters into second reaction zone, the first burst of logistics obtaining in step 1) passed into second reaction zone to be contacted with molecular sieve catalyst, under 430 ℃～530 ℃, 0.1MPa～0.8MPa condition, molecular sieve catalyst stops 30h～100h in second reaction zone, produces second burst of logistics;
Second burst of described logistics comprises ethene, propylene, butylene, C
1～C
4alkane and C
5above component;
Described second reaction zone at least comprises a moving-burden bed reactor;
In first burst of described logistics, add and pass into second reaction zone after material thinner and contact with molecular sieve catalyst;
Described material thinner is water vapour;
3) by step 2) in after the second burst of logistics and the methanol feedstock heat exchange in step 1) that produce, through dehydration, carry out separated after oxide removal, obtain second reaction zone returns, second reaction zone discharging and the 3rd reaction zone feeds, second reaction zone returns are incorporated to first burst of logistics and are circulated to step 2);
Described second reaction zone returns comprise ethene, butylene and C
2～C
4alkane, described second reaction zone discharging comprises C
1alkane and propylene, the 3rd described reaction zone feeds comprises C
5above component; 4) molecular sieve catalyst behind second reaction zone enters into the 3rd reaction zone, the 3rd reaction zone feeds obtaining in step 3) is passed into the 3rd reaction zone to be contacted with molecular sieve catalyst, under 465 ℃～540 ℃, 0.1MPa～0.5MPa condition, molecular sieve catalyst stops 30h～100h in the 3rd reaction zone, produces the 3rd burst of logistics;
The 3rd burst of described logistics comprises propylene, ethene, butylene, C
1～C
4alkane and C
5above hydrocarbon;
The 3rd described reaction zone at least comprises a moving-burden bed reactor;
Molecular sieve catalyst is transported to the first reaction zone continuously after mixing with catalyst diluent, the slow continuous moving of molecular sieve catalyst, flow through successively the first reaction zone, second reaction zone, the 3rd reaction zone, molecular sieve catalyst behind the 3rd reaction zone is regularly regenerated and is obtained regenerated catalyst after collecting, and regenerated catalyst is incorporated to off and on and in molecular sieve catalyst, is circulated to step 1);
5) carry out after the 3rd burst of logistics obtaining in step 4) carried out to heat exchange with second reaction zone charging separatedly, separation obtains ethene, butylene and C
2～C
4alkane is incorporated to first burst of logistics and is circulated to step 2);
Reaction raw materials stream in the first described reaction zone, second reaction zone and the 3rd reaction zone flows and is adverse current with molecular sieve catalyst.
2. the semicontinuous method that use moving bed technique according to claim 1 is propylene by methanol conversion, is characterized in that, described regenerated catalyst is 0～3:7 with the mass ratio that is not incorporated to the molecular sieve catalyst before regenerated catalyst.
3. the semicontinuous method that use moving bed technique according to claim 1 is propylene by methanol conversion, is characterized in that, the WHSV of the first described reaction zone, second reaction zone and the 3rd reaction zone is 0.1～20hr
-1.
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| 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 |
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