CN102276402A - Combined reaction apparatus for producing low-carbon olefin - Google Patents
Combined reaction apparatus for producing low-carbon olefin Download PDFInfo
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- CN102276402A CN102276402A CN2010101998252A CN201010199825A CN102276402A CN 102276402 A CN102276402 A CN 102276402A CN 2010101998252 A CN2010101998252 A CN 2010101998252A CN 201010199825 A CN201010199825 A CN 201010199825A CN 102276402 A CN102276402 A CN 102276402A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention relates to a combined reaction apparatus for producing low carbon olefin. The apparatus is mainly used for solving a problem in prior arts of low low-carbon olefin yield. According to the invention, a combined reaction apparatus for producing low carbon olefin is adopted. The apparatus mainly comprises a main reaction zone 2, a first riser 13, a second riser 23, a first reclaiming zone 18, a second reclaiming zone 30, an auxiliary sedimentation zone 25, gas-solid separating equipment and catalyst circulating pipes. With the technical schemes, the problem is well solved. Therefore, the apparatus can be applied in industrialized productions of low-carbon olefin.
Description
Technical field
The present invention relates to a kind of composite reaction device of producing low-carbon alkene.
Technical background
Low-carbon alkene, promptly ethene and propylene are important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene and propylene are to produce by petroleum path, but because limited supply of petroleum resources and higher price, the cost of being produced propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms producing light olefins.Wherein, the alternative materials that is used for low-carbon alkene production that one class is important is an oxygenatedchemicals, for example alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed by coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, as methyl alcohol, can be made by coal or Sweet natural gas, and technology is very ripe, can realize up to a million tonnes industrial scale.Because the popularity in oxygenatedchemicals source is added and is transformed the economy that generates low-carbon alkene technology, so be subjected to increasing attention by the technology of oxygen-containing compound conversion to produce olefine (OTO).
In the US4499327 patent silicoaluminophosphamolecular molecular sieves catalyzer is applied to methanol conversion system olefin process and studies in great detail, think that SAPO-34 is the first-selected catalyzer of MTO technology.The SAPO-34 catalyzer has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction times of low-carbon alkene 10 seconds, more even reach in the reaction time range of riser tube.
Announced among the US6166282 that a kind of oxygenate conversion is the technology and the reactor of low-carbon alkene, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu reaction of gas speed is finished, after rising to the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Because reaction after product gas and catalyzer sharp separation have effectively prevented the generation of secondary reaction.Through analog calculation, to compare with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all significantly reduce.But yield of light olefins is lower in this method.
Announced among the CN1723262 that it is low-carbon alkene technology that the multiple riser reaction unit that has central catalyst return is used for oxygenate conversion, this covering device comprises a plurality of riser reactors, gas solid separation district, a plurality of offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the disengaging zone of setting, catalyzer and product gas are separated.But yield of light olefins is lower in this method.
In Chinese invention patent 200810043971.9, announced a kind of method that improves yield of light olefins, it is that the first reaction zone top of low-carbon alkene is provided with one second reaction zone that this method adopts in methanol conversion, and this second reaction zone diameter is greater than first reaction zone, to increase the residence time of product gas in second reaction zone of first reaction zone outlet, make unreacted methanol, dme that generates and carbon four above hydrocarbon continue reaction, reach the purpose that improves yield of light olefins, this method comprises that also the charging of second reaction zone can be through isolating freshening carbon four above hydrocarbon.Though this method can improve the yield of low-carbon alkene to a certain extent, but because the catalyzer that first reaction zone comes out has had more carbon distribution, and the carbon four above hydrocarbon pyrolysiss need higher catalyst activity, therefore the carbon four above hydrocarbon changing effects in second reaction zone are still on the low side in this method, cause yield of light olefins lower.
All there is the lower problem of yield of light olefins in prior art.The present invention has solved the problems referred to above targetedly.
Summary of the invention
Technical problem to be solved by this invention is the lower problem of yield of light olefins that exists in the prior art, and a kind of composite reaction device of new production low-carbon alkene is provided.This device is used for the production of low-carbon alkene, has the yield of light olefins advantage of higher.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of composite reaction device of producing low-carbon alkene, mainly comprise main reaction region 2, first riser tube 13, second riser tube 23, first breeding blanket 18, second breeding blanket 30, auxiliary negative area 25, gas-solid separation equipment and catalyst recirculation pipeline etc., 18 tops, first breeding blanket link to each other with revivifier negative area 19, the bottom links to each other with second breeding blanket 30, first breeding blanket 18 links to each other with the stripping zone 33 of main reactor 8 by inclined tube 6 to be generated, first breeding blanket 18 links to each other with the main reaction region 2 of main reactor 8 by regenerator sloped tube, 30 bottoms, second breeding blanket have two catalyst outlets, link to each other with second riser tube 23 with first riser tube 13 respectively, 23 outlets link to each other with auxiliary negative area 25 first riser tube 13 with second riser tube, auxiliary 25 bottoms, negative area link to each other with stripping zone 24, stripping zone 24 bottoms have catalyst outlet, link to each other main reactor 8 with first breeding blanket 18, revivifier 19 and 25 tops, auxiliary negative area are equipped with pneumatic outlet.
In the technique scheme, described main reaction region 2 is a fast fluidized bed; Described molecular sieve comprises SAPO-34 or ZSM-5; Be equipped with gas-solid separation equipment before the described pneumatic outlet, be cyclonic separator; The main reaction region charging comprises methyl alcohol, and first riser tube 13 or 23 chargings of second riser tube are selected from the above hydrocarbon mixture of C4, ethene or petroleum naphtha; Described first riser tube 13 and 23 outlets of second riser tube all are provided with cyclonic separator; The described carbon deposition quantity of catalyst massfraction of first riser tube 13 or second riser tube 23 that enters is less than 0.5%; Describedly return the carbon deposition quantity of catalyst massfraction of main reaction region 2 between 0.5～2.0% from first breeding blanket 18; The described carbon deposition quantity of catalyst massfraction of first riser tube 13 or second riser tube 23 that enters is less than 0.5%; Temperature of reaction in the described main reaction region 2 is 400～500 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 0.8～2.0 meter per second; Temperature of reaction in first riser tube 13 is 510～650 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 3.0～10.0 meter per seconds; Temperature of reaction in second riser tube 23 is 500～630 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 3.0～10.0 meter per seconds; Regenerated catalyst 50～80% in described first breeding blanket 18 enters second breeding blanket 30, and 20-50% returns main reaction region 2; Regenerated catalyst 30～70% in described second breeding blanket 18 enters first riser tube 13,30～70% and enters second riser tube 23.
Among the present invention, can also add a certain amount of thinner in main reaction region and first riser tube, the second riser tube charging, be selected from water vapour, the weight ratio of thinner and raw material charging is 0～1: between 1.
The inventor is by discovering, C 4 olefin or ethene can generate low-carbon alkenes such as propylene under certain conditions.Be provided with main reaction region and assisted reaction district in the method for the invention, main reaction region is used for methanol conversion system alkene, the assisted reaction district comprises first riser tube and second riser tube, be used to transform light hydrocarbons such as carbon four above heavy hydrocarbons (as the higher mixed c 4 of olefin(e) centent, light naphthar etc.) or ethene, thereby reach the purpose that improves yield of light olefins.Simultaneously, because requiring of methanol conversion and heavy hydrocarbon or light hydrocarbon conversion is different, be provided with the two-stage breeding blanket, oxygen deprivation regeneration is carried out in first breeding blanket, be mainly main reaction region the high-selectivity catalyst that has a certain amount of carbon distribution is provided, oxygen enrichment regeneration is carried out in second breeding blanket, and the district provides high activated catalyst for assisted reaction.And the temperature of the catalyzer that comes from second breeding blanket is all higher, helps carbon four above hydrocarbon and ethene and transforms to low-carbon alkene.In addition,, can increase the amount of burnt of revivifier, solve the lower problem of main reaction region coking yield by the reaction in assisted reaction district.Therefore, adopt described method of the present invention, both can effectively improve the yield of purpose product low-carbon alkene, optimized the energy utilization again, have process economy preferably.
Adopt technical scheme of the present invention: described main reaction region 2 is fast fluidized bed; Described molecular sieve comprises SAPO-34 or ZSM-5; Be equipped with gas-solid separation equipment before the described pneumatic outlet, be cyclonic separator; The main reaction region charging comprises methyl alcohol, and first riser tube 13 or 23 chargings of second riser tube are selected from the above hydrocarbon mixture of C4, ethene or petroleum naphtha; Described first riser tube 13 and 23 outlets of second riser tube all are provided with cyclonic separator; The described carbon deposition quantity of catalyst massfraction of first riser tube 13 or second riser tube 23 that enters is less than 0.5%; Describedly return the carbon deposition quantity of catalyst massfraction of main reaction region 2 between 0.5～2.0% from first breeding blanket 18; The described carbon deposition quantity of catalyst massfraction of first riser tube 13 or second riser tube 23 that enters is less than 0.5%; Temperature of reaction in the described main reaction region 2 is 400～500 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 0.8～2.0 meter per second; Temperature of reaction in first riser tube 13 is 510～650 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 3.0～10.0 meter per seconds; Temperature of reaction in second riser tube 23 is 500～630 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 3.0～10.0 meter per seconds; Regenerated catalyst 50～80% in described first breeding blanket 18 enters second breeding blanket 30,20～50% and returns main reaction region 2; Regenerated catalyst 30～70% in described second breeding blanket 18 enters first riser tube 13,30～70% enter second riser tube 23, low-carbon alkene carbon back yield reaches 80.19% (weight) in the product stream I, yield of light olefins reaches 48.36% (weight) in product stream II and the III, has obtained better technical effect.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
Among Fig. 1,1 is the main reaction region bottom feed; 2 is main reaction region; 3 are the circulation inclined tube; 4 is external warmer; 5 is that gas returns the main reactor pipeline in the external warmer; 6 is inclined tube to be generated; 7 is regenerator sloped tube; 8 is main reactor; 9 is gas-solid cyclone separator; 10 is the product stream outlet line; 11 is the first riser tube raw material charging; 12 are reclaimable catalyst lifting medium feeding line; 13 is first riser reactor; 14 is the lifting section in the reclaimable catalyst transfer line; 15 for carrying the delivery medium feeding line of regenerated catalyst to the second riser reactor; 16 is gas-solid cyclone separator; 17 is the second riser tube raw material charging; 18 is first breeding blanket; 19 is the revivifier negative area; 20 is gas-solid cyclone separator; 21 is the regenerated flue gas outlet line; 22 for carrying the delivery medium feeding line of regenerated catalyst to the first riser reactor; 23 is second riser reactor; 24 is stripping zone; 25 are auxiliary negative area; 26 is the product stream outlet line; 27 is stripping medium inlet pipeline; 28 is inclined tube to be generated; 29 are regenerated catalyst conveying standpipe; 30 is second breeding blanket; 31 is the first breeding blanket regenerating medium feeding line; 32 is the second breeding blanket regenerating medium feeding line; 33 is the main reactor stripping zone.
The raw material that comprises methyl alcohol enters main reaction region 2, contact with the catalyzer that comprises molecular sieve, generate the product stream I, form decaying catalyst simultaneously, product stream I after gas-solid separator 9 separates enters centrifugal station by outlet line 10, an isolated decaying catalyst part is returned main reaction region 2, a part enters first breeding blanket, 18 regeneration of revivifier, one enters second breeding blanket 30 regenerated catalyst that forms, one returns main reaction region 2, one enters first riser tube 13 regenerated catalyst in second breeding blanket 18, contact with raw material from pipeline 11, generate the product stream II, one enters second riser tube 23 in assisted reaction district, contacts with raw material from pipeline 17, generate the product stream III, product stream II and III all enter auxiliary negative area 25 together with catalyzer, and product stream II and III after gas solid separation enter centrifugal station by pipeline 26, are back to first breeding blanket 18 of revivifier behind isolated catalyzer process stripping zone 24 strippings.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
In small-sized reaction regeneration device as shown in Figure 1, main reaction region is a fast fluidized bed, revivifier is provided with two-stage regeneration, first breeding blanket is positioned at top, second breeding blanket, the assisted reaction district is provided with two riser tubes, and wherein the first riser tube top is positioned at auxiliary negative area and stripping stage inside, and second riser tube is and assists the outside, negative area, regenerating medium is an air, and the stripping medium is a water vapour.The main reaction region average reaction temperature is 450 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, and linear gas velocity is 1.25 meter per seconds; The first riser reactor medial temperature is 558 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, and linear gas velocity is 5.0 meter per seconds; The second riser reactor medial temperature is 550 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, and linear gas velocity is 5.7 meter per seconds.The main reaction region bottom feed is that purity is 99.5% methyl alcohol, charging is 2 kilograms/hour, catalyzer is SAPO-34, the first riser reactor bottom feed is a mixed c 4, olefin(e) centent is 88% (weight), inlet amount is 0.54 kilogram/hour, the riser reaction zone bottom feed adds water vapour as thinner simultaneously, the weight ratio of water vapour and mixed c 4 is 1: 1, the second riser reactor bottom feed is 47% lighter hydrocarbons for the ethene mass content, wherein also comprise methane 9%, ethane 12%, propane 22%, all the other 8% are hydrogen, CO, CO
2Deng, the regenerated catalyst carbon deposition quantity massfraction that returns main reaction region from first breeding blanket is 1.25%, the regenerated catalyst carbon deposition quantity massfraction that enters two riser reactors from second breeding blanket is that 0.27%, the first breeding blanket temperature is 648 ℃, and the second breeding blanket temperature is 677 ℃.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and low-carbon alkene carbon back yield reaches 80.19% (weight) in the product stream I, and yield of light olefins reaches 41.25% (weight) in product stream II and the III.
[embodiment 2]
According to embodiment 1 described condition, the main reaction region average reaction temperature is 400 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and linear gas velocity is 2.0 meter per seconds; The first riser reactor medial temperature is 510 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and linear gas velocity is 100 meter per seconds; The second riser reactor medial temperature is 500 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and linear gas velocity is 10.0 meter per seconds.The main reaction region bottom feed is that purity is 99.5% methyl alcohol, charging is 1.74 kilograms/hour, catalyzer is SAPO-34, the first riser reactor bottom feed is a mixed c 4, olefin(e) centent is 88% (weight), inlet amount is 0.24 kilogram/hour, the riser reaction zone bottom feed adds water vapour as thinner simultaneously, the weight ratio of water vapour and mixed c 4 is 1: 1, the second riser reactor bottom feed is 47% lighter hydrocarbons for the ethene mass content, wherein also comprise methane 9%, ethane 12%, propane 22%, all the other 8% are hydrogen, CO, CO
2Deng, the regenerated catalyst carbon deposition quantity massfraction that returns main reaction region from first breeding blanket is 0.5%, the regenerated catalyst carbon deposition quantity massfraction that enters two riser reactors from second breeding blanket is 0.16%, the stability that keeps catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, low-carbon alkene carbon back yield reaches 77.97% (weight) in the product stream I, and yield of light olefins reaches 38.45% (weight) in product stream II and the III.
[embodiment 3]
According to embodiment 1 described condition, the main reaction region average reaction temperature is 500 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and linear gas velocity is 0.8 meter per second; The first riser reactor medial temperature is 650 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and linear gas velocity is 3.0 meter per seconds; The second riser reactor medial temperature is 630 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and linear gas velocity is 3.0 meter per seconds.The main reaction region bottom feed is that purity is 99.5% methyl alcohol, charging is 2.96 kilograms/hour, catalyzer is SAPO-34, the first riser reactor bottom feed is a mixed c 4, olefin(e) centent is 61% (weight), inlet amount is 0.67 kilogram/hour, the riser reaction zone bottom feed adds water vapour as thinner simultaneously, the weight ratio of water vapour and mixed c 4 is 1: 1, the second riser reactor bottom feed is 31% lighter hydrocarbons for the ethene mass content, wherein also comprise methane 10.2%, ethane 18%, propane 27%, all the other 13.8% are hydrogen, CO, CO
2Deng, the regenerated catalyst carbon deposition quantity massfraction that returns main reaction region from first breeding blanket is 2.0%, the regenerated catalyst carbon deposition quantity massfraction that enters two riser reactors from second breeding blanket is 0.5%, the stability that keeps catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, low-carbon alkene carbon back yield reaches 7628% (weight) in the product stream I, and yield of light olefins reaches 35.22% (weight) in product stream II and the III.
[embodiment 4]
In small-sized reaction regeneration device as shown in Figure 1, the main reaction region average reaction temperature is 425 ℃, and the first riser reactor medial temperature is 610 ℃, and the second riser reactor medial temperature is 610 ℃.Catalyzer is ZSM-5, and the first riser reactor bottom feed is a light naphthar, forms to see Table 1.The riser reaction zone bottom feed adds water vapour as thinner simultaneously, the weight ratio of water vapour and mixed c 4 is 1: 1, the second riser reactor bottom feed is that olefin(e) centent is at carbon four～carbon six hydrocarbon mixtures more than 70% (wherein carbon four hydrocarbon total mass marks are more than 85%), the regenerated catalyst carbon deposition quantity massfraction that enters two riser reactors from second breeding blanket is 0.16%, the stability that keeps catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, low-carbon alkene carbon back yield reaches 67.25% (weight) in the product stream I, and yield of light olefins reaches 48.36% (weight) in product stream II and the III.
Table 1 light naphthar is formed distribution
| Initial boiling point, ℃ | 40 |
| Final boiling point, ℃ | 162 |
| Alkane, weight % | 65.18 |
| Normal paraffin, weight % | 32.54 |
| Alkene, weight % | 0.17 |
| Naphthenic hydrocarbon, weight % | 28.44 |
| Aromatic hydrocarbons, weight % | 6.21 |
Obviously, adopt method of the present invention, can reach the purpose that improves yield of light olefins, have bigger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (10)
1. composite reaction device of producing low-carbon alkene, mainly comprise main reaction region (2), first riser tube (13), second riser tube (23), first breeding blanket (18), second breeding blanket (30), auxiliary negative area (25), gas-solid separation equipment and catalyst recirculation pipeline etc., top, first breeding blanket (18) links to each other with revivifier negative area (19), the bottom links to each other with second breeding blanket (30), first breeding blanket (18) links to each other with the stripping zone (33) of main reactor (8) by inclined tube to be generated (6), first breeding blanket (18) links to each other with the main reaction region (2) of main reactor (8) by regenerator sloped tube, bottom, second breeding blanket (30) has two catalyst outlets, link to each other with second riser tube (23) with first riser tube (13) respectively, outlet links to each other with auxiliary negative area (25) first riser tube (13) with second riser tube (23), auxiliary bottom, negative area (25) links to each other with stripping zone (24), stripping zone (24) bottom has catalyst outlet, link to each other main reactor (8) with first breeding blanket (18), revivifier (19) and top, auxiliary negative area (25) are equipped with pneumatic outlet.
2. according to the composite reaction device of the described production low-carbon alkene of claim 1, it is characterized in that described main reaction region (2) is fast fluidized bed; Described molecular sieve comprises SAPO-34 or ZSM-5.
3. according to the composite reaction device of the described production low-carbon alkene of claim 1, it is characterized in that being equipped with gas-solid separation equipment before the described pneumatic outlet, be cyclonic separator.
4. according to the composite reaction device of the described production low-carbon alkene of claim 1, it is characterized in that the main reaction region charging comprises methyl alcohol, first riser tube (13) or second riser tube (23) charging are selected from the above hydrocarbon mixture of C4, ethene or petroleum naphtha.
5. according to the composite reaction device of the described production low-carbon alkene of claim 1, it is characterized in that the outlet of described first riser tube (13) and second riser tube (23) all is provided with cyclonic separator.
6. according to the composite reaction device of the described production low-carbon alkene of claim 1, it is characterized in that the described carbon deposition quantity of catalyst massfraction of first riser tube (13) or second riser tube (23) that enters is less than 0.5%.
7. according to the composite reaction device of the described production low-carbon alkene of claim 1, it is characterized in that describedly returning the carbon deposition quantity of catalyst massfraction of main reaction region (2) between 0.5～2.0% from first breeding blanket (18).
8. according to the composite reaction device of the described production low-carbon alkene of claim 1, it is characterized in that the described carbon deposition quantity of catalyst massfraction of first riser tube (13) or second riser tube (23) that enters is less than 0.5%.
9. according to the composite reaction device of the described production low-carbon alkene of claim 1, it is characterized in that the temperature of reaction in the described main reaction region (2) is 400～500 ℃, reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 0.8～2.0 meter per second; Temperature of reaction in first riser tube (13) is 510～650 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 3.0～10.0 meter per seconds; Temperature of reaction in second riser tube (23) is 500～630 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 3.0～10.0 meter per seconds.
10. according to the production method of the described low-carbon alkene of claim 1, it is characterized in that the regenerated catalyst 50～80% in described first breeding blanket (18) enters second breeding blanket (30), 20～50% return main reaction region (2); Regenerated catalyst 30～70% in described second breeding blanket (18) enters first riser tube (13), and 30～70% enter second riser tube (23).
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539610A (en) * | 2012-07-09 | 2014-01-29 | 中国石油化工集团公司 | Device for producing alkene from oxygenated compound |
| CN103539616A (en) * | 2012-07-09 | 2014-01-29 | 中国石油化工集团公司 | Method for preparing olefins from oxygen-containing compound |
| CN103539611A (en) * | 2012-07-09 | 2014-01-29 | 中国石油化工集团公司 | Device for preparing olefins by using oxygen-containing compounds |
| CN103539598A (en) * | 2012-07-09 | 2014-01-29 | 中国石油化工集团公司 | Method for preparing light olefins from oxygen-containing compound |
| CN103739429A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Reaction device for low-carbon olefin preparation from methanol |
| CN103772091A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for manufacturing low-carbon alkene from methanol |
| CN107540498A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | By methanol or the method for dimethyl ether conversion preparing aromatic hydrocarbon and low-carbon alkene |
| CN107540496A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Methanol or the method for dimethyl ether production aromatic hydrocarbons and low-carbon alkene |
| CN107540492A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | By methanol or the method for dimethyl ether production aromatic hydrocarbons and low-carbon alkene |
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