CN101172916A - Preparation of propene - Google Patents
Preparation of propene Download PDFInfo
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- CN101172916A CN101172916A CNA2006101178613A CN200610117861A CN101172916A CN 101172916 A CN101172916 A CN 101172916A CN A2006101178613 A CNA2006101178613 A CN A2006101178613A CN 200610117861 A CN200610117861 A CN 200610117861A CN 101172916 A CN101172916 A CN 101172916A
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Abstract
The invention relates to a preparation method of propylene, and mainly solves the technical problems of high investment, large energy consumption and short regeneration period of the catalyst of the prior art. The invention takes methyl alcohol and dimethyl ether as raw materials, wherein, the weight proportion of methyl alcohol and dimethyl ether is 0 to 100 to 100 to 0. The preparation method comprises the steps as follow: (a) the raw materials is firstly contacted with catalyst 1 which comprises alumina to generate a first reaction effluent; (b) the first reaction effluent is contacted with crystalloid sillico aluminate catalyst 2 which has the mol ratio of silicate to aluminum (Sio2AL2O3) of at least 10 to form a second reaction effluent; and the second reaction effluent is separated to obtain the product of the propylene. The invention preferably solves the technical problems mentioned above, and the invention can be applied to the industrial production of the propylene for increasing the yield.
Description
Technical field
The present invention relates to a kind of method of producing propylene, particularly produce the method for propylene about methyl alcohol and dme segmentation catalyzed conversion.
Background technology
Petrochemical complex is a mainstay industry important in the national economy, for industry, agricultural, departments such as traffic and national defence provide a large amount of industrial chemicals, is one of related and branch of industry that drive property is stronger in the national economy.Propylene and ethene then are to constitute modern petrochemical complex of paramount importance two big basic materials.
Propylene is mainly used in produces polypropylene, isopropyl benzene, oxo-alcohols, vinyl cyanide, propylene oxide, vinylformic acid, Virahol etc., and wherein polypropylene accounts for the over half of world's propylene demand.At present, 67% propylene is produced the byproduct of ethene from steam cracking in the world, and 30% produces the byproduct of vapour, diesel oil from refinery catalytic cracking (FCC), and a small amount of (about 3%) is obtained by dehydrogenating propane and ethene-butylene metathesis reaction.Estimate that following propylene demand growth speed is faster than supply.
Higher in view of the growth rate of demand of propylene, and traditional production model presents the pressure of " supply falls short of demand ", and therefore replenishing the propylene demand need be by means of other various propylene enhancing new technology.
All the time; coal or Sweet natural gas preparing synthetic gas, synthesising gas systeming carbinol and alkene isolation technique have had the mass-producing mature experience; but the process by methanol to olefins is breakpoint and the difficult point of synthetic gas to this industrial chain of alkene, and this solution of key technology can be for providing a new raw material route by non-oil resource production basic organic ethene, propylene.Especially in the last few years, it is high that the demand of ethene and propylene continues, and under the deficient day by day situation of petroleum resources.How to hew out a non-oil resource and produce the Coal Chemical Industry variation route of propylene, for greatly alleviating China's oil situation in short supply, promote the great-leap-forward development of the heavy chemical industry of China and the structural adjustment of raw material route, have important strategic meaning and society, economic benefit.
Document CN1166478A, disclose a kind of method of being produced low-carbon alkenes such as ethene, propylene by methyl alcohol or dme, this method is catalyzer with the aluminium phosphate molecular sieve, adopts the ciculation fluidized formula processing method of upstriker dense bed, in 500~570 ℃ of preferred temperature of reaction, air speed 2~6 hours
-1And under 0.01~0.05MPa condition, make methyl alcohol or dme cracking produce low-carbon alkenes such as ethene, propylene.This method one side, temperature is higher, and the purpose product selectivity is low, adopts fluidization to have cost of investment and the higher technical disadvantages of running cost simultaneously.
Document CN1356299A discloses a kind of processing method and system thereof that produces low-carbon alkene by methyl alcohol or dme.This process using silicoaluminophosphamolecular molecular sieves (SAPO-34) is as catalyzer, utilize the ultrashort contact reactor of gas-solid cocurrent flow descending formula fluidized-bed, catalyzer contacts in the ultrashort contact reactor of gas-solid cocurrent flow descending formula fluidized-bed with raw material, the reactant flow direction is descending; Catalyzer and reaction product go out to enter the gas-solid quick disconnector that is arranged on this reactor lower part behind the reactor and carry out sharp separation; Isolated catalyzer enters charcoal regeneration in the revivifier, and catalyzer is cyclic regeneration in system, and reaction cycle is carried out.This technology dme or conversion of methanol are greater than 98%.But this method exists equally, and the ethylene, propylene selectivity is low, cost of investment and the higher technical disadvantages of running cost.
Document CN1704390A discloses a kind of method of methanol conversion system alkene, this method employing Zn-SAPO-34 molecular sieve and binding agent are as the catalyzer of methanol conversion system alkene, 300~500 ℃ of temperature of reaction, reaction pressure is a normal pressure, and the methyl alcohol weight space velocity is 1.0~10 hours
-1, water/methyl alcohol weight ratio is that reaction generates low-carbon alkene under 0~5 condition.This method catalyst life is short, needs by fluidized-bed process the flow process complexity.
Problems such as the technology of above-mentioned bibliographical information mainly exists life of catalyst shorter, needs to adopt fluidization, and investment is high, and energy consumption is big.
Summary of the invention
Technical problem to be solved by this invention is that to overcome the life of catalyst that exists in the technical literature in the past shorter, and investment is high, and the problem that energy consumption is big provides a kind of new method of producing propylene.This method has that catalyst stability is good, and energy consumption is low, the advantage that propene yield is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing propylene, with methyl alcohol and dme is raw material, wherein the weight ratio of methyl alcohol and dme is 0~100: 100~0, may further comprise the steps successively: (a) raw material at first contacts with salic catalyzer 1, generates first strand of reaction effluent; (b) first strand of reaction effluent and silica alumina ratio SiO
2/ Al
2O
3Be at least 2 contacts of 10 crystal aluminosilicate catalyzer, generate second reaction effluent that contains propylene, obtain propylene product through separation.
Catalyzer 1 preferred version is γ-Al in the technique scheme
2O
3Catalyzer 2 preferred versions are at least a for being selected from ZSM molecular sieve, beta-molecular sieve, mordenite or the Y zeolite, its silica alumina ratio SiO
2/ Al
2O
3Preferable range is 20~500; The more preferably scheme of catalyzer 2 is silica alumina ratio SiO
2/ Al
2O
3It is 30~300 ZSM-5 molecular sieve catalyst.Catalyzer 1 temperature of reaction preferable range is 200~480 ℃, and reaction weight space velocity preferable range is 0.1~10 hour
-1, the reaction pressure preferable range is 0.01~2MPa; The temperature of reaction of catalyzer 1 more preferably scope is 250~380 ℃, and reaction weight space velocity more preferably scope is 0.5~5 hour
-1, reaction pressure more preferably scope is 0.05~1MPa.Catalyzer 2 temperature of reaction preferable range are 400~580 ℃, and reaction weight space velocity preferable range is 0.1~20 hour
-1, reaction pressure more preferably scope is 0.01~2MPa; The temperature of reaction of catalyzer 2 more preferably scope is 430~530 ℃, and reaction weight space velocity more preferably scope is 0.5~10 hour
-1, reaction pressure more preferably scope is 0.05~1MPa.The weight ratio preferable range of methyl alcohol and dme is 5~50: 95~50.
Adopt the dual catalyst bed among the present invention, catalyzer 1 is mainly aluminum oxide, realizes the abundant conversion of methyl alcohol to dme, and catalyzer 2 is mainly molecular sieve catalyst, is used for the reaction of the catalytic cracking propylene of methyl alcohol and dme.It is strong exothermic process that methyl alcohol and dme are produced low-carbon alkene, and a large amount of fundamental researchs shows, no matter be that employing methyl alcohol is raw material, still adopting dme is raw material, the distribution no significant difference of final olefin product, but methyl alcohol can carry out at low temperatures to the process of dme, and this process also is strong exothermic process, so just can share the heat effect burden that follow-up methyl alcohol and dme are produced the low-carbon alkene reaction process.In addition, for adopting fixed-bed process, the concentrated heat release of dehydration can cause the higher temperature rise of reactor bed, especially the temperature of catalyst active center may exceed catalyzer apparent temperature tens degree even go up more than the Baidu, and too high local temperature rise is very fatal to the influence of catalyst life, especially can aggravate catalyzer coking inactivation greatly, shorten stable period.Simultaneously, concentrate strong heat release also to bring big difficulty for reactor design and engineering amplification, how to remove heat fast and guarantee the range of reaction temperature of catalyzer the best, it is the where the shoe pinches that reactor amplifies always, although the isothermal of shell and tube reactor on can realization theory exists scale to amplify difficulty equally.
Catalyzer 1 adopts cold operation to realize that most methanol conversion are dme among the present invention, and purpose is to relax the concentrated heat release in the methanol-to-olefins process and too high, the catalyzer rapid deactivation of local temperature rise that causes.Simultaneously, when methyl alcohol reacted the dme that generates by catalyzer 1, the methanol-to-olefins process that a large amount of water of by-product can be catalyzer 2 provided effective diluting effect, thereby reached maximized propene yield and prolong the catalyzer purpose of stable period.Simultaneously, just can solve the problem of removing heat problem and reactor amplification difficulty with fixed bed reaction technology.
Adopting technical scheme of the present invention, is γ-Al at catalyzer 1
2O
3, temperature of reaction is 250~380 ℃, the reaction weight space velocity is 0.5~5 hour
-1, reaction pressure is 0.05~1MPa; Catalyzer 2 is silica alumina ratio SiO
2/ Al
2O
3Be 30~300 ZSM-5 molecular sieve, and temperature of reaction is 430~530 ℃, the reaction weight space velocity is 0.5~10 hour
-1, reaction pressure is under the condition of 0.05~1MPa, and the propylene once through yield can reach 46%, and catalyst life can remain on more than 300 hours, had obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1~5]
According to silica alumina ratio SiO
2/ Al
2O
3Be that 80 proportional arrangement is siliceous, the slip of aluminium, template and water, stirred 20 hours under the room temperature.Crystallization 50~120 hours under 140~210 ℃ temperature is then washed crystallization liquid afterwards, is promptly obtained the ZSM-5 molecular sieve after the oven dry, roasting.After the ZSM-5 molecular sieve adding 60 gram silica gel mixing with 100 grams, extrusion moulding, and, make reaction bed 2 required ZSM-5 type catalyzer 2 after 500 ℃ of roastings 180 ℃ of oven dry.
The specific surface area of beds 1 catalyst system therefor 1 is 200 meters
2/ gram, Al
2O
3Content is γ-Al of 99.7%
2O
3Catalyzer.
Above-mentioned catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 3: 1, and wherein reaction zone 1 reaction conditions is, 380 ℃ of temperature, pressure 0.1MPa, reaction zone 1 reaction effluent enters reaction zone 2,480 ℃ of reaction zone 2 temperature of reaction, and reaction pressure is 0.1MPa.Dme is 1.5: 1 with the methanol quality ratio in the raw material that uses in the experiment, based on the result such as the table 1 that react under the catalyzer 2 Different Weight air speed conditions:
The different air speed reaction results of table 1
Numbering | 1 | 2 | 3 | 4 | 5 |
Air speed, hour -1 | 1.33 | 2.67 | 4.00 | 5.33 | 18.00 |
Yield of ethene, % | 18.21 | 17.34 | 15.82 | 13.92 | 8.55 |
Propene yield, % | 40.88 | 42.57 | 44.59 | 45.84 | 40.45 |
Carbon four yields, % | 21.14 | 21.61 | 22.42 | 22.53 | 21.91 |
Carbon five yields, % | 6.80 | 6.84 | 7.16 | 8.41 | 9.37 |
Carbon six yields, % | 1.99 | 1.87 | 2.00 | 2.22 | 2.44 |
Dme and methyl alcohol total conversion rate, % | 100 | 100 | 99.87 | 99.11 | 93.93 |
[embodiment 6~10]
According to each step and the operational condition of embodiment 1, just change: the silica alumina ratio SiO of ZSM-5 molecular sieve catalyst 2
2/ Al
2O
3Be 200.Catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 5: 1 in the experiment, and wherein reaction zone 1 reaction conditions is, 280 ℃ of temperature, and pressure 0.3MPa, reaction zone 1 reaction effluent enters reaction zone 2.Reaction zone 2 reaction pressures are 0.3MPa, are 1.5 hours based on the weight space velocity of catalyzer 2 raw materials
-1, dme is 3: 1 with the methanol quality ratio in the raw material that uses in the experiment, the result such as the table 2 of reaction zone 2 differential responses temperature:
The result of table 2 differential responses temperature
Numbering | 6 | 7 | 8 | 9 | 10 |
Temperature | 529 | 500 | 478 | 447 | 430 |
Yield of ethene, % | 19.88 | 18.73 | 16.27 | 14.47 | 13.55 |
Propene yield, % | 49.47 | 47.38 | 46.15 | 43.37 | 41.32 |
C 4 | 15.00 | 18.09 | 21.69 | 25.80 | 28.08 |
C 5 | 3.65 | 4.67 | 5.73 | 6.98 | 7.29 |
C 6 | 1.78 | 0.93 | 1.30 | 1.48 | 1.38 |
Dme and methyl alcohol total conversion rate, % | 100.00 | 100.00 | 99.24 | 97.10 | 95.34 |
[embodiment 11]
According to each step and the operational condition of embodiment 1, just change: the silica alumina ratio SiO of ZSM-5 molecular sieve catalyst 2
2/ Al
2O
3Be 20.Catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 1: 1 in the experiment, and wherein reaction zone 1 reaction conditions is, 450 ℃ of temperature, and pressure 1MPa, reaction zone 1 reaction effluent enters reaction zone 2.480 ℃ of reaction zone 2 temperature of reaction, reaction pressure is 1MPa, is 1.5 hours based on the weight space velocity of catalyzer 2 methanol feedstocks
-1, the raw material dme that uses in the experiment is 0: 1 with the methanol quality ratio, reaction result is: propene yield 43.1%, yield of ethene 14.3%, methanol conversion 100%.
[embodiment 12]
According to each step and the operational condition of embodiment 1, just change: the silica alumina ratio SiO of ZSM-5 molecular sieve catalyst 2
2/ Al
2O
3Be 380.Catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 1: 1 in the experiment, and wherein reaction zone 1 reaction conditions is, 270 ℃ of temperature, and pressure 0.8MPa, reaction zone 1 reaction effluent enters reaction zone 2.500 ℃ of reaction zone 2 temperature of reaction, reaction pressure is 0.8MPa, is 5 hours based on the weight space velocity of catalyzer 2 dme raw materials
-1, dme is 1: 0 with the methanol quality ratio in the raw material that uses in the experiment, reaction result is: propene yield 40.2%, yield of ethene 20.6%, dimethyl ether conversion rate 100%.
[embodiment 13]
According to each step and the operational condition of embodiment 1, just change: the silica alumina ratio SiO of ZSM-5 molecular sieve catalyst 2
2/ Al
2O
3Be 300.Catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 2: 1 in the experiment, and wherein reaction zone 1 reaction conditions is, 330 ℃ of temperature, and pressure 0.4MPa, reaction zone 1 reaction effluent enters reaction zone 2.580 ℃ of reaction zone 2 temperature of reaction, reaction pressure is 0.4MPa, is 1.2 hours based on the air speed of catalyzer 2 raw materials
-1, dme is 10: 1 with the methanol quality ratio in the raw material that uses in the experiment, reaction result is: propene yield 43.8%, yield of ethene 24.8%, dme and methyl alcohol total conversion rate 100%.
[embodiment 14]
According to each step and the operational condition of embodiment 1, just change: the silica alumina ratio SiO of ZSM-5 molecular sieve catalyst 2
2/ Al
2O
3Be 100.Catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 1: 1 in the experiment, and wherein reaction zone 1 reaction conditions is, 250 ℃ of temperature, and pressure 1MPa, reaction zone 1 reaction effluent enters reaction zone 2.530 ℃ of reaction zone 2 temperature of reaction, reaction pressure is 1MPa, is 1.5 hours based on the air speed of catalyzer 2 raw materials
-1, dme is 5: 1 with the methanol quality ratio in the raw material that uses in the experiment, reaction result is: propene yield 43.3%, yield of ethene 18.8%, dme and methyl alcohol total conversion rate 100%.
[embodiment 15]
According to each step and the operational condition of embodiment 1, just change: the silica alumina ratio SiO of ZSM-5 molecular sieve catalyst 2
2/ Al
2O
3Be 20.Catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 3: 1 in the experiment, and wherein reaction zone 1 reaction conditions is, 250 ℃ of temperature, and pressure 0.7MPa, reaction zone 1 reaction effluent enters reaction zone 2.480 ℃ of reaction zone 2 temperature of reaction, reaction pressure is 0.7MPa, is 2.8 hours based on the weight space velocity of catalyzer 2 raw materials
-1, methyl alcohol and dme mass ratio are 1: 1 in the raw material that uses in the experiment, reaction result is: propene yield 44.7%, yield of ethene 16.1%, dme and methyl alcohol total conversion rate 100%.
[embodiment 16]
According to each step and the operational condition of embodiment 1, just change: catalyzer 2 is a mordenite, its silica alumina ratio SiO
2/ Al
2O
3Be 600.Catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 0.5: 1 in the experiment, and wherein reaction zone 1 reaction conditions is, 250 ℃ of temperature, and pressure 1.2MPa, reaction zone 1 reaction effluent enters reaction zone 2.580 ℃ of reaction zone 2 temperature of reaction, reaction pressure is 1.2MPa, is 20.0 hours based on the weight space velocity of catalyzer 2 raw materials
-1, methyl alcohol and dme mass ratio are 1: 0 in the raw material that uses in the experiment, reaction result is: propene yield 38.7%, yield of ethene 20.1%, methanol conversion 100%.
[embodiment 17]
According to each step and the operational condition of embodiment 1, just change: catalyzer 2 is a beta-molecular sieve, its silica alumina ratio SiO
2/ Al
2O
3Be 450.Catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 2: 1 in the experiment, and wherein reaction zone 1 reaction conditions is, 280 ℃ of temperature, and pressure 0.1MPa, reaction zone 1 reaction effluent enters reaction zone 2.530 ℃ of reaction zone 2 temperature of reaction, reaction pressure is 0.1MPa, is 1.0 hours based on the weight space velocity of catalyzer 2 raw materials
-1, methyl alcohol and dme mass ratio are 0: 1 in the raw material that uses in the experiment, reaction result is: and propene yield 40.4%, yield of ethene 15.6%, the dimethyl ether conversion rate is 100%.
[embodiment 18]
According to each step and the operational condition of embodiment 1, just change: the silica alumina ratio SiO of ZSM-5 molecular sieve catalyst 2
2/ Al
2O
3Be 60.Catalyzer 1, catalyzer 2 are respectively charged in reaction zone 1 and the reaction zone 2 by mass ratio at 1: 1 in the experiment, wherein reaction zone 1 reaction conditions is, 320 ℃ of temperature, pressure 0.1MPa, reaction zone 1 reaction effluent enters reaction zone 2,460 ℃ of reaction zone 2 temperature of reaction, reaction pressure is 0.1MPa, is 0.8 hour based on the weight space velocity of catalyzer 2 methanol feedstocks
-1, methyl alcohol and dme mass ratio are 1: 0 in the raw material that uses in the experiment, change propylene in time and the yield of ethene variation tendency is as shown in table 3
The experiment of table 3 catalyst stability
Reaction times (hour) | Yield of ethene, % | Propene yield, % |
1.3 | 16.4 | 39.8 |
3.1 | 16.4 | 40.1 |
10.4 | 15.8 | 41.5 |
12.5 | 16.2 | 40.4 |
14.1 | 15.9 | 40.7 |
15.3 | 15.8 | 41.3 |
16.6 | 16.7 | 40.7 |
16.9 | 16.4 | 40.7 |
17.6 | 16.3 | 41.1 |
19.2 | 15.4 | 43.9 |
21.7 | 14.8 | 39.0 |
23.0 | 14.9 | 40.8 |
35.9 | 12.2 | 35.3 |
40.9 | 14.9 | 40.0 |
45.2 | 14.9 | 40.6 |
50.2 | 14.0 | 40.8 |
59.2 | 14.1 | 39.8 |
61.4 | 14.0 | 39.8 |
63.1 | 14.2 | 39.8 |
65.8 | 14.5 | 39.5 |
68.1 | 13.8 | 39.1 |
70.3 | 13.8 | 38.8 |
72.6 | 14.0 | 39.0 |
83.0 | 13.5 | 40.3 |
87.6 | 13.6 | 39.3 |
92.1 | 13.4 | 41.2 |
97.1 | 13.3 | 39.3 |
100.1 | 13.3 | 39.8 |
111.1 | 14.8 | 42.4 |
117.1 | 14.0 | 40.8 |
123.1 | 13.3 | 39.3 |
139.2 | 14.6 | 42.9 |
154.1 | 13.0 | 39.7 |
163.1 | 13.5 | 40.4 |
176.4 | 13.2 | 42.3 |
191.1 | 12.6 | 42.4 |
206.3 | 11.9 | 42.7 |
213.1 | 12.0 | 41.6 |
234.6 | 11.2 | 40.6 |
252.4 | 11.4 | 40.8 |
267.7 | 10.9 | 41.0 |
283.1 | 11.1 | 44.0 |
301.8 | 10.5 | 42.4 |
305.7 | 10.1 | 41.5 |
311.3 | 10.2 | 41.9 |
314.9 | 9.7 | 41.4 |
319.9 | 10.6 | 41.0 |
Claims (9)
1. a method of producing propylene is a raw material with methyl alcohol and dme, and wherein the weight ratio of methyl alcohol and dme is 0~100: 100~0, may further comprise the steps successively:
A) raw material at first contacts with salic catalyzer 1, generates first strand of reaction effluent;
B) first strand of reaction effluent and silica alumina ratio SiO
2/ Al
2O
3Be at least 2 contacts of 10 crystal aluminosilicate catalyzer, generate second reaction effluent that contains propylene, obtain propylene product through separation.
2. according to the described method of producing propylene of claim 1, it is characterized in that catalyzer 1 is γ-Al
2O
3
3. according to the described method of producing propylene of claim 1, it is characterized in that catalyzer 2 is selected from least a in ZSM molecular sieve, beta-molecular sieve, mordenite or the Y zeolite, its silica alumina ratio SiO
2/ Al
2O
3Be 20~500.
4. according to the described method of producing propylene of claim 3, it is characterized in that catalyzer 2 is silica alumina ratio SiO
2/ Al
2O
3It is 30~300 ZSM-5 molecular sieve catalyst.
5. according to the described method of producing propylene of claim 1, it is characterized in that catalyzer 1 temperature of reaction is 200~480 ℃, the reaction weight space velocity is 0.1~10 hour
-1, reaction pressure is 0.01~2MPa.
6. according to the described method of producing propylene of claim 5, it is characterized in that catalyzer 1 temperature of reaction is 250~380 ℃, the reaction weight space velocity is 0.5~5 hour
-1, reaction pressure is 0.05~1MPa.
7. according to the described method of producing propylene of claim 1, it is characterized in that catalyzer 2 temperature of reaction are 400~580 ℃, the reaction weight space velocity is 0.1~20 hour
-1, reaction pressure is 0.01~2MPa.
8. according to the described method of producing propylene of claim 7, it is characterized in that catalyzer 2 temperature of reaction are 430~530 ℃, the reaction weight space velocity is 0.5~10 hour
-1, reaction pressure is 0.05~1MPa.
9. according to the described method of producing propylene of claim 1, the weight ratio that it is characterized in that methyl alcohol and dme is 5~50: 95~50.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103561866A (en) * | 2011-03-15 | 2014-02-05 | 科莱恩产品(德国)有限公司 | Process for manufacture of a zeolite based catalyst for the conversion of methanol to olefins |
CN105085147A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparing low carbon olefins from oxygen-containing compound |
-
2006
- 2006-11-02 CN CNB2006101178613A patent/CN100567226C/en active Active
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103561866A (en) * | 2011-03-15 | 2014-02-05 | 科莱恩产品(德国)有限公司 | Process for manufacture of a zeolite based catalyst for the conversion of methanol to olefins |
US10112188B2 (en) | 2011-03-15 | 2018-10-30 | Clariant Produkte (Deutschland) Gmbh | Process for manufacture of a zeolite based catalyst for the conversion of methanol to olefins |
CN105085147A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparing low carbon olefins from oxygen-containing compound |
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 |
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