CN103360196B - A kind of method by methyl alcohol highly selective preparing propone - Google Patents
A kind of method by methyl alcohol highly selective preparing propone Download PDFInfo
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- CN103360196B CN103360196B CN201210088912.XA CN201210088912A CN103360196B CN 103360196 B CN103360196 B CN 103360196B CN 201210088912 A CN201210088912 A CN 201210088912A CN 103360196 B CN103360196 B CN 103360196B
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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
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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
Abstract
By a method for methyl alcohol highly selective preparing propone, comprise methyl alcohol and introduce the first reactor through overcooled regenerated catalyst, being obtained by reacting the first reaction product and the first reclaimable catalyst; First reclaimable catalyst partly or entirely introduces revivifier regeneration; First reaction product and regenerated catalyst and/or the first reclaimable catalyst and/or the 3rd reclaimable catalyst are introduced the second reactor reaction, obtains the second reaction product and the second reclaimable catalyst, the second reaction product is introduced product separation system and is separated and obtains being rich in C
4-C
8the material of alkene and propylene; Second reclaimable catalyst introduces revivifier regeneration; What described product separation system separation obtained is rich in C
4-C
8the 3rd reactor contact reacts introduced by the material of alkene and regenerated catalyst, obtains the 3rd reclaimable catalyst and the 3rd reaction product, and the product separation system described in the 3rd reaction product introducing is separated; 3rd reclaimable catalyst partly or entirely introduces revivifier regeneration; Wherein, described catalyzer comprises modified mesoporous molecular sieve.The method is used for methanol conversion and has higher productivity of propylene.
Description
Technical field
The present invention relates to a kind of method preparing hydrocarbon from non-hydrocarbon compound, furtherly, the present invention relates to a kind of combined method by preparing propylene from methanol.
Background technology
Propylene is basic organic chemical industry raw material, and its demand is increasing.The traditional method mainly naphtha cracking of preparing propone, but along with the exhaustion of petroleum resources, the cost and risk being prepared propylene by petroleum naphtha progressively improves, and therefore produces propylene by alternative materials and becomes extremely important.Be alkene (Methanol to Olefins is called for short MTO) by Sweet natural gas and biomass-making again by methanol conversion for methyl alcohol be most promising alternative route, the key of this route is that methyl alcohol maximum is converted into propylene.
The method of current producing low-carbon olefin through methanol transformation, mainly comprises two kinds, and a kind of method uses SAPO molecular sieve catalyst, such as method disclosed in CN1065853C, CN1156416A, US6844476, US6740790; Another method uses the catalyzer such as containing the ZSM-5 molecular sieve of ZSM-5 molecular sieve or modification containing the catalyzer with MFI structure (or claiming MFI structure) molecular sieve.In order to improve productivity of low carbon olefin hydrocarbon, methyl alcohol adopts multi-reaction-area to transform usually, such as US6797851 discloses a kind of reactive system adopting double-reaction area, dual catalyst, first reaction zone utilizes ZSM-5 molecular sieve catalyzed conversion oxygenatedchemicals, the C4+ alkene that second reaction zone utilizes ZSM-35 further catalyzed conversion first reaction zone to produce.Method disclosed in CN200810203273.0, generates in dme, the second reactor and is transformed in the second reactor that HZSM-5 is housed by the product in the first reactor in the first reactor.
But existing methanol conversion process, productivity of propylene is not high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of being produced propylene by methyl alcohol highly selective, and the method uses multi-reaction-area reaction and modified mesoporous molecular sieve catalyst, has higher productivity of propylene.
The invention provides a kind of method of preparing propylene from methanol, comprising:
A. methyl alcohol with introduce the first reactor through overcooled regenerated catalyst and react, make methanol conversion generate dme, obtain the first reaction product and the first reclaimable catalyst; First reclaimable catalyst partly or entirely introduces revivifier regeneration;
B. the first reaction product and regenerated catalyst and/or the first reclaimable catalyst and/or the 3rd reclaimable catalyst introduce the second reactor reaction, first reaction product is transformed and generates hydrocarbon, obtain the second reaction product and the second reclaimable catalyst, the second reaction product is introduced product separation system separation and is obtained being rich in C
4-C
8the logistics of alkene and propylene; Second reclaimable catalyst introduces revivifier regeneration;
What C. described product separation system separation obtained is rich in C
4-C
8the 3rd reactor contact reacts introduced by the material of alkene and regenerated catalyst, obtains the 3rd reclaimable catalyst and the 3rd reaction product, and the product separation system described in the 3rd reaction product introducing is separated; 3rd reclaimable catalyst partly or entirely introduces revivifier regeneration;
Wherein, described catalyzer comprises modified mesoporous molecular sieve.
Methanol oxidation provided by the invention transforms the method generating propylene, adopts containing modified mesoporous molecular sieve catalyst and multi-region reaction, makes methyl alcohol, dme, is rich in C
4-C
8the logistics of alkene is reacted with catalyst exposure in different reaction zones under reaction conditions suitable separately, and three class reactions is coupled, and improves the selectivity that methanol conversion is propylene, reduces the energy consumption in preparing propylene from methanol process.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for preparing propylene from methanol provided by the invention.Wherein
1-first reactor (methanol conversion),
11-reactor 1 feeding line,
Spent agent (reclaimable catalyst) transfer lime of 13-reactor 1,
V11-transfer lime 13 leads to reactor 2 catalyst stream control valve,
V12-transfer lime 13 leads to revivifier 4 catalyst stream control valve,
131-reactor 1 to reactor 2 spent agent transfer lime,
132-reactor 1 to revivifier 4 spent agent transfer lime,
14-reactor 1 reacting product outlet pipeline;
2-second reactor (dimethyl ether conversion reactor),
21-reactor 2 feeding line,
22-reactor 2 feeding line,
The spent agent transfer lime of 23-reactor 2 to revivifier,
V21-transfer lime 23 leads to revivifier 4 catalyst stream control valve,
24-reactor 2 reacting product outlet pipeline;
3-the 3rd reactor (C
4-C
8olefin reactor),
31-reactor 3 feeding line,
32-reactor 3 feeding line,
The spent agent transfer lime of 33-reactor 3,
V31-transfer lime 33 leads to reactor 2 catalyst stream control valve,
V32-transfer lime 33 leads to revivifier 4 catalyst stream control valve,
331-reactor 3 to reactor 2 spent agent transfer lime,
332-reactor 3 to revivifier 4 spent agent transfer lime,
34-reactor 3 reacting product outlet pipeline;
4-revivifier,
41-regenerator line of pipes,
42-regenerated flue gas line of pipes,
V41-regenerator transfer lime 41 leads to reactor 1 catalyst stream control valve,
V42-regenerator transfer lime 41 leads to reactor 2 catalyst stream control valve,
V43-regenerator transfer lime 41 leads to reactor 3 catalyst stream control valve,
411-revivifier 4 to reactor 1 regenerator transfer lime,
412-revivifier 4 to reactor 2 regenerator transfer lime,
413-revivifier 4 to reactor 3 regenerator transfer lime;
5-heat collector,
51-heat collector heat-obtaining medium entrance pipeline,
52-heat collector heat-obtaining media outlet pipeline;
6-interchanger,
61-is rich in C
4-C
8olefin stream enters the pipeline of interchanger,
62-mix products outlet line.
Embodiment
In the method for preparing propylene from methanol provided by the invention, regenerated catalyst through cooling is introduced the first reactor, methyl alcohol is introduced the first reactor, carry out reaction highly selective with the catalyst exposure in the first reactor and be converted into dme, (reclaimable catalyst the present invention is referred to as spent agent to obtain the first reaction product and the first reclaimable catalyst, regenerated catalyst the present invention is referred to as regenerator), first reaction product is separated with the first reclaimable catalyst, the first reclaimable catalyst that separation obtains is through stripping, part is introduced revivifier regeneration or is all introduced revivifier regeneration, the first reaction product after being separated with the first reclaimable catalyst, introduce the second reactor to transform further.The temperature of reaction of the first reactor is 200-350 DEG C, is preferably 220-320 DEG C; Reaction pressure (absolute pressure) is 0.11 ~ 0.50MPa, preferably 0.20 ~ 0.45MPa; Weight hourly space velocity is 0.1 ~ 50h
-1, be preferably 0.2 ~ 40h
-1.The regenerated catalyst introducing the first reactor is preferably 5 ~ 50 with the weight ratio (the present invention is called the agent-oil ratio of the first reactor) of the methyl alcohol introducing the first reactor.In first reactor, methanol conversion is preferably more than 70%, and the selectivity of dme is preferably more than 99%.
The present invention introduces methyl alcohol by introducing methanol feedstock in the first reactor, introduce in the methanol feedstock of the first reactor, the content of methyl alcohol is 5-100 % by weight, preferred 30-100 % by weight, more preferably 80-100 % by weight, can containing impurity as water etc., and the content of impurity is preferably more than 95 % by weight, more preferably no more than 70 % by weight, further preferably more than 20 % by weight.The crude carbinol that described methanol feedstock obtains through gasification, synthesis as Sweet natural gas, coal, oil-sand, oil etc. from various fossil oil also can be the methyl alcohol in other source.In the present invention, methyl alcohol can liquid phase feeding, also can with reaction product or the laggard row gas-phase feed of other thermal source heat exchange.
First reactor can be riser reactor, fluidized-bed reactor and by multiple above-mentioned reactors in series and/or the compound reactor that composes in parallel, and the first described reactor can be one or more.Preferred first reactor is fluidized-bed reactor, and described fluidized-bed reactor is selected from one or more in particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor and fast bed reactor.
In the method for preparing propylene from methanol provided by the invention, first reaction product is introduced the second reactor, react with the described catalyst exposure of introducing second reactor, first reaction product is transformed and generates hydrocarbon, the described catalyzer of described introducing second reactor is the regenerated catalyst from revivifier and/or the reclaimable catalyst from the first reactor and/or the reclaimable catalyst from the 3rd reactor, preferably, the described catalyzer of described introducing second reactor comprises regenerated catalyst and the 3rd reclaimable catalyst and/or the first reclaimable catalyst, wherein the part by weight of regenerated catalyst and the 3rd reclaimable catalyst is preferably 1: 0 ~ 3, can be such as 1: 0.1 ~ 3, the part by weight of regenerated catalyst and the first reclaimable catalyst is preferably 1: 0 ~ 3, can be such as 1: 0.1 ~ 3, in the described catalyzer of preferred described introducing second reactor, the part by weight of the first reclaimable catalyst and the 3rd reclaimable catalyst is preferably 1: 0.5 ~ 2.5.The temperature of reaction of the second reactor is 400-550 DEG C, is preferably 420-530 DEG C, is more preferably 450 ~ 500 DEG C; Reaction pressure (absolute pressure) is 0.11 ~ 0.50MPa, preferably 0.15 ~ 0.45MPa; Weight hourly space velocity is 0.5 ~ 40h
-1, be preferably 1.0 ~ 35h
-1.The agent-oil ratio (introducing the described catalyzer of the second reactor and the introducing methyl alcohol of the second reactor and the weight ratio of dme weight sum) of the second reactor is 4 ~ 30, second reactor can be riser reactor, fluidized-bed reactor and by multiple above-mentioned reactors in series and/or the compound reactor that composes in parallel, and the second described reactor can be one or more.Preferred second reactor is fluidized-bed reactor, and described fluidized-bed reactor is selected from one or more in particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor and fast bed reactor.
Preferably, from the first reaction product of the first reactor, carry out diluting rear introducing second reactor with thinner, to improve the selectivity of low-carbon alkene in conversion process of oxocompound, thinner can be one or more in nitrogen, water vapour, small molecules alkane, thinner is 0.01 ~ 0.8: 1 with the introducing methyl alcohol of the second reactor and the weight ratio of dme weight sum, is preferably 0.02 ~ 0.7: 1.
Second reactor, except introducing the first described reaction product, can also be introduced or not introduce external material, and described external material is preferably methyl alcohol and/or dme, and described external material is 0 ~ 1: 1 with the part by weight from the first reactor content.Preferably, introduce in the material (comprising the first reaction product and external material) of the second reactor, methyl alcohol is no more than 1, preferably more than 0.3 with the ratio of the weight content of dme.
First reaction product obtains the second reaction product and the second reclaimable catalyst after introducing and reacting with the described catalyst exposure of introducing second reactor in the second reactor, second reaction product is separated with the second reclaimable catalyst, described separation, can be that the second reaction product of being obtained by the second reactor and the second reclaimable catalyst are drawn respectively from the difference outlet of the second reactor, second reaction product introduces product separation system after flowing through the catalyzer isolated further and wherein carry, second reclaimable catalyst is all or part of introducing revivifier regeneration after stripping, second reaction product introduces product separation system.In product separation system, reaction product is separated as required and obtains required material, such as propylene, be rich in C
4~ C
8the cut of alkene and dry gas etc.
The method of preparing propylene from methanol provided by the invention, that in the 3rd reactor, introduces that regenerated catalyst and described product separation system obtain is rich in C
4-C
8the cut of alkene, described in be rich in C
4-C
8the cut of alkene reacts at the 3rd reactor and catalyst exposure wherein, obtain the 3rd reaction product and the 3rd reclaimable catalyst that comprise propylene, the 3rd described reaction product is drawn the 3rd reactor with the 3rd reclaimable catalyst and is separated, 3rd reclaimable catalyst is through stripping rear section or all introduce revivifier regeneration, product separation system described in 3rd reaction product introducing, preferably, introduce product separation system after the second reaction product that the 3rd reaction product and the second reactor obtain mixes to be separated.The temperature of reaction of the 3rd reactor is 500-650 DEG C, is preferably 520-640 DEG C; Reaction pressure (absolute pressure) is 0.11 ~ 0.50MPa, preferably 0.15 ~ 0.45MPa; Weight hourly space velocity is 1 ~ 20h
-1, be preferably 1.5 ~ 35h
-1.The regenerated catalyst introducing the 3rd reactor is rich in C with described in introducing the 3rd reactor
4-C
8the weight ratio (agent-oil ratio of the 3rd reactor) of olefin fraction is 5-40.
3rd reactor can be riser reactor, fluidized-bed reactor and by multiple above-mentioned reactors in series and/or the compound reactor that composes in parallel, and the first described reactor can be one or more.Preferred 3rd reactor is fluidized-bed reactor, and described fluidized-bed reactor is selected from one or more in particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor and fast bed reactor.
Described fluid bed reactor catalysis agent bed density is at 50-600kg/m
3, be preferably 80-500kg/m
3.
Describedly be rich in C
4-C
8c in the cut of alkene
4-C
8theatotal olefinsacontent is generally more than 30 % by weight, can be 30 ~ 100 % by weight, preferably more than 40 % by weight, preferably more than 50 % by weight, alkane and aromatic hydrocarbons can be contained in raw material, the content of these materials generally below 70 % by weight, preferably below 60 % by weight, preferably below 50 % by weight.What described product separation system obtained is rich in C
4-C
8the cut boiling range of alkene is preferably 10 ~ 85 DEG C.
C is rich in from product separation system
4-C
8olefin fraction, when entering the 3rd reactor, preferably dilutes with thinner, and to improve the selectivity of low-carbon alkene in conversion process, thinner can be one or more in nitrogen, water vapour, small molecules alkane, described thinner and be describedly rich in C
4-C
8the weight ratio of olefin fraction is preferably 0.1 ~ 0.8: 1.
3rd reactor can supplement or not supplement other and externally be rich in C
4-C
8the material of alkene, as derived from steam cracking C
4, C
5cut, pyrolysis gasoline, catalytic cracking liquefied gas, petroleum naphtha, one or more in the light olefin in light coker naphtha, oxygenate conversion product, etherificate C-4-fraction.Describedly be rich in C
4-C
8the boiling range of the cut of alkene is preferably between 10 ~ 85 DEG C.
The method of preparing propylene from methanol provided by the invention, is rich in C
4-C
8the coking yield that olefin fraction transforms is low, can improve to a certain extent and be rich in C
4-C
8the preheating temperature of olefin fraction, self thermal equilibrium of better setting device.Be rich in C
4-C
8olefin fraction can carry out heat exchange with the product stream of first, second, third reactor, or is heated by process furnace, obtains enough heats.C
4~ C
8alkene preheating temperature at 200 ~ 600 DEG C, preferably at 300 ~ 550 DEG C.
The method of preparing propylene from methanol provided by the invention, spent agent is introduced revivifier regeneration Posterior circle and use, described regeneration, can be existing method, and the temperature of regenerated catalyst is preferably 680 ~ 720 DEG C.
Provided by the invention by the method for preparing propylene from methanol, described catalyzer comprises the mesoporous molecular sieve of modification, described modified mesoporous molecular sieve preferably comprises phosphorus and is selected from the molecular sieve of one or more modifying elements in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi and RE, and wherein phosphorus content is with P
2o
5meter is preferably 1.3 ~ 15 % by weight, and modifying element content is 0.5 ~ 20 % by weight with oxide basis.The mesoporous molecular sieve of described modification is more preferably the mesoporous molecular sieve of the phosphorous and rare earth of one or more modifications in VIII race's metal, I B race metal and alkaline-earth metal; In described modified mesoporous molecular sieve, phosphorus content is with P
2o
5count 1.3 ~ 15 % by weight, content of rare earth is with RE
2o
3count 0.5 ~ 15 % by weight, modified metal content is with M
xo
ycount 0.7 ~ 15 % by weight, sodium oxide content is no more than 0.3 % by weight, wherein M represents modified metal, x represents the atomicity of M, y represents the number needed for oxidation state meeting M, M is preferably one or more in VIII race's metal, I B race metal, II B race metal and alkaline-earth metal, is preferably one or more in Fe, Zn, Mg, Ag and Ni.Described mesoporous molecular sieve is preferably five-membered ring structure molecular sieve, and described five-membered ring structure molecular sieves is as ZSM-5 molecular sieve and/or ZRP molecular sieve.Described mesoporous molecular sieve can be prepared according to existing method, and such as ZRP molecular sieve can referenced patent USP5, the method preparation of 232,675.Preferably, containing the ZSM-5 molecular sieve comprising phosphorus and transition metal in described catalyzer, more preferably described catalyzer contains and comprises phosphorus, the ZSM-5 molecular sieve of rare earth and modified metal element and/or comprise phosphorus, the ZRP molecular sieve of rare earth and modified metal element, described modified metal element is preferably VIII race's metal, I B race metal, one or more in II B race metal and alkaline-earth metal, described modified metal element is more preferably Fe, Zn, Mg, one or more in Ag and Ni, describedly comprise phosphorus, in the ZSM-5 molecular sieve of rare earth and modified metal element, phosphorus content is with P
2o
5count 1.3 ~ 15 % by weight, content of rare earth is with RE
2o
3count 0.5 ~ 15 % by weight, modified metal content is with M
xo
ycount 0.7 ~ 15 % by weight, sodium oxide content is no more than 0.3 % by weight, the described phosphorus content that to comprise in the ZRP molecular sieve of phosphorus, rare earth and modified metal element is with P
2o
5count 1.3 ~ 15 % by weight, content of rare earth is with RE
2o
3count 0.5 ~ 15 % by weight, modified metal content is with M
xo
ycount 0.7 ~ 15 % by weight, sodium oxide content is no more than the modified metal element described in 0.3 % by weight, M representative.
Also containing the conventional matrix of catalyzer and binding agent in described catalyzer, described matrix can be natural or synthetic, warp or the clay without various chemistry/or physical treatment, such as kaolin, halloysite; Described binding agent can be one or more in heat-resistant inorganic oxide and/or precursors of inorganic oxides such as pseudo-boehmite, Alumina gel, aluminum oxide, silica-alumina and silicon sol.Preferably, in described catalyzer, modified mesoporous molecular sieve content is 15 ~ 80 % by weight, and the content of matrix is 15 ~ 60 % by weight, and the content of binding agent is 5 ~ 40 % by weight (with oxide basis).
Described catalyzer can adopt existing method to prepare, such as, can be prepared as follows catalyzer: by the precursor of inorganic oxide, such as Alumina gel, pseudo-boehmite, silicon sol, silicon-aluminum sol silica-alumina gel or multiple mixture wherein, mix by preset blending ratio with clay, stir, with mineral acid, example hydrochloric acid, nitric acid, phosphoric acid, slurry pH value is adjusted to 2 ~ 4 by sulfuric acid, keep this pH value, the molecular sieve pulp adding predetermined amount after 0 ~ 2 hour is left standstill at 20 ~ 80 DEG C, and the slurries of solid content 15 ~ 25 % by weight are mixed with decationized Y sieve water, homogeneous, spraying dry, wash away free sodium ion, dry.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
The preparation method of the five-ring high-silica zeolite of phosphorous and rare earth used in example is as follows: get 100 grams of (butt) ZRP molecular sieves (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, SiO
2/ Al
2o
3=60 (mol ratios), RE
2o
3content is 2.0 % by weight), according to molecular sieve (butt): ammonium sulfate: decationized Y sieve water=100: the weight ratio of 25: 2000 ion-exchange 1 hour at 90 DEG C, exchanges once after filtration more according to the method described above.Atomic absorption spectrum to record in this molecular sieve sodium content (with Na
2o counts) be 0.04 % by weight.By 13.8 grams of pseudo-boehmites (Shandong Aluminum Plant's product, Al
2o
395 % by weight, solid content 30 % by weight), 9.0 grams of industrial phosphoric acids (phosphorus acid content 85 % by weight) add above-mentioned ammonium after mixing with 200 grams of decationized Y sieve water and exchange in the molecular sieve obtained, stir, after 110 DEG C of dryings, 800 DEG C, within aging 4 hours, namely obtain phosphorus content (with P in 100% steam atmosphere
2o
5meter) be the five-ring high-silica zeolite of the phosphorous and rare earth of 5 % by weight.
In example, the five-ring high-silica zeolite of the phosphorous and rare earth of any one or multiple modification in Fe, Zn, Mg, Ag, Ni used is according to following steps modification: by obtained phosphorous and rare-earth five-membered ring high-silica zeolite 100 grams 50 grams of Fe (NO
3)
3(concentration is 4.5 % by weight, Fe (NO to solution
3)
3purity is greater than 99%) flood 3 hours, five-ring high-silica zeolite after dipping was 120 DEG C of dryings 2 hours, 500 DEG C of roastings 2 hours, obtain the phosphorous and rare-earth five-membered ring high-silica zeolite containing the heavy % of Fe (with metal oxide) 1.5, hereinafter referred to as Fe-ZRP-1.5, Mg-ZRP-1.5, Ni-ZRP-1.5 can be prepared accordingly.
The preparation of used catalyst in embodiment: (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, containing Al at 175 kilograms of Alumina gel
2o
311.4 % by weight, pH value is 2 ~ 3) in add 62.5 kilograms of kaolin (Suzhou china clay company Industrial products, solid content 80 % by weight), add 100 kilograms of Fe-ZRP-1.5 molecular sieve pulps (solid content is 30 % by weight) and 162.5 kilograms of decationized Y sieve water again, homogeneous, spraying dry, be 6 by deionized water wash to pH value, dry, roasting 3 hours at 500 DEG C, obtain catalyst sample A, the catalyst B containing Mg-ZRP-1.5, catalyzer C containing Ni-ZRP-1.5 can be prepared accordingly.
Live catalyst all carries out the aging pre-treatment of water vapour before the use, and aging pretreatment condition is: 790 DEG C, 100% steam atmosphere, digestion time 8h.
Test methyl alcohol (Beijing Chemical Plant's product) used, its character is in table 1.
Testing apparatus schematic diagram is as shown in Figure 1.Methyl alcohol sprays into reactor 1 from pipeline 11, and from pipeline 411, and carries out contact reacts through the regenerated catalyst of heat collector 5 heat-obtaining, directly draws reactor 1 by pipeline 14 after reaction product isolates the catalyzer wherein carried.Be separated the spent agent obtained to be drawn by pipeline 13, part spent agent, by catalyst stream control valve V11, is delivered to reactor 2 by pipeline 131, and part spent agent, by catalyst stream control valve V12, is delivered to revivifier 4 by pipeline 132.
Carry out the reaction product stream of autoreactor 1, without separation, directly introduce reactor 2 by pipeline 22, external methyl alcohol and/or dme can introduce reactor 2 by pipeline 21 simultaneously, regenerator from pipeline 412 and/or the spent agent from pipeline 131 and/or introduce reactor 2 from after the spent agent mixing of pipeline 331, the reaction product obtained introduces product separation system after isolating the catalyzer wherein carried, and is separated and obtains object product, such as propylene and be rich in C
4-C
8olefin fraction logistics.Be separated the spent agent obtained to be drawn by pipeline 23, by catalyst stream control valve V21, be delivered to revivifier 4 by pipeline 23.
What product separation system obtained is rich in C
4-C
8the cut logistics of alkene and the outlet streams of reactor 1,2,3 carry out heat exchange, and introduce reactor 3 by pipeline 32, external is rich in C
4-C
8olefin stream can introduce reactor 3 by pipeline 31 simultaneously, and with the regenerator contact reacts from pipeline 413, the reaction oil gas product separation obtained is incorporated to the outlet streams of reactor 2 again after going out the catalyzer carried wherein.Be separated the spent agent obtained and draw reactor by pipeline 33, part spent agent, by catalyst stream control valve V31, is delivered to reactor 2 by pipeline 331, and part spent agent, by catalyst stream control valve V32, is delivered to revivifier 4 by pipeline 332.
In embodiment and comparative example, the reaction pressure of reactor 1,2,3 is 0.21MPa (absolute pressure).
Table 1
| Content, % by weight | Density, g/mL (20 DEG C) | Molecular weight | Boiling point (DEG C) |
| ≥99.5 | 0.792 | 32.04 | 64.5 |
Embodiment 1
Adopt catalyst A, the regenerated catalyst introducing fast bed reactor 1 of 500 DEG C is cooled to from revivifier and through heat collector, with the methyl alcohol contact reacts introducing fast bed reactor 1, temperature of reaction is 250 DEG C, the product be obtained by reacting and catalyst separating, be separated the reclaimable catalyst part obtained and enter revivifier 4, part enters fast bed reactor 2, and the part by weight of the two is 50: 50.
Mixture from the regenerated catalyst of revivifier 4, the reclaimable catalyst (the first spent agent) carrying out autoreactor 1 and the reclaimable catalyst (the 3rd spent agent) that carrys out autoreactor 3 introduces fast bed reactor 2, with the reaction product contact reacts of the fast bed reactor 1 of introducing fast bed reactor 2, temperature of reaction is 450 DEG C, is 30: 35: 35 from the regenerated catalyst of revivifier 4, the reclaimable catalyst carrying out autoreactor 1, the part by weight that carrys out the reclaimable catalyst of autoreactor 3; The product that fast bed reactor 2 is obtained by reacting is separated with reclaimable catalyst, is separated the reclaimable catalyst (the second spent agent) obtained and after stripping, enters revivifier 4, regeneration temperature 680 DEG C; The reaction product of fast bed reactor 2 introduces product separation system, obtaining propylene, being rich in C through being separated
4-C
8olefin fraction.
What product separation system obtained is rich in C
4-C
8olefin fraction (boiling range is the cut of 10 ~ 85 DEG C) introduces fast bed reactor 3, and with the regenerated catalyst contact reacts from revivifier 4, temperature of reaction is 590 DEG C.The reclaimable catalyst part obtained after speed bed bioreactor 3 reacts enters revivifier 4, and part enters fast bed reactor 2, and the part by weight of the two is 60: 40 (entering revivifier 4: enter reactor 2).
Reaction conditions and the results are shown in Table 2.
Embodiment 2
Adopt catalyst A, methyl alcohol introduces fast bed reactor 1, with the regenerated catalyst contact reacts being cooled to 550 DEG C from revivifier and through heat collector introducing fast bed reactor 1, temperature of reaction is 260 DEG C, by reaction product and catalyst separating, reaction product introduces fast bed reactor 2, and the reclaimable catalyst part obtained enters revivifier 4, part enters reactor 2, the two ratio be 80: 20 (enter revivifier front).
The reaction product of fast bed reactor 1 introduces fast bed reactor 2, with the mixture contact reacts introducing the regenerated catalyst from revivifier 4 of fast bed reactor 2 and the reclaimable catalyst from fast bed reactor 1, the reclaimable catalyst from fast bed reactor 3, temperature of reaction is 470 DEG C.The reaction product that fast bed reactor 2 is obtained by reacting is separated with reclaimable catalyst, and reclaimable catalyst introduces revivifier 4, and the reaction product that fast bed reactor 2 obtains introduces product separation system.
Product separation system is separated and obtains being rich in the products such as C4-C8 olefin stream (boiling range is the cut of 10 ~ 85 DEG C) and propylene.Be rich in C
4-C
8olefin stream introduces fast bed reactor 3, react at 600 DEG C after contacting with the regenerated catalyst from revivifier 4, reaction product is separated with reclaimable catalyst, the reclaimable catalyst part obtained enters revivifier 4, part enters fast bed reactor 2, the two ratio be 80: 20 (enter revivifier front), reaction product introduces product separation system.
Reaction conditions and the results are shown in Table 2.
Embodiment 3,
Reaction process is with embodiment 1, and difference is reaction conditions and catalyzer.Reaction conditions and the results are shown in Table 2.
Embodiment 4,
Reaction process is with embodiment 2, and difference is reaction conditions and catalyzer.Reaction conditions and the results are shown in Table 2.
Comparative example 1
Employing fluidized-bed reactor carries out effect during oxygenatedchemicals catalysis conversion method.According to the flow process shown in accompanying drawing 1, wherein, do not use reactor 1,3, methyl alcohol is introduced in reactor 2 and react, the results are shown in Table 3.Reaction conditions and the results are shown in Table 2.
Comparative example 2
According to the method for embodiment 2, do not use reactor 3.
Embodiment 5,
With reference to the method for embodiment 3, unlike, the reclaimable catalyst of reactor 1 and reactor 3 all introduces revivifier regeneration, does not introduce reactor 2.
Comparative example 3
According to the method for embodiment 5, unlike not using reactor 1, methyl alcohol is directly introduced reactor 2, reaction conditions and the results are shown in Table 3.
Comparative example 4
According to the method for comparative example 3, the reclaimable catalyst of reactor 3 is introduced reactor 2, reaction conditions and the results are shown in Table 3.
Embodiment 6
With reference to embodiment 5, the reclaimable catalyst of reactor 1 all introduces revivifier regeneration, does not introduce reactor 2.Reaction conditions and the results are shown in Table 3.
Embodiment 7
With reference to embodiment 5, the reclaimable catalyst of reactor 3 all introduces revivifier regeneration, does not introduce reactor 2.Reaction conditions and the results are shown in Table 3.
Table 2
Table 3
*according to methanol feeding amount, be productivity of propylene (carbon back balance) by transforming the propylene carbon number amount produced divided by methyl alcohol carbon number amount.
From table 2 and table 3, method provided by the invention has higher productivity of propylene, can be converted into propylene by containing methyl alcohol highly selective.
Claims (11)
1. a method for preparing propylene from methanol, comprising:
A. by methyl alcohol with introduce the first reactor through overcooled regenerated catalyst and react, obtain the first reaction product and the first reclaimable catalyst; First reclaimable catalyst partly or entirely introduces revivifier regeneration; The first described reactor is riser reactor, fluidized-bed reactor or the compound reactor that is made up of fluidized-bed reactor and riser reactor;
B. the first reaction product and regenerated catalyst and/or the first reclaimable catalyst and/or the 3rd reclaimable catalyst are introduced the second reactor, be obtained by reacting the second reaction product and the second reclaimable catalyst, the second reaction product is introduced product separation system and is separated and obtains being rich in C
4-C
8the material of alkene and propylene; Second reclaimable catalyst introduces revivifier regeneration; The second described reactor is riser reactor, fluidized-bed reactor or the compound reactor that is made up of fluidized-bed reactor and riser reactor;
What C. described product separation system separation obtained is rich in C
4-C
8the 3rd reactor contact reacts introduced by the material of alkene and regenerated catalyst, obtains the 3rd reclaimable catalyst and the 3rd reaction product, and the product separation system described in the 3rd reaction product introducing is separated; 3rd reclaimable catalyst partly or entirely introduces revivifier regeneration; The 3rd described reactor is riser reactor, fluidized-bed reactor or the compound reactor that is made up of fluidized-bed reactor and riser reactor;
Wherein, described catalyzer comprises modified mesoporous molecular sieve; Described modified mesoporous molecular sieve is the mesoporous molecular sieve comprising phosphorus, rare earth and modified metal, and the described mesoporous molecular sieve comprising phosphorus, rare earth and modified metal comprises with P
2o
5count the phosphorus of 1.3 ~ 15 % by weight, with RE
2o
3meter 0.5 ~ 15 % by weight rare earth and with M
xo
ythe modified metal of meter 0.7 ~ 15 % by weight, described M represents modified metal, x represents the atomicity of M, and y represents the number needed for oxidation state meeting M, described modified metal be selected from group VIII metal, I B race metal, II B race metal, alkali earth metal one or more;
In step B, the part by weight of regenerated catalyst and the 3rd reclaimable catalyst is 1: 0 ~ 3, and the part by weight of regenerated catalyst and the first reclaimable catalyst is 1: 0 ~ 3;
The regenerated catalyst introducing the first reactor is 5 ~ 50 with the weight ratio of the methyl alcohol introducing the first reactor, the described catalyzer introducing the second reactor is 4 ~ 30 with the introducing methyl alcohol of the second reactor and the weight ratio of dme weight sum, and the regenerated catalyst introducing the 3rd reactor is rich in C with described in introducing the 3rd reactor
4-C
8the weight of olefin fraction is 5-40.
2. in accordance with the method for claim 1, it is characterized in that, the temperature of reaction of the first described reactor is 200 ~ 350 DEG C, and reaction absolute pressure is 0.11-0.5MPa, and weight hourly space velocity is 0.1 ~ 100h
-1; The temperature of reaction of the second described reactor is 400 ~ 550 DEG C, and reaction absolute pressure is 0.11-0.5MPa, and weight hourly space velocity is 0.5 ~ 50h
-1; The 3rd described reactor reaction temperature is 510 ~ 650 DEG C, and reaction absolute pressure 0.11-0.5MPa, weight hourly space velocity is 1 ~ 20h
-1.
3. in accordance with the method for claim 2, it is characterized in that, the temperature of reaction of described first reactor is 220 ~ 320 DEG C, and the temperature of reaction of described second reactor is 420 DEG C ~ 530 DEG C, and the temperature of described 3rd reactor is 520 ~ 640 DEG C.
4. in accordance with the method for claim 1, it is characterized in that, the compound reactor that the first described reactor, the second reactor and the 3rd reactor are respectively riser reactor, fluidized-bed reactor or are made up of fluidized-bed reactor and riser reactor; Described fluidized-bed reactor be selected from particulate fluidization bed bioreactor, bubbling bed reactor, turbulent bed reactor and fast bed reactor one or more.
5. in accordance with the method for claim 1, it is characterized in that, described is rich in C
4-C
8olefin feed is preheated to 200 ~ 600 DEG C and introduces the 3rd reactor.
6. in accordance with the method for claim 1, it is characterized in that, in step B, the weight ratio of regenerated catalyst and the 3rd reclaimable catalyst is 1: 0.1 ~ 3, and the weight ratio of regenerated catalyst and the first reclaimable catalyst is 1: 0.1 ~ 3.
7. according to the method described in claim 1 or 6, it is characterized in that, in step B, the part by weight of the first reclaimable catalyst and the 3rd reclaimable catalyst is 1: 0.5 ~ 2.5.
8. in accordance with the method for claim 1, it is characterized in that, described modified mesoporous molecular sieve is comprise the ZSM-5 molecular sieve of phosphorus, rare earth and modified metal and/or comprise the ZRP molecular sieve of phosphorus, rare earth and modified metal, described modified metal be selected from group VIII metal, I B race, II B race metal, alkali earth metal one or more, wherein said comprise phosphorus, rare earth and modified metal ZSM-5 molecular sieve and the described ZRP molecular sieve comprising phosphorus, rare earth and modified metal comprise separately with P
2o
5count the phosphorus of 1.3 ~ 15 % by weight, with RE
2o
3meter 0.5 ~ 15 % by weight rare earth and with M
xo
vthe modified metal of meter 0.7 ~ 15 % by weight.
9. according to the method described in claim 1 or 8, it is characterized in that, described modified metal is one or more in Fe, Zn, Mg, Ag and Ni.
10. according to the method described in claim 1 or 8, it is characterized in that, described catalyzer comprises the modified mesoporous molecular sieve described in 15 ~ 85 % by weight, the binding agent of matrix and 5 ~ 40 % by weight of 15 ~ 60 % by weight.
11. in accordance with the method for claim 9, it is characterized in that, described catalyzer comprises the modified mesoporous molecular sieve described in 15 ~ 85 % by weight, the binding agent of matrix and 5 ~ 40 % by weight of 15 ~ 60 % by weight.
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