CN101830769B - Method for converting methanol into propylene - Google Patents
Method for converting methanol into propylene Download PDFInfo
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- CN101830769B CN101830769B CN2010101722187A CN201010172218A CN101830769B CN 101830769 B CN101830769 B CN 101830769B CN 2010101722187 A CN2010101722187 A CN 2010101722187A CN 201010172218 A CN201010172218 A CN 201010172218A CN 101830769 B CN101830769 B CN 101830769B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 288
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 160
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 53
- 239000000047 product Substances 0.000 claims abstract description 38
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 30
- 239000000376 reactant Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 238000010517 secondary reaction Methods 0.000 claims abstract description 9
- 239000001294 propane Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000470 constituent Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 10
- 238000009395 breeding Methods 0.000 claims description 7
- 230000001488 breeding effect Effects 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 23
- 230000008021 deposition Effects 0.000 description 14
- 230000008929 regeneration Effects 0.000 description 14
- 238000011069 regeneration method Methods 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 239000003915 liquefied petroleum gas Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000003502 gasoline Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 239000002737 fuel gas Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229960004217 benzyl alcohol Drugs 0.000 description 3
- 238000005094 computer simulation Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for converting methanol into propylene, which comprises the following steps of: introducing methanol into a methanol reaction zone to perform reaction so as to obtain a mixture of the methanol, dimethyl ether and water; dividing the mixture into a plurality of reactant streams; feeding the first reactant stream to a first reaction zone to perform reaction to obtain a product stream, mixing the product stream and any one of the other reactant streams, feeding the mixture to the first reaction zone to perform reaction until the product stream is mixed with the last reactant stream and feeding the mixture to the first reaction zone to perform reaction so as to obtain a primary reaction product stream; separating the primary reaction product stream to obtain the propylene, propane, C1 to C2 hydrocarbon, C4 hydrocarbon, C5 to C6 hydrocarbon and hydrocarbons with more than seven carbon atoms; circulating the C1 to C2 hydrocarbon and the C4 hydrocarbon to the first reaction zone to perform reaction continuously; feeding the C5 to C6 hydrocarbon and part of the hydrocarbons with more than seven carbon atoms to the second reaction zone to perform reaction so as to obtain a secondary reaction product stream; and separating the secondary reaction product stream to obtain the propylene. The method is suitable for the reactions with high heat discharge and temperature sensitivity such as the reaction for preparing the propylene from the methanol and has the advantages of high target selectivity, continuous and stable reaction and high efficiency.
Description
Technical field
The present invention relates to the preparation method of propylene, relating in particular to a kind of is the method for propylene with methanol conversion.
Background technology
Propylene is the necessary a kind of basic chemical industry raw material of modern chemistry industry; Along with the continuous development of industrial economy, the tomorrow requirement amount will constantly increase, and traditional propylene industrial production basically all is raw material with the petroleum base; Like steam cracking of oil etc.; And oil, is faced with in the long run and is about to exhausted crisis through overexploitation consumption for many years as a kind of Nonrenewable resources; Receive simultaneously again on short terms factors such as geography, economy, politics to influence price volalility violent, so this area is sought a kind ofly can substitute the method that oil is the raw material production propylene always.
The preparing propylene from methanol technology is a kind of non-oil resource production of propylene technology, has great application prospect.Fixed bed preparing propylene from methanol (MTP) technology of the technological and German Lurgi of the fluidized-bed methanol-to-olefins (MTO) that the mainly contains Uop Inc. company of present comparative maturity in the world.The former mainly prepares ethene and propylene, and the latter mainly prepares propylene.
Fluidization mainly adopts the SAPO-34 catalyzer, and this technology has very high selectivity to low-carbon alkene, but propylene list selectivity is not high, needs to adopt the mode of product secondary reaction, improve the propylene selectivity, so technology investment is relatively large.Except Uop Inc., the domestic exploitation that also has Dalian Chemiclophysics Inst., Chinese Academy of Sciences, Tsing-Hua University to be engaged in fluidized-bed process.
Bed technology patent merchant mainly is a German Lurgi company, and this technology propylene list selectivity is higher.The technology and the employed catalyzer of German Lurgi company fixed bed preparing propylene from methanol are disclosed among European patent EP 0448000B1 and the Chinese patent CN1431982A; The data that is disclosed according to the disclosed content of patent and Lurgi company; Its process method has higher propene yield, simultaneously by-product small amount of ethylene, LPG (LPG liquefied petroleum gas) and gasoline etc.Because catalyzer needs in-situ regeneration in the fixed bed, so Lurgi company switches to address the above problem through a plurality of fixed-bed reactor are set in its commercialization demonstration unit, and the system device requirement is high, the problem of complicated operation but caused simultaneously.
ZSM-5 is a kind of sieve catalyst with mesopore character, has medium carbon distribution speed.Moving bed technique is a kind of successive reaction regeneration techniques, the catalyzer that is particularly useful for having medium carbon distribution speed.It both can not need very high wear resistance requirement simultaneously again as the regeneration of circulating fluidized bed successive reaction.
Publication number is to disclose a kind of moving-bed preparing propylene from methanol technology in the one Chinese patent application of CN1803738A and the one Chinese patent application that publication number is CN101023048A; Through controlling certain catalyst circulation rate and particular treatment method, improve the selectivity of propylene.Yet the heat energy power of removing of moving-burden bed reactor itself a little less than, and preparing propylene from methanol reaction is strong exothermic process, removes if heat is untimely in the reactor drum; Not only cause temperature of reaction to improve rapidly; The propylene selectivity descends, and will cause the reactor drum temperature runaway when serious, causes security incident.And in above-mentioned two patented claims and the not mentioned heat problem of removing that how to solve in the moving-bed.
Therefore, design and develop and have the moving-burden bed reactor of removing heat energy power by force and be the method for propylene, have great importance for improving propylene selectivity and reaction stability with methanol conversion.
Summary of the invention
The invention provides a kind of is the method for propylene with methanol conversion, and what mainly solved strong exothermal reaction in the present preparing propylene from methanol moving-burden bed reactor removes heat, production is discontinuous and the propylene selectivity is lower problem.
A kind of is the method for propylene with methanol conversion, may further comprise the steps:
(1) methyl alcohol is fed methanol reaction zone and catalyzer contact reacts, reaction obtains the mixture of methyl alcohol, dme and water;
(2) mixture with above-mentioned methyl alcohol, dme and water is divided into some bursts of reactant flow, and first burst of reactant flow sent into first reaction zone, with the catalyzer contact reacts; Obtain product stream; Product stream is sent into first reaction zone after one reactant flow is mixed arbitrarily with other, with the catalyzer contact reacts, flows and sends into first reaction zone after one reactant flow is mixed at last until product; With the catalyzer contact reacts, obtain being rich in the primary first-order equation product stream of propylene;
(3) above-mentioned primary first-order equation product stream is sent into the disengaging zone, behind dehydration and oxide removal, obtain propylene, propane, C respectively
1-C
2Hydrocarbon, C
4Hydrocarbon, C
5-C
6Hydrocarbon and C
7The heavy constituent of above hydrocarbon;
(4) with C
1-C
2Hydrocarbon and C
4Hydrocarbon be circulated to first reaction zone and continue reaction;
(5) with C
5-C
6Hydrocarbon and portion C
7Second reaction zone is sent in the heavy constituent of above hydrocarbon, with the catalyzer contact reacts, obtains containing the secondary reaction product stream of propylene;
Described portion C
7The quality of the heavy constituent of above hydrocarbon is C
7Below 30% of heavy constituent total mass of above hydrocarbon, remaining C
7The heavy constituent of above hydrocarbon are as by product;
(6) above-mentioned secondary reaction product stream is sent into the disengaging zone, obtain propylene, propane, C respectively
1-C
2Hydrocarbon, C
4Hydrocarbon, C
5-C
6Hydrocarbon and C
7The heavy constituent of above hydrocarbon;
(7) discharge from second reaction zone behind the described catalyst carbon deposit, get into and be circulated to methanol reaction zone after regenerating in the breeding blanket.When the catalyst carbon deposition inactivation to a certain degree, methyl alcohol can penetrate beds, need send catalyzer into breeding blanket regeneration this moment, to keep the reactive behavior and the selectivity of optimum.
Described methanol reaction zone, first reaction zone and second reaction zone preferably are made up of the setting moving-burden bed reactor that several are connected in series; The bottom of each moving-burden bed reactor is connected (for example, can connect) through pipeline with the top of its next moving-burden bed reactor.This set can guarantee that catalyzer relies on self gravitation to move from top to bottom, and from top to bottom successively through each moving-burden bed reactor, makes material benzenemethanol and catalyzer form cross-flow; Can also cut down the consumption of energy simultaneously.
Described methanol reaction zone is at least one moving-burden bed reactor.
Described first reaction zone is at least two setting moving-burden bed reactors that are connected in series, and the number of share of stock of described reactant flow is identical with the number of the first reaction zone moving-burden bed reactor.
Described second reaction zone is at least one moving-burden bed reactor.
The present invention can adjust the quantity of each reaction zone moving-burden bed reactor according to the size of production capacity.
Total number of moving-burden bed reactor is preferably 4-8 in described methanol reaction zone, first reaction zone and second reaction zone, to practice thrift cost.
Described methanol reaction zone, first reaction zone and second reaction zone are 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 in moving-burden bed reactor, can removes the reaction heat that produces in the reaction process.Between each moving-burden bed reactor, heat-exchanger rig is set, is convenient to the temperature of reaction of the per step reaction of better control.Can place between moving bed reaction wall and the beds heat-exchanger rig and/or between beds and the beds when specifically being provided with.
Be provided with chilling device in described first reaction zone, mix with any one reactant flow from the effusive Quench liquid of chilling device.
When thermal discharge is excessive; In the moving-burden bed reactor and the heat-exchanger rig between each moving-burden bed reactor still can't remove reaction heat; Set up chilling device and can effectively remove unnecessary reaction heat this moment between moving-burden bed reactor, be used for rapidly the temperature of product stream being reduced to the temperature in of next moving-burden bed reactor.Quench liquid in the chilling device can adopt the mixture of methyl alcohol or water or methyl alcohol and water.
Described Quench liquid is selected from methyl alcohol or water or both mixtures, when adopting the mixture of methyl alcohol or methyl alcohol and water, can improve the raw material treatment capacity simultaneously.
Described catalyzer can select for use methyl alcohol to prepare propylene catalyzer commonly used, preferred ZSM-5 sieve catalyst.
The preparing propylene from methanol reaction is at first dewatered on catalyzer by material benzenemethanol and is generated the mixture of dme, first alcohol and water; Methyl alcohol and dme continue the hydrocarbon compound that the reaction generation contains propylene on catalyzer subsequently; Two-step reaction is thermopositive reaction; In order to reduce the thermal load of single moving-burden bed reactor, the present invention is placed on above-mentioned two-step reaction in the different reaction zones and carries out, and promptly carries out in the methanol reaction zone and first reaction zone respectively.
Dehydration of methanol is generally carried out at 250 ℃-300 ℃, further generates the hydrocarbons temperature of 450 ℃-500 ℃ of needs then that contains propylene.Therefore, the temperature in of described methanol reaction zone is 250 ℃-300 ℃, and the temperature in of each moving-burden bed reactor all keeps identical in the methanol reaction zone; The temperature in of described first reaction zone is 450 ℃-500 ℃, and the temperature in of each moving-burden bed reactor all keeps identical in first reaction zone.
The temperature in of described second reaction zone is preferably high 15 ℃-30 ℃ than the temperature in of first reaction zone, and the temperature in of each moving-burden bed reactor all keeps identical in second reaction.
Because it is strong exothermal reaction that methyl alcohol, dme and water mixture further change the hydrocarbons that contains propylene into; Therefore preferably reaction is divided into a plurality of carrying out in first reaction zone; Both can disperse reaction heat; Through on moving-burden bed reactor, adding heat-exchanger rig and chilling device, can with temperature rise control in lower scope, improve the propylene selectivity simultaneously.In principle, the moving-burden bed reactor number is many more, and temperature control is good more, but can cause facility investment to increase, and operation is complicated more, and therefore first reaction zone generally is preferably 3-5 moving-burden bed reactors.
Methyl alcohol, dme obtain being rich in the product stream of propylene after through primary first-order equation, and by product comprises propane, C
1-C
2Hydrocarbon, C
4Hydrocarbon, C
5-C
6Hydrocarbon and C
7The heavy constituent of above hydrocarbon, the low by product of economic worth is (like C
5-C
6Hydrocarbon and C
7The heavy constituent of above hydrocarbon) can further be converted into propylene through secondary reaction.Because the second reaction zone inner catalyst part carbon distribution, the active reduction in order to compensate activity, satisfied the demand of hydrocarbon cracking reaction simultaneously, and the temperature of reaction of second reaction zone is a little more than first reaction zone.Because reaction of the present invention belongs to the reaction of temperature sensitive class; Temperature of reaction is bigger to the influence of propylene selectivity; So each reactor drum keeps identical interior each reactor drum of temperature, second reaction zone also to keep identical temperature in first reaction zone, to obtain the highest propylene selectivity.
The present invention has following advantage:
(1) the present invention is divided into a plurality of carrying out with reaction, and the multiply raw material is sample introduction respectively, reduces the thermal discharge of single reactor drum;
(2) the present invention through in the reactor drum device and/or device set up heat-exchanger rig, remove heat of reaction rapidly;
(3) the present invention sets up chilling device at the first maximum reaction zone of thermal discharge, strengthens removing heat energy power, improves the raw material treatment capacity simultaneously.
(4) the present invention adopts the second reaction zone freshening portion of product, improves the propylene selectivity.
(5) the present invention adopts the multi-reaction-area arranged superposed, catalyzer continuous flow regeneration, and realization response is secular to be carried out continuously.
(6) the inventive method can solve the heat problem of removing of heat of reaction in the existing moving-burden bed reactor preferably, makes that methyl alcohol, dimethyl ether conversion are that the stable temperature range of being reflected at of propylene is carried out, and have high propylene selectivity and reaction stability.Through the reactor drum layout and the successive reaction regeneration of continous way up and down, realized the continuity of catalyzer and product stream simultaneously, production process can be carried out continuously, efficient is higher.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method;
Fig. 2 is the process flow diagram of a kind of reactor drum of the inventive method employing;
Raw material and product stream dot, and catalyst stream representes that with solid line for the purpose of simplifying the description, parts such as well heater, part interchanger, disengaging zone, breeding blanket, pipeline, valve omit in the drawings.
Embodiment
Like Fig. 1, shown in Figure 2, adopt a moving-burden bed reactor with methanol reaction zone, first reaction zone adopts three moving-burden bed reactors, and it is example that second reaction zone adopts a moving-burden bed reactor, specifies.
Material benzenemethanol is through interchanger heat exchange to methanol reaction zone temperature in (select 250 ℃-300 ℃ according to practical situation in a steady state value); Get into methyl alcohol moving-burden bed reactor D1 subsequently; Get into annular beds 2 through pipe core 1; After catalyzer contacts, generate mixture than methyl alcohol, dme and the water of methanol reaction zone temperature in comparatively high temps, this mixture flows out from the outlet 4 of methyl alcohol moving-burden bed reactor D1; Simultaneously 3 pairs of these mixtures of heat exchanging pipe of methyl alcohol moving-burden bed reactor D1 wall setting carry out a heat exchange, with this mixture (being the reaction product in the methyl alcohol moving-burden bed reactor D1) heat exchange to 300 ℃-400 ℃.
The reaction product of coming out from methyl alcohol moving-burden bed reactor D1 is at first mixed (not marking the figure) with water vapour from general facilities; Use process furnace (not marking among the figure) to be heated to the first reaction zone temperature in (select 450 ℃-500 ℃ according to practical situation in a steady state value) subsequently; And (decide according to practical situation according to certain ratio; Present embodiment is selected weight ratio 1: 1.4: 1.8) be divided into reactant flow a, reactant flow b and three bursts of reactant flow of reactant flow c (can be divided into some strands) according to practical situation, send into three moving-burden bed reactors of moving-burden bed reactor D2, moving-burden bed reactor D3, moving-burden bed reactor D4 (quantity of moving-burden bed reactor is identical with the number of share of stock of reactant flow) in first reaction zone respectively.
Reactant flow a, flows out from the outlet 5 of moving-burden bed reactor D2 after ring catalyst bed catalyzed reaction through moving-burden bed reactor D2, and a large amount of heat parts of emitting are simultaneously removed through the heat exchanging pipe of moving-burden bed reactor D2 wall; Reacting product stream that comes out from the outlet 5 of moving-burden bed reactor D2 and reactant flow b and cold shot liquid 12 mixed mixture flow 6 from methyl alcohol moving-burden bed reactor D1; In interchanger R1, further be cooled to the first reaction zone temperature in; Get into moving-burden bed reactor D3 subsequently; After ring catalyst bed catalyzed reaction, flow out from the outlet 7 of reactor drum D3, a large amount of heat parts of emitting are simultaneously removed through the heat exchanging pipe of reactor drum D3 wall.
From the reactant flow of the outlet 7 of moving-burden bed reactor D3 and reactant flow c and cold shot liquid 13 mixed mixture flow 8 from methyl alcohol moving-burden bed reactor D1; In interchanger R2, further be cooled to the first reaction zone temperature in; Get into moving-burden bed reactor D4 subsequently; After the ring catalyst bed continues catalyzed reaction, flow out from the outlet of moving-burden bed reactor D4, a large amount of heat parts of emitting are simultaneously removed through the heat exchanging pipe of moving-burden bed reactor D4 wall.
Wherein, the temperature in of moving-burden bed reactor D2, moving-burden bed reactor D3, moving-burden bed reactor D4 all keeps identical.
At last, will send into disengaging zone (not marking the figure) from the reacting product stream that is rich in propylene 14 that moving-burden bed reactor D4 comes out and separate, the by product that obtains propylene and do not contain propylene, by product mainly comprise C
1-C
2Hydrocarbon, propane, C
4Hydrocarbon, C
5-C
6Hydrocarbon and C
7The heavy constituent of above hydrocarbon (are C
7+ hydrocarbon refers to the hydrocarbon compound of carbonatoms>=7).C after the separation
1-C
2Hydrocarbon and C
4Hydrocarbon after interchanger (not marking among the figure) heat exchange, further use process furnace (not marking among the figure) to be heated to the first reaction zone temperature in, mix subsequently with from the product of methanol reaction zone stream 4, get into first reaction zone.By product C after the separation
5-C
6Hydrocarbon and account for C
7The C of the amount below 30% of the heavy constituent total mass of above hydrocarbon
7The heavy constituent of above hydrocarbon are after interchanger (not marking among the figure) heat exchange; Further use process furnace (not marking among the figure) to be heated to the second reaction zone temperature in (higher 15 ℃-30 ℃) than first reaction zone temperature; Send into the moving-burden bed reactor D5 of second reaction zone subsequently; After secondary reaction was carried out in the catalysis of ring catalyst bed, the product stream 16 that reaction generates flowed out from the outlet of moving-burden bed reactor D5, and a large amount of heat parts of emitting are simultaneously removed through the heat exchanging pipe of moving-burden bed reactor D5 wall.
The product stream 16 that reaction generates among the moving-burden bed reactor D5 is sent into the disengaging zone and is separated, and obtains propylene.
At first send into the methyl alcohol moving-burden bed reactor D1 of methanol reaction zone together through feeding equipment (not marking among the figure) with the live catalyst of adding from the regenerated catalyst of breeding blanket; Slowly move down through gravity; The catalyzer that comes out from methyl alcohol moving-burden bed reactor D1 relies on gravity respectively through catalyst tube 9, catalyst tube 10, catalyst tube 11; Moving-burden bed reactor D2, moving-burden bed reactor D3, moving-burden bed reactor D4 through first reaction zone successively, the catalyzer from the moving-burden bed reactor D4 of first reaction zone relies on gravity to send into the moving-burden bed reactor D5 of second reaction zone through catalyst tube equally subsequently.The catalyzer that comes out from moving-burden bed reactor D5 is the carbon distribution inactivation, sends into catalyzer bunker for collecting 17, subsequently carbon deposition catalyst 18 is sent into breeding blanket regeneration.
The revivifier of breeding blanket adopts successive moving-burden bed reactor or fluidized-bed reactor, thereby realizes the successive reaction regeneration of catalyzer.
Embodiment 1
The catalyzer that present embodiment adopted is that particle is the spherical catalyzer of ZSM-5 molecular sieve of 1.6mm-2mm, and the raw material that is adopted is a methyl alcohol.
Methanol reaction zone adopts a moving-burden bed reactor, and temperature in is 250 ℃, atmospheric operation.
First reaction zone adopted three moving-burden bed reactors, and each temperature in is 500 ℃, and atmospheric operation, the mixture of methyl alcohol, dme and water were divided into three bursts of reactant flow by weight 1: 1.4: 1.8; Cold shot liquid adopts methyl alcohol.
Second reaction zone adopts a moving-burden bed reactor, and temperature in is 525 ℃, atmospheric operation.
The carbon deposition catalyst carbon deposition quantity that shifts out from the beds bottom is sent it into revivifier regeneration less than 2%, and the carbon deposition quantity of catalyst after the regeneration is lower than 0.5% (sedimentary carbon distribution quality on carbon deposition quantity=unit weight catalyzer).
Other operation is with above-mentioned embodiment.
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 208333kg/h, the propylene amount that is generated is 66573kg/h, and methanol conversion is greater than 99%.
Table 1 material balance
| Material | Mass flow |
| Methyl alcohol | 208333kg/h |
| Propylene | 66573kg/h |
| LPG | 5887kg/h |
| Gasoline | 16725kg/h |
| Water (comprising micro oxygen containing compound) | 117485kg/h |
| Fuel gas # | 1581kg/h |
| * such as 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 the hydro carbons of C3-C4, is mainly alkane, comprises small amounts of olefins; Gasoline mainly is the above heavy constituent of C7, and water is micro oxygen containing compounds such as the product of the methanol dehydration dme that comprises not reacted Trace Methanol and generation, aldehydes, and fuel gas mainly is a small amount of C1-C2 hydrocarbon component, and coke is the carbon laydown on the catalyzer, down with.
Each product is converted into the butt percentage composition that dewaters later, has listed products distribution with respect to material benzenemethanol, as shown in table 2.
Table 2 products distribution
| Product | The butt percentage |
| Propylene | 73.28％ |
| LPG | 6.48％ |
| Gasoline | 18.41％ |
| Fuel gas | 1.74％ |
| Coke | 0.09％ |
Embodiment 2
The catalyzer that present embodiment adopted is that particle is the spherical catalyzer of ZSM-5 molecular sieve of 1.6mm-2mm, and the raw material that is adopted is a methyl alcohol.
Methanol reaction zone adopts two moving-burden bed reactors, and each temperature in is 280 ℃, atmospheric operation.
First reaction zone adopts four moving-burden bed reactors, and each temperature in is 450 ℃, atmospheric operation, and the mixture of methyl alcohol, dme and water was by weight 1: 1.4: 1.8: 1.2 are divided into four bursts of reactant flow; Cold shot liquid adopts the mixture of methyl alcohol and water.
Second reaction zone adopts a moving-burden bed reactor, and temperature in is 465 ℃, atmospheric operation.
The carbon deposition catalyst carbon deposition quantity that shifts out from the beds bottom is sent it into revivifier regeneration less than 2%, and the carbon deposition quantity of catalyst after the regeneration is lower than 0.5% (sedimentary carbon distribution quality on carbon deposition quantity=unit weight catalyzer).
Other operation is with embodiment 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 208333kg/h, the propylene amount that is generated is 66711kg/h, and methanol conversion is greater than 99%.
Table 3 material balance
| Material | The material flow rate |
| Methyl alcohol | 208333kg/h |
| Propylene | 66711kg/h |
| LPG | 6620kg/h |
| Gasoline | 16205kg/h |
| Water (comprising micro oxygen containing compound) | 117396kg/h |
| Fuel gas # | 1319kg/h |
| * such as coke | 82kg/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 that dewaters later, has listed products distribution with respect to material benzenemethanol, as shown in table 4.
Table 4 products distribution
| Product | The butt percentage |
| Propylene | 73.36％ |
| LPG | 7.28％ |
| Gasoline | 17.82％ |
| Fuel gas | 1.45％ |
| Coke | 0.09％ |
Embodiment 3
The catalyzer that present embodiment adopted is that particle is the spherical catalyzer of ZSM-5 molecular sieve of 2mm-3mm, and the raw material that is adopted is a methyl alcohol.
Methanol reaction zone adopts a moving-burden bed reactor, and each temperature in is 300 ℃, atmospheric operation.
First reaction zone adopted three moving-burden bed reactors, and each temperature in is 450 ℃, and atmospheric operation, the mixture of methyl alcohol, dme and water were divided into three bursts of reactant flow by weight 1: 1.4: 1.8; Cold shot liquid adopts the mixture of methyl alcohol and water.
Second reaction zone adopts a moving-burden bed reactor, and temperature in is 480 ℃, atmospheric operation.
The carbon deposition catalyst carbon deposition quantity that shifts out from the beds bottom is sent it into revivifier regeneration less than 2%, and the carbon deposition quantity of catalyst after the regeneration is lower than 0.5% (sedimentary carbon distribution quality on carbon deposition quantity=unit weight catalyzer).
Other operation is with embodiment 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 208333kg/h, the propylene amount that is generated is 67329kg/h, and methanol conversion is greater than 99%.
Table 5 material balance
| Material | The material flow rate |
| Methyl alcohol | 208333kg/hr |
| Propylene | 67329kg/hr |
| LPG | 7697kg/hr |
| Gasoline | 14195kg/hr |
| Water (comprising micro oxygen containing compound) | 117459kg/hr |
| Fuel gas # | 1454kg/hr |
| * such as coke | 200kg/hr |
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 that dewaters later, has listed products distribution with respect to material benzenemethanol, as shown in table 6.
Table 6 products distribution
| Product | The butt percentage |
| Propylene | 74.09％ |
| LPG | 8.47％ |
| Gasoline | 15.62％ |
| Fuel gas | 1.60％ |
| Coke | 0.22％ |
Find out from above-mentioned three embodiment, according to method disclosed by the invention and reactor technology, can obtain temperature control preferably, thereby make the propylene selectivity keep higher level.In addition, in scope disclosed by the invention, operate, the product selectivity rangeability is less.
Claims (5)
1. one kind is the method for propylene with methanol conversion, may further comprise the steps:
(1) methyl alcohol is fed methanol reaction zone and catalyzer contact reacts, reaction obtains the mixture of methyl alcohol, dme and water;
(2) mixture with above-mentioned methyl alcohol, dme and water is divided into some bursts of reactant flow, and first burst of reactant flow sent into first reaction zone, with the catalyzer contact reacts; Obtain product stream; Product stream is sent into first reaction zone after one reactant flow is mixed arbitrarily with other, with the catalyzer contact reacts, flows and sends into first reaction zone after one reactant flow is mixed at last until product; With the catalyzer contact reacts, obtain being rich in the primary first-order equation product stream of propylene;
(3) above-mentioned primary first-order equation product stream is sent into the disengaging zone, behind dehydration and oxide removal, obtain propylene, propane, C respectively
1-C
2Hydrocarbon, C
4Hydrocarbon, C
5-C
6Hydrocarbon and C
7The heavy constituent of above hydrocarbon;
(4) with C
1-C
2Hydrocarbon and C
4Hydrocarbon be circulated to first reaction zone and continue reaction;
(5) with C
5-C
6Hydrocarbon and portion C
7Second reaction zone is sent in the heavy constituent of above hydrocarbon, with the catalyzer contact reacts, obtains containing the secondary reaction product stream of propylene;
Described portion C
7The quality of the heavy constituent of above hydrocarbon is C
7Below 30% of heavy constituent total mass of above hydrocarbon;
(6) above-mentioned secondary reaction product stream is sent into the disengaging zone, obtain propylene, propane, C respectively
1-C
2Hydrocarbon, C
4Hydrocarbon, C
5-C
6Hydrocarbon and C
7The heavy constituent of above hydrocarbon;
(7) discharge from second reaction zone behind the described catalyst carbon deposit, get into and be circulated to methanol reaction zone after regenerating in the breeding blanket;
Described methanol reaction zone, first reaction zone and second reaction zone are made up of the setting moving-burden bed reactor that several are connected in series;
Wherein, described methanol reaction zone is at least one moving-burden bed reactor;
Described first reaction zone is at least two setting moving-burden bed reactors that are connected in series, and the number of share of stock of described reactant flow is identical with the number of the first reaction zone moving-burden bed reactor;
Described second reaction zone is at least one moving-burden bed reactor;
Total number of moving-burden bed reactor is 4-8 in described methanol reaction zone, first reaction zone and second reaction zone.
2. method according to claim 1 is characterized in that: described methanol reaction zone, first reaction zone and second reaction zone are equipped with heat-exchanger rig;
Described heat-exchanger rig is in moving-burden bed reactor and/or between each moving-burden bed reactor;
Be provided with chilling device in described first reaction zone, mix with any one reactant flow from the effusive Quench liquid of chilling device;
Described Quench liquid is selected from methyl alcohol or water or both mixtures.
3. method according to claim 1 is characterized in that, the temperature in of described methanol reaction zone is 250 ℃-300 ℃, and the temperature in of each moving-burden bed reactor all keeps identical in the methanol reaction zone.
4. method according to claim 1 is characterized in that, the temperature in of described first reaction zone is 450 ℃-500 ℃, and the temperature in of each moving-burden bed reactor all keeps identical in first reaction zone.
5. method according to claim 4 is characterized in that, the temperature in of described second reaction zone is higher 15 ℃-30 ℃ than the temperature in of first reaction zone, and the temperature in of each moving-burden bed reactor all keeps identical in second reaction zone.
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| CN102240527A (en) * | 2011-04-21 | 2011-11-16 | 浙江大学 | Apparatus with multistage moving bed reaction system for technology of preparing propylene by methanol |
| CN102276407B (en) * | 2011-04-21 | 2014-03-12 | 浙江大学 | Method for controlling temperature of multistage moving-bed reactor |
| CN102276408B (en) * | 2011-06-30 | 2013-07-24 | 洛阳市科创石化科技开发有限公司 | Method for producing propylene from methanol or dimethyl ether |
| CN102344328B (en) * | 2011-07-25 | 2014-03-12 | 浙江大学 | Semi-continuous method for converting methyl alcohol into propylene by using moving bed technology |
| CN103157502B (en) * | 2011-12-19 | 2015-04-15 | 中国科学院大连化学物理研究所 | Catalyst of preparing ethylene and propylene by carbinol and / or dimethyl ether, preparing method and application thereof |
| CN103360196B (en) * | 2012-03-30 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method by methyl alcohol highly selective preparing propone |
| CN103360198B (en) * | 2012-03-30 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of combination process of methyl alcohol highly selective preparing propone |
| CN102942435B (en) * | 2012-11-06 | 2014-12-17 | 浙江大学 | Reaction technology using moving bed technique to convert methanol into propylene |
| CN105085147B (en) * | 2014-05-14 | 2017-09-15 | 中国石油化工股份有限公司 | The method of preparing low-carbon olefin from oxygen-containing compounds |
| CN106140033B (en) * | 2015-04-02 | 2018-07-06 | 中石化广州工程有限公司 | A kind of adding method of catalyst |
| CN104876784B (en) * | 2015-05-11 | 2017-08-04 | 浙江大学 | A kind of technique that propylene is produced by raw material of oxygenatedchemicals |
| CN105419849A (en) * | 2015-11-09 | 2016-03-23 | 赛鼎工程有限公司 | Energy-saving type technology for manufacturing gasoline by converting methanol |
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| CN101367694B (en) * | 2008-09-18 | 2012-06-13 | 浙江大学 | Horizontal moving bed reactor for preparing propylene with oxygen-containing compound as raw material |
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