CN102276380B - Method for producing dimethyl ether in process for producing low-carbon olefin by using methanol - Google Patents
Method for producing dimethyl ether in process for producing low-carbon olefin by using methanol Download PDFInfo
- Publication number
- CN102276380B CN102276380B CN201010199717.5A CN201010199717A CN102276380B CN 102276380 B CN102276380 B CN 102276380B CN 201010199717 A CN201010199717 A CN 201010199717A CN 102276380 B CN102276380 B CN 102276380B
- Authority
- CN
- China
- Prior art keywords
- reactor
- sapo
- spent agent
- methanol
- dimethyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for producing dimethyl ether in the process for producing low-carbon olefin by using methanol, and mainly solves the problem that the dimethyl ether production catalyst system is single in the prior art. The method mainly comprises the following steps that: a) raw materials containing the methanol and a molecular sieve catalyst are contacted in a first reactor to form a material flow I containing the low-carbon olefin and the catalyst; b) the catalyst in the material flow I is subjected to gas-solid separation so as to form a spent catalyst which enters a precipitator, the first part exchanges heat with the raw materials and then enters a second reactor, the second part returns to the first reactor, and the third part is regenerated and stripped and then enters the first reactor; and c) the raw materials containing the methanol and the spent catalyst are contacted in the second reactor to form a product material flow II containing the dimethyl ether, and the material flow II is merged into the material flow I and then flows out of the precipitator. The technical scheme that heat exchange medium which exchanges heat with the spent catalyst enters the first reactor better solves the problem, and can be used for the industrial production of the low-carbon olefin through methanol transformation.
Description
Technical field
The present invention relates to the method for producing dimethyl ether in process for producing low-carbon olefin by using methanol.
Background technology
Low-carbon alkene, is defined as ethene and propylene here, is two kinds of important basic chemical industry raw materials, and its demand is in continuous increase.Ethene, propylene are mainly to make by petroleum path traditionally, but due to the limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people start to greatly develop substitute energy transformation technology, and as the technique of oxygen-containing compound conversion to produce olefine (OTO), oxygenatedchemicals comprises methyl alcohol, ethanol, dme, methyl ethyl ether, methylcarbonate etc.Have many technology to can be used to produce oxygenatedchemicals, raw material comprises coal, Sweet natural gas, biomass etc.As methyl alcohol, can be made by coal or Sweet natural gas, technique is very ripe, can realize the industrial scale of up to a million tonnes.Popularity due to oxygenatedchemicals source, add and transform the economy that generates low-carbon alkene technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), particularly the technique by preparing olefin by conversion of methanol (MTO) is subject to increasing attention.
Dme (DME) is as a kind of emerging basic chemical raw materials, and excellent performance, has the advantages such as burning highly effective, cleaning, safety as domestic fuel and automobile fuel, is the desirable alternative fuel of diesel oil and liquefied petroleum gas (LPG).Can be used as the propellent of aerosol, substitute Chlorofluorocarbons (CFCs) (fluorine Lyons), third (fourth) alkane gas that liquefies, become the 4th generation propellent main body.Dme is also important industrial chemicals, at medicine, agricultural chemicals and dyestuffs industries, is widely used.
In US4499327 patent, silicoaluminophosphamolecular molecular sieve catalyst is applied to preparing olefin by conversion of methanol technique and studies in detail, think that SAPO-34 is the first-selected catalyzer of MTO technique.SAPO-34 catalyzer has very high light olefin selectivity, and activity is also higher, and can make methanol conversion is reaction times of light olefin to be less than the degree of 10 seconds, even reaches in the reaction time range of riser tube.
In CN1962594A patent, adopt fluid bed reactor methanol gas phase dehydration preparing dimethy ether, catalyzer adopts gama-alumina, and reaction conversion ratio reaches 89%, and selectivity is greater than 99%, and fluidized-bed inner catalyst upgrades, regeneration is easy, can keep catalyst activity stable.But this process design is unreasonable, and temperature of reaction is higher.
For MTO technology, on SAPO-34 catalyzer, long-pending a certain amount of carbon can effectively improve the selectivity of low-carbon alkene in reaction product, and has a best catalyst carbon deposit weight range to make in product the selectivity of low-carbon alkene the highest.Current methanol-to-olefins method, on catalyst surface, control and adhere to certain coke content, effectively improved the selectivity of low-carbon alkene in product, the meanwhile also corresponding raising with the increase of coke content of the selectivity of dme in product, along with catalyzer coke content further increases, the selectivity of dme increases substantially, and therefore, needs independent separating device to isolate dme a small amount of in product.
Summary of the invention
Technical problem to be solved by this invention is that in prior art, dme is produced the single problem of catalyst system, and the method for by-product dme in a kind of new preparing light olefins from methanol is provided.The method, for the production of low-carbon alkene, has advantages of and can utilize the carbon deposited catalyst of methanol-to-olefins to produce dme, energy effective utilization.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows, the method of by-product dme in preparing light olefins from methanol, mainly comprise the following steps: a) raw material that comprises methyl alcohol is contacted under condition for validity in the first reactor with molecular sieve catalyst, generate the logistics I that comprises low-carbon alkene, catalyzer; B) catalyzer in logistics I forms spent agent and enters settling vessel after gas solid separation, in settling vessel, spent agent is at least divided into three parts, first part enters the second reactor after heat transferring medium heat exchange, second section returns to the first reactor through circulation line, third part through pipeline to be generated enter revivifier regeneration, stripper stripping enters the first reactor by regeneration pipeline; C) raw material containing methyl alcohol contacts in the second reactor with spent agent, generates the product logistics II that comprises dme, and the catalyzer that logistics II is carried secretly enters settling vessel after gas solid separation, and logistics II flows out settling vessel after being incorporated to logistics I; Wherein, described heat transferring medium is the raw material that comprises methyl alcohol, enters the first reactor with the heat transferring medium after spent agent heat exchange.
In technique scheme, the first reactor fast fluidized bed reactor, the second reactor is riser reactor, and molecular sieve catalyst comprises and is selected from SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44 or SAPO-56 silicoaluminophosphamolecular molecular sieve catalyst; The temperature of reaction of the first reactor is 350～600 ℃, and reaction pressure is counted 001～0.3MPa with gauge pressure, and linear gas velocity is 0.8～2.5 meter per second; Temperature of reaction in the second reactor is 150～380 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 3.0～10.0 meter per seconds.Molecular sieve catalyst is selected from SAPO-34 silicoaluminophosphamolecular molecular sieve catalyst; The temperature of reaction of the first reactor is preferably 400～500 ℃, and reaction pressure is preferably 0.1～0.2MPa in gauge pressure, and linear gas velocity is preferably 1.0～1.5 meter per seconds; Temperature of reaction in the second reactor is preferably 250～350 ℃, and reaction pressure is preferably 0.1～0.2MPa in gauge pressure, and linear gas velocity is preferably 5.0～8.0 meter per seconds.Spent agent is in mass flux ratio first part in settling vessel: second section: third part=0.01～10: 1: 0.01～10.Spent agent is in the preferred first part of mass flux ratio in settling vessel: second section: third part=0.05～1: 1: 0.05～1.Spent agent temperature after heat transferring medium heat exchange is cooled to 200～350 ℃.Spent agent temperature after heat transferring medium heat exchange is preferably cooled to 250～300 ℃.In settling vessel, the average coke content of spent agent is 1～9%.In settling vessel, the average coke content of spent agent is preferably 2～6%.
Adopt method of the present invention, in settling vessel, spent agent first carries out heat exchange with methyl alcohol in interchanger, send into again riser tube and methanol mixed, reaction is removed separation circuit after generating and mixing containing the product of dme and the product of methanol-to-olefins, can effectively improve the output of methanol-to-olefins by product dme; Methyl alcohol after heat exchange is incorporated to the reactor that hot methanol enters methanol-to-olefins, the heat of effective recycling spent agent.Riser tube bottom has cold methanol nozzle, by regulating riser tube hot methanol charging and cold methanol charging ratio can effectively control the bed temperature in riser tube.Therefore, method of the present invention can effectively utilize the spent agent in methanol to olefins reaction to prepare dme, makes full use of dme separating device effective output that increases dme, in addition, and can also effective recycling spent agent heat.
Adopt technical scheme of the present invention: the first reactor is fast fluidized bed, the second reactor is riser tube, and molecular sieve comprises silicoaluminophosphamolecular molecular sieve catalysts such as being selected from SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, SAPO-56.The temperature of reaction of the first reactor is 350～600 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 0.8～2.5 meter per second; The temperature of reaction of the second reactor is 150～380 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 3.0～10.0 meter per seconds.Spent agent is in mass flux ratio first part in settling vessel: second section: third part=0.01～10: 1: 0.01～10.Spent agent temperature after heat transferring medium heat exchange is cooled to 200～350 ℃.The average coke content of settling vessel inner catalyst is 1～9%.In product, ethene+propylene carbon base absorption rate can reach 63.71% weight, and the yield of dme can reach 20.45% weight simultaneously.Obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is settling vessel; 2 is the second reactor; 3 is fast bed pipeline; 4 is cold methanol; 5 is interchanger; 6 is hot methanol; 7 is circulation line; 8 is the first reactor; 9 is pipeline to be generated; 10 is regeneration pipeline; 11 is revivifier; 12 is stripper.
Raw material hot methanol 6 enters reactor from the first reactor 8 bottoms, contact and react with the catalyzer of regeneration pipeline 10 with catalyst recycle line 7, gas-solid mixture enters the catalyst settler 1 of reaction unit after sharp separation, and the interior gaseous products of settling vessel 1 enters follow-up centrifugal station after cyclonic separator is deviate from catalyzer.Spent agent in settling vessel is divided into three parts, first part's spent agent enters the second reactor 2 after fast bed pipeline 3 enters interchanger 5 and cold methanol 4 heat exchange, the cold methanol 4 spraying into nozzle with hot methanol 6 contacts, and its product and catalyzer enter settling vessel 1 after gas solid separation; Cold methanol 4 is incorporated to hot methanol 6 and enters the first reactor 8 after interchanger 5 heat exchange; Second section spent agent returns to the first reactor 8 through circulation line 7; Third part enters revivifier 11 through pipeline 9 to be generated, and the carbon deposited catalyst that enters revivifier 11 enters stripper 12 after contacting with regenerating medium and burning, and the regenerated catalyst after stripping is delivered to the first reactor 8 through regeneration pipeline 10.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1～4]
On reaction unit as shown in Figure 1, raw material is methyl alcohol, and the first reactor adopts fast fluidized bed, and the second reactor is riser tube, and temperature of reaction is 450 ℃, and in reactor, linear gas velocity is 1.5 meter per seconds; Riser temperature is 300 ℃, in riser tube, linear gas velocity is 8.0 meter per seconds, reactor and riser tube are 0.01MPa in gauge pressure, controlling heat exchanger exit spent agent temperature is 250 ℃, the thief hole of spent agent is positioned at pipeline 9 to be generated, and on catalyzer, the analysis of carbon content adopts Infrared Carbon-sulphur high speed analysis instrument.The coke content of controlling reclaimable catalyst is 5.9% (weight percent), the mass rate of reclaimable catalyst three parts is remained on to quick pipeline flow: circulation line flow: pipeline to be generated flow=0.1: 1: 0.1, make system run all right, control conveniently.Catalyzer adopts respectively SAPO-34, SAPO-11, SAPO-18, the SAPO-56 modified catalyst of spray-dried moulding.Reactor outlet product adopts online gas chromatographic analysis, and experimental result is in Table 1.
Table 1
| Parameter | Catalyst type | Ethene carbon base absorption rate, % (weight) | Propylene carbon base absorption rate, % (weight) | Yield of dimethyl ether, % (weight) |
| |
SAPO-34 | 34.53 | 27.40 | 20.48 |
| |
SAPO-11 | 6.81 | 18.48 | 25.60 |
| Embodiment 3 | SAPO-18 | 32.62 | 22.69 | 18.24 |
| Embodiment 4 | SAPO-56 | 22.90 | 18.17 | 20.45 |
[embodiment 5～8]
According to the condition described in embodiment 1, just change the temperature of the first reactor, experimental result is in Table 2.
Table 2
| Parameter | The first temperature of reactor, ℃ | Ethene carbon base absorption rate, % (weight) | Propylene carbon base absorption rate, % (weight) | Yield of dimethyl ether, % (weight) |
| |
350 | 20.24 | 21.25 | 23.09 |
| Embodiment 6 | 400 | 32.49 | 27.28 | 20.18 |
| |
500 | 36.99 | 24.49 | 19.48 |
| |
600 | 42.18 | 16.57 | 18.89 |
[embodiment 9～11]
Condition according to described in embodiment 1, just changes riser temperature, and experimental result is in Table 3.
Table 3
| Parameter | Riser temperature, ℃ | Ethene carbon base absorption rate, % (weight) | Propylene carbon base absorption rate, % (weight) | Yield of dimethyl ether, % (weight) |
| Embodiment 9 | 150 | 34.39 | 27.42 | 10.79 |
| |
350 | 34.69 | 27.39 | 17.54 |
| |
380 | 34.85 | 27.47 | 16.94 |
[embodiment 12～14]
Condition according to described in embodiment 1, just changes reactor linear speed, and experimental result is in Table 4.
Table 4
| Parameter | Reactor linear speed, meter per second | Ethene carbon base absorption rate, % (weight) | Propylene carbon base absorption rate, % (weight) | Yield of dimethyl ether, % (weight) |
| |
0.8 | 30.24 | 20.17 | 20.24 |
| Embodiment 13 | 1.0 | 35.22 | 28.49 | 20.45 |
| Embodiment 14 | 2.5 | 32.01 | 22.72 | 20.55 |
[embodiment 15～17]
Condition according to described in embodiment 1, just changes riser tube linear speed, and experimental result is in Table 5.
Table 5
| Parameter | Reactor linear speed, meter per second | Ethene carbon base absorption rate, % (weight) | Propylene carbon base absorption rate, % (weight) | Yield of dimethyl ether, % (weight) |
| Embodiment 15 | 3.0 | 34.41 | 27.27 | 20.85 |
| Embodiment 16 | 5.0 | 34.46 | 26.34 | 19.99 |
| Embodiment 17 | 10 | 34.49 | 26.37 | 10.04 |
[embodiment 18～20]
According to the condition described in embodiment 1, reactor and riser tube adopt same press operation, change the pressure of reactor, riser tube, and experimental result is in Table 6.
Table 6
| Parameter | The pressure of reactor and revivifier, MPa | Ethene carbon base absorption rate, % (weight) | Propylene carbon base absorption rate, % (weight) | Yield of dimethyl ether, % (weight) |
| Embodiment 18 | 0.1 | 33.47 | 26.92 | 20.27 |
| Embodiment 19 | 0.2 | 32.50 | 26.14 | 20.75 |
| Embodiment 20 | 0.3 | 27.80 | 23.33 | 21.20 |
[embodiment 21～25]
According to the condition described in embodiment 1, just change the ratio of the mass rate of reclaimable catalyst three parts, experimental result is in Table 7.
Table 7
| Parameter | Quick pipeline: circulation line: pipeline to be generated (mass flux ratio) | Ethene carbon base absorption rate, % (weight) | Propylene carbon base absorption rate, % (weight) | Yield of dimethyl ether, % (weight) |
| Embodiment 21 | 0.05∶1∶0.1 | 35.22 | 27.89 | 5.78 |
| Embodiment 22 | 1∶1∶0.1 | 33.12 | 26.21 | 15.55 |
| Embodiment 23 | 0.1∶1∶0.05 | 29.78 | 25.33 | 12.48 |
| Embodiment 24 | 0.1∶1∶1 | 34.54 | 27.43 | 18.64 |
| Embodiment 25 | 1∶1∶0.05 | 26.24 | 23.96 | 7.55 |
[embodiment 26～29]
According to the condition described in embodiment 1, just change the coke content of reclaimable catalyst, experimental result is in Table 8.
Table 8
| Parameter | Spent agent coke content, % (weight) | Ethene carbon base absorption rate, % (weight) | Propylene carbon base absorption rate, % (weight) | Yield of dimethyl ether, % (weight) |
| Embodiment 26 | 1.00 | 31.24 | 28.37 | 23.37 |
| Embodiment 27 | 2.05 | 32.68 | 28.04 | 20.97 |
| Embodiment 28 | 7.50 | 30.27 | 20.96 | 15.48 |
| Embodiment 29 | 9.20 | 28.72 | 16.09 | 12.64 |
[embodiment 30～31]
According to the condition described in embodiment 1, just change heat exchanger exit spent agent temperature, experimental result is in Table 9.
Table 9
| Parameter | Heat exchanger exit spent agent temperature, ℃ | Ethene carbon base absorption rate, % (weight) | Propylene carbon base absorption rate, % (weight) | Yield of dimethyl ether, % (weight) |
| Embodiment 30 | 200 | 33.41 | 26.32 | 16.44 |
| Embodiment 21 | 350 | 34.53 | 27.37 | 18.63 |
In experimentation, the temperature of heat exchanger exit spent agent and riser temperature are controlled to close scope, can allow the temperature of riser tube be more prone to control.
Obviously, adopt method of the present invention, can effectively utilize the spent agent in methanol to olefins reaction to prepare dme, effectively increase the output of dme, improve the utilization ratio of dme separating device, and can rationally recycle spent agent heat, and easy to operate, be easy to control, can be used in the industrial production of low-carbon alkene.
Claims (5)
1. the method for producing dimethyl ether in process for producing low-carbon olefin by using methanol, mainly comprises the following steps:
A) raw material that comprises methyl alcohol is contacted under condition for validity in the first reactor with molecular sieve catalyst, generate the stream I that comprises low-carbon alkene, catalyzer;
B) catalyzer in stream I forms spent agent and enters settling vessel after gas solid separation, in settling vessel, spent agent is at least divided into three parts, first part enters the second reactor after heat transferring medium heat exchange, second section returns to the first reactor through circulation line, third part through pipeline to be generated enter revivifier regeneration, stripper stripping enters the first reactor by regeneration pipeline;
C) raw material containing methyl alcohol contacts in the second reactor with spent agent, generates the product stream I I that comprises dme, and the catalyzer that stream I I carries secretly enters settling vessel after gas solid separation, and stream I I flows out settling vessel after being incorporated to stream I;
Wherein, described heat transferring medium is the raw material that comprises methyl alcohol, enters the first reactor with the heat transferring medium after spent agent heat exchange; The first reactor fast fluidized bed reactor, the second reactor is riser reactor, molecular sieve catalyst comprises and is selected from SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44 or SAPO-56 silicoaluminophosphamolecular molecular sieve catalyst; The temperature of reaction of the first reactor is 350～600 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 0.8～2.5 meter per second; Temperature of reaction in the second reactor is 150～380 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 3.0～10.0 meter per seconds;
Spent agent is in mass flux ratio first part in settling vessel: second section: third part=0.01～10: 1: 0.01～10; Spent agent temperature after heat transferring medium heat exchange is cooled to 200～350 ℃; In settling vessel, the average coke content of spent agent is 1～9%.
2. the method for producing dimethyl ether in process for producing low-carbon olefin by using methanol according to claim 1, is characterized in that molecular sieve catalyst is selected from SAPO-34 silicoaluminophosphamolecular molecular sieve catalyst; The temperature of reaction of the first reactor is 400～500 ℃, and reaction pressure is counted 0.1～0.2MPa with gauge pressure, and linear gas velocity is 1.0～1.5 meter per seconds; Temperature of reaction in the second reactor is 250～350 ℃, and reaction pressure is counted 0.1～0.2MPa with gauge pressure, and linear gas velocity is 5.0～8.0 meter per seconds.
3. the method for producing dimethyl ether in process for producing low-carbon olefin by using methanol according to claim 1, is characterized in that in settling vessel that spent agent is in mass flux ratio first part: second section: third part=0.05～1: 1: 0.05～1.
4. the method for producing dimethyl ether in process for producing low-carbon olefin by using methanol according to claim 1, is characterized in that spent agent temperature after heat transferring medium heat exchange is cooled to 250～300 ℃.
5. the method for producing dimethyl ether in process for producing low-carbon olefin by using methanol according to claim 1, is characterized in that the average coke content of spent agent in settling vessel is 2～6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010199717.5A CN102276380B (en) | 2010-06-11 | 2010-06-11 | Method for producing dimethyl ether in process for producing low-carbon olefin by using methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010199717.5A CN102276380B (en) | 2010-06-11 | 2010-06-11 | Method for producing dimethyl ether in process for producing low-carbon olefin by using methanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102276380A CN102276380A (en) | 2011-12-14 |
| CN102276380B true CN102276380B (en) | 2014-01-22 |
Family
ID=45102174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010199717.5A Active CN102276380B (en) | 2010-06-11 | 2010-06-11 | Method for producing dimethyl ether in process for producing low-carbon olefin by using methanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102276380B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6472569B1 (en) * | 1999-04-16 | 2002-10-29 | Phillips Petroleum Company | Silicoaluminophosphate material, a method of making such improved material and the use thereof in the conversion of oxygenated hydrocarbons to an olefin and/or an ether |
| CN101104575B (en) * | 2006-07-13 | 2010-05-12 | 中国石油化工股份有限公司 | Method for producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion |
| CN101152997B (en) * | 2006-09-29 | 2011-04-20 | 中国石油化工股份有限公司 | Liquefaction catalytic conversion method for producing dimethyl ether with methanol |
| CN101152998B (en) * | 2006-09-29 | 2011-04-20 | 中国石油化工股份有限公司 | Double-reaction area liquefaction catalytic conversion method for producing dimethyl ether with methanol |
| CN101205172B (en) * | 2006-12-22 | 2011-04-20 | 中国石油化工股份有限公司 | Method for producing dimethyl ether by fluidized catalytic gas-phase dehydration of methanol |
| CN101239871B (en) * | 2007-02-07 | 2011-05-18 | 中国石油化工股份有限公司 | Method for increasing selectivity of low-carbon olefins in methanol or dimethyl ether converting process |
| CN101239874A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Reaction device for converting oxygen-containing compound to low-carbon olefins |
| EP2022565A1 (en) * | 2007-07-06 | 2009-02-11 | Casale Chemicals S.A. | Process for preparing silicoaluminoposphate (SAPO) molecular sieves, catalysts containing said sieves and catalytic dehydration processes using said catalysts |
-
2010
- 2010-06-11 CN CN201010199717.5A patent/CN102276380B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102276380A (en) | 2011-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101279877B (en) | Method for increasing yield of ethylene and propone in conversion process of oxocompound | |
| CN101348404B (en) | Method for improving ethylene and propene yield in methyl alcohol or dimethyl ether conversion process | |
| CN101270023B (en) | Method for improving yield of light olefin hydrocarbon | |
| CN101239869B (en) | Process for converting methanol or dimethyl ether to low-carbon olefins | |
| CN101270017B (en) | Process for producing light olefin hydrocarbon with oxygen-containing compound conversion | |
| CN101279875A (en) | Method for increasing production of ethylene and propone | |
| CN101279873B (en) | Method for preparing low-carbon olefin hydrocarbon with methanol or dimethyl ether | |
| CN102276386B (en) | Production method of light olefins | |
| CN101402539B (en) | Process for producing light olefins with methanol or dimethyl ether | |
| CN101239873B (en) | Method for converting oxygen-containing compound to low-carbon olefins | |
| CN101293803B (en) | Method for converting oxygen-containing compounds into low carbon olefin hydrocarbon | |
| CN101270020B (en) | Method for preparing low carbon olefin hydrocarbon with methanol | |
| CN101260014B (en) | Method for producing low-carbon olefins from oxygen-containing compound | |
| CN102295507B (en) | Method for converting methanol or dimethyl ether into low-carbon olefin | |
| CN101279876B (en) | Method for preparing ethylene and propone with oxocompound | |
| CN103121901B (en) | The method of converting oxygen-containing compound to low-carbon olefins | |
| CN102276379B (en) | Method for coproducing dimethyl ether serving as byproduct in process of preparing low-carbon olefin through methanol conversion | |
| CN102276380B (en) | Method for producing dimethyl ether in process for producing low-carbon olefin by using methanol | |
| CN102276381B (en) | Method for improving selectivity of light olefins prepared from conversion of oxygenated compound | |
| CN103121890B (en) | Method for producing low carbon olefin with oxygen compound | |
| CN102464534B (en) | Method for producing low-carbon olefins from methanol | |
| CN101293802A (en) | Method for preparing light olefin hydrocarbon with methanol or dimethyl ether | |
| CN102276383B (en) | Method of reducing runoff of catalysts in conversion of oxygen containing compounds to low carbon olefins | |
| CN101279874B (en) | Method for preparing low-carbon olefin hydrocarbon with methanol or dimethyl ether | |
| CN102276382A (en) | Method of coproduction of dimethyl ether in methanol-to-low carbon olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |