CN102875297B - The method of low-carbon alkene is prepared with methyl alcohol and petroleum naphtha - Google Patents
The method of low-carbon alkene is prepared with methyl alcohol and petroleum naphtha Download PDFInfo
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P30/40—Ethylene production
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Abstract
The present invention relates to a kind of method that low-carbon alkene prepared by methyl alcohol and petroleum naphtha, mainly solve the problem that in prior art, yield of light olefins is low.The present invention mainly comprises the following steps by adopting: the raw material that (1) comprises petroleum naphtha enters riser tube I, contact with regenerated catalyst, product stream and catalyzer enter settling vessel, after gas solid separation, product stream enters centrifugal station, isolated more than C4 hydrocarbon enters riser tube II, contacts with regenerated catalyst, and product stream and catalyzer enter settling vessel; (2) catalyzer in settling vessel is at least divided into two portions after stripping, and a part enters revivifier regeneration, and a part enters riser tube III, and with the contact raw comprising methyl alcohol, product stream and the catalyzer of generation enter settling vessel; Wherein, settling vessel is positioned at revivifier top, and the entrance end of riser tube I and II is positioned at revivifier, and the technical scheme that exit end is positioned at settling vessel solves the problems referred to above preferably, can be used in the industrial production of low-carbon alkene.
Description
Technical field
The present invention relates to a kind of method that low-carbon alkene prepared by methyl alcohol and petroleum naphtha.
Technical background
Low-carbon alkene, i.e. ethene and propylene, be two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are produced by petroleum path, but due to the limited supply of petroleum resources and higher price, produce ethene by petroleum resources, the cost of propylene constantly increases.In recent years, people start to greatly develop the technology that alternative materials transforms ethene processed, propylene.Wherein, the important alternative materials for light olefin production of one class is oxygenatedchemicals, such as 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, and as methyl alcohol, can be obtained by coal or Sweet natural gas, technique is very ripe, can realize the industrial scale of up to a million tonnes.Due to the popularity in oxygenatedchemicals source, add the economy transforming and generate light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), be particularly subject to increasing attention by the technique of preparing olefin by conversion of methanol (MTO).
Petroleum naphtha is a kind of light-end products, is cut corresponding cut by crude distillation or oil secondary processing and is obtained.Its boiling spread is determined according to need, is generally wider boiling range, as 20-220 DEG C.Petroleum naphtha is pyrolysis in tubular furnace preparing ethylene, and propylene and catalytic reforming produce the important source material of benzene,toluene,xylene.As cracking stock, in requiring petroleum naphtha to form, the content of alkane and naphthenic hydrocarbon is not less than 70% (volume).Naphtha catalytic pyrolysis preparing low-carbon alkene is then under catalyzer existent condition, carries out cracking to obtain the production process of low-carbon alkene to petroleum hydrocarbon.Compare with traditional tube furnace steam heat cracking, this process reaction temperature is about lower than steam cracking reaction 50 ~ 200 DEG C, and energy consumption significantly reduces; Cracking furnace pipe inwall coking rate also can reduce, thus can prolong operation cycle, increases the boiler tube life-span; Carbon emission simultaneously also can reduce, and alleviates pollution, and can adjust the product mix flexibly.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene is disclosed in US6166282, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, after rising to the fast subregion that internal diameter diminishes rapidly, special gas-solid separation equipment initial gross separation is adopted to go out most entrained catalyst.Due to reaction after product gas and catalyzer sharp separation, effectively prevent the generation of secondary reaction.Through analog calculation, compared with traditional bubbling fluidization bed bioreactor, needed for this fast fluidized bed reactor internal diameter and catalyzer, reserve all greatly reduces.
The multiple riser reaction unit disclosed in CN1723262 with central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises multiple riser reactor, gas solid separation district, multiple offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the disengaging zone of setting, catalyzer and gas product are separated.But there is the lower shortcoming of yield of light olefins in the method.
Disclose a kind of method of methanol production propylene in EP0448000 and EP0882692, first methyl alcohol be converted into DME and water, then mixture is transported to First reactor, and add steam in this reactor.In the first reactor, methyl alcohol and (or) dme or its mixture and catalyst exposure react, catalyzer adopts the special ZSM-5 catalyzer containing ZnO and CdO, temperature of reaction 280 ~ 570 DEG C, pressure 0.01 ~ 0.1MPa, preparing with propylene is the product of main hydro carbons.Heavier product is as C
5 +hydrocarbon continues to carry out reacting the hydro carbons be converted into based on propylene in second reactor, after cooling, send separator back to.Product is compressed, refining further after can obtain the chemical grade propylene that purity is 97%.But adopt multiple fixed-bed reactor in this technique, because the activity of catalyzer limits, therefore need frequent blocked operation, and heat-obtaining problem is also very complicated.
US 20070083071 discloses the processing method that a kind of hydrocarbon catalytic pyrolysis produces ethene, propylene, hydrocarbon feed is converted into the product comprising low-carbon alkene in catalytic cracker, then product stream is separated into C2 ~ C3 alkane, C2 ~ C3 alkene, the three kinds of logistics of C4+ hydrocarbon by series of process, C2 ~ C3 alkane is returned tube cracking furnace and carries out thermo-cracking, C4+ hydrocarbon returns catalytic cracker and carries out catalytic pyrolysis, finally obtains the ethene of higher yields, propylene product.The method adopts riser reactor, and reactant residence time is shorter, and low-carbon alkene product once through yield is lower.
Due to naphtha catalytic cracking and preparing olefin by conversion of methanol react object product---low-carbon alkene is identical, and main ingredient kind separately in product is roughly the same, the catalyst system adopted is also roughly the same, and from reaction mechanism angle, all there is the process being cracked into small molecules hydro carbons by macromole hydrocarbon or intermediate, therefore these two kinds of Technologies are had ready conditions and are coupled.The present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that the yield of light olefins that exists in prior art is not high, provides a kind of method preparing low-carbon alkene with methyl alcohol and petroleum naphtha newly.The method is used for, in the production of low-carbon alkene, having the advantage that yield of light olefins is higher.
For solving the problem, the technical solution used in the present invention is as follows: the method for low-carbon alkene prepared by a kind of methyl alcohol and petroleum naphtha, mainly comprise the following steps: the raw material that (1) comprises petroleum naphtha enters riser tube I, contact with regenerated catalyst, generate the product stream comprising low-carbon alkene and enter settling vessel together with catalyzer, after gas solid separation, product stream enters centrifugal station, separation obtains low-carbon alkene product, isolated more than C4 hydrocarbon enters riser tube II, contact with regenerated catalyst, generate the product stream comprising low-carbon alkene and enter described settling vessel together with catalyzer, (2) catalyzer in described settling vessel is at least divided into two portions after stripping, a part enters revivifier regeneration, the described regenerated catalyst formed enters riser tube I and II, a part enters riser tube III, with the contact raw comprising methyl alcohol, generate the product stream comprising low-carbon alkene and enter described settling vessel together with catalyzer, wherein, settling vessel and revivifier coaxially arranged, settling vessel is positioned at revivifier top, and the entrance end of riser tube I and II is positioned at revivifier, and exit end is positioned at settling vessel.
In technique scheme, described catalyzer comprises ZSM-5 molecular sieve, SiO
2/ Al
2o
3mol ratio is 10 ~ 100; Described regenerated catalyst coke content massfraction is 0.01 ~ 0.5%; Also comprise water vapour in described riser tube I charging, the weight ratio of water vapour and petroleum naphtha is 0.05 ~ 1.5: 1; Described petroleum naphtha boiling range is between 20 DEG C ~ 220 DEG C; In described riser tube I, reaction conditions is: temperature of reaction is 580 ~ 690 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In riser tube II, reaction conditions is: temperature of reaction is 560 ~ 660 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In riser tube III, reaction conditions is: temperature of reaction is 425 ~ 500 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; Catalyzer in described settling vessel is at least divided into two portions after stripping, and 40 ~ 70% weight enter revivifier regeneration, and 30 ~ 60% weight enter riser tube III; Described riser tube III outlet is arranged slightly revolves.
ZSM-5 molecular sieve of the present invention can adopt method known in the field, as hydrothermal synthesis method, be prepared, described molecular sieve catalyst optionally load can have the metal of dehydrogenation functionality, the metal of dehydrogenation functionality is selected from least one in I B in the periodic table of elements, II B, VB, VI B, VII B or VIII race, and the method for the metal load of dehydrogenation functionality on ZSM-5 molecular sieve can be adopted method known in the field, as pickling process or coprecipitation method.After the ZSM-5 molecular sieve of load dehydrogenation functionality metal prepares, add binding agent, make mixed slurry, adopt spray drying process to carry out drying and moulding, then the catalyst fines after shaping is placed in stoving oven and carries out roasting, after cooling, obtain catalyst sample.Binding agent can select SiO
2, Al
2o
3deng.
Adopt method of the present invention, arrange three riser tubes, it is low-carbon alkene that riser tube I is mainly used in convert naphtha, and riser tube II is mainly used in transforming more than the C4 hydrocarbon separated, and it is low-carbon alkene that riser tube III is used for converting methanol.Riser tube I and riser tube II main body are positioned at revivifier, temperature of reaction is high, regenerated catalyst activity is high, be conducive to the generation low-carbon alkene of petroleum naphtha and more than C4 hydrocarbon high conversion in riser tube, from riser tube I and riser tube II, catalyzer out has a certain amount of carbon distribution, but catalyst activity is still very high, can be further used for methanol conversion is low-carbon alkene, carbon distribution simultaneously on catalyzer can contribute to the raising of selectivity of light olefin, catalyzer simultaneously in settling vessel is through thermo-negative reaction such as high-carbon hydrocarbon cracking, after stripping, the temperature range that can be reduced to preparing olefin by conversion of methanol falls in temperature, what ensure methyl alcohol highly selective is converted into low-carbon alkene.Therefore, adopt method of the present invention, the object improving yield of light olefins can be reached.
Adopt technical scheme of the present invention: described catalyzer comprises ZSM-5 molecular sieve, SiO
2/ Al
2o
3mol ratio is 10 ~ 100; Described regenerated catalyst coke content massfraction is 0.01 ~ 0.5%; Also comprise water vapour in described riser tube I charging, the weight ratio of water vapour and petroleum naphtha is 0.05 ~ 1.5: 1; Described petroleum naphtha boiling range is between 20 DEG C ~ 220 DEG C; In described riser tube I, reaction conditions is: temperature of reaction is 580 ~ 690 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In riser tube II, reaction conditions is: temperature of reaction is 560 ~ 660 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In riser tube III, reaction conditions is: temperature of reaction is 425 ~ 500 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; Catalyzer in described settling vessel is at least divided into two portions after stripping, and 40 ~ 70% weight enter revivifier regeneration, and 30 ~ 60% weight enter riser tube III; Described riser tube III outlet is arranged slightly revolves, and low-carbon alkene carbon base absorption rate can reach 62.19% weight, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is regenerating medium source line; 2 is plug valve to be generated; 3 is methanol feed line; 4 is riser tube III lower lift section; 5 is degas zone, riser tube I bottom; 6 is naphtha feed pipeline; 7 is riser tube I; 8 is riser tube III; 9 is catalyzer enters riser tube III pipeline from settling vessel; 10 is revivifier; 11 is regeneration standpipe; 12 is riser tube II; 13 is degassed medium inlet pipeline; 14 is stripping fluid source line; 15 is revivifier gas-solid cyclone separator; 16 is exhanst gas outlet; 17 is settling vessel; 18 is stripping zone; 19 is gas-solid cyclone separator; 20 slightly revolve for riser tube III exports; 21 is products export pipeline; 22 is more than C4 hydrocarbon feeding line; 23 is degassed medium inlet pipeline; 24 is overflow weir; 25 is degas zone, riser tube II bottom.
The raw material comprising petroleum naphtha enters riser tube I 7, contact with regenerated catalyst, generate the product stream comprising low-carbon alkene and enter settling vessel 17 together with catalyzer, after gas solid separation, product stream enters centrifugal station, and be separated and obtain low-carbon alkene product, isolated more than C4 hydrocarbon enters riser tube II 12, contact with regenerated catalyst, generate the product stream comprising low-carbon alkene and enter described settling vessel 17 together with catalyzer; Catalyzer in described settling vessel 17 is at least divided into two portions after stripping, a part enters revivifier 10 through regeneration standpipe 11 and regenerates, the described regenerated catalyst formed enters riser tube I7 and II 12, a part enters riser tube III8 through pipeline 9, with the contact raw comprising methyl alcohol, generate the product stream comprising low-carbon alkene and enter described settling vessel 17 together with catalyzer.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
In reaction unit as shown in Figure 1, feed naphtha enters riser tube I, contact with regenerated catalyst, generate the product stream comprising low-carbon alkene and enter settling vessel together with catalyzer, after gas solid separation, product stream enters centrifugal station, separation obtains low-carbon alkene product, isolated more than C4 hydrocarbon enters riser tube II, contact with regenerated catalyst, generate the product stream comprising low-carbon alkene and enter described settling vessel together with catalyzer, catalyzer in described settling vessel is divided into two portions after stripping, 40% weight enters revivifier regeneration, the described regenerated catalyst formed enters riser tube I and II, 60% weight enters riser tube III, contact with methanol feedstock, generate the product stream comprising low-carbon alkene and enter described settling vessel together with catalyzer.Settling vessel and revivifier coaxially arranged, settling vessel is positioned at revivifier top, and the entrance end of riser tube I and II is positioned at revivifier, and exit end is positioned at settling vessel.Described catalyzer is ZSM-5, ZSM-5 molecular sieve SiO
2/ Al
2o
3mol ratio is 10, and regenerated catalyst coke content massfraction is 0.01%, also comprises water vapour in riser tube I charging, and the weight ratio of water vapour and petroleum naphtha is 0.05: 1, and petroleum naphtha composition is in table 1.In riser tube I, reaction conditions is: temperature of reaction is 580 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds; In riser tube II, reaction conditions is: temperature of reaction is 560 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds; In riser tube III, reaction conditions is: temperature of reaction is 425 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds.Described riser tube III outlet is arranged slightly revolves.Methyl alcohol and naphtha feed weight ratio are 1: 1.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 53.34% weight.
Table 1 petroleum naphtha typical case composition
| Initial boiling point, DEG C | 40 |
| Final boiling point, DEG C | 162 |
| Positive structure and isoparaffin, % by weight | 65.18 |
| Alkene, % by weight | 0.17 |
| Naphthenic hydrocarbon, % by weight | 28.44 |
| Aromatic hydrocarbons, % by weight | 6.21 |
[embodiment 2]
According to the condition described in embodiment 1 and step, the catalyzer in described settling vessel is divided into two portions after stripping, and 70% weight enters revivifier regeneration, and 30% weight enters riser tube III.ZSM-5 molecular sieve SiO
2/ Al
2o
3mol ratio is 100, and regenerated catalyst coke content massfraction is 0.5%, also comprises water vapour in riser tube I charging, and the weight ratio of water vapour and petroleum naphtha is 1.5: 1.In riser tube I, reaction conditions is: temperature of reaction is 690 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 10 meter per seconds; In riser tube II, reaction conditions is: temperature of reaction is 660 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 10 meter per seconds; In riser tube III, reaction conditions is: temperature of reaction is 500 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 10 meter per seconds.Methyl alcohol and naphtha feed weight ratio are 0.5: 1.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 47.14% weight.
[embodiment 3]
According to the condition described in embodiment 1 and step, the catalyzer in described settling vessel is divided into two portions after stripping, and 50% weight enters revivifier regeneration, and 50% weight enters riser tube III.ZSM-5 molecular sieve SiO
2/ Al
2o
3mol ratio is 50, and regenerated catalyst coke content massfraction is 0.1%, also comprises water vapour in riser tube I charging, and the weight ratio of water vapour and petroleum naphtha is 0.5: 1.In riser tube I, reaction conditions is: temperature of reaction is 650 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 6 meter per seconds; In riser tube II, reaction conditions is: temperature of reaction is 640 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 5 meter per seconds; In riser tube III, reaction conditions is: temperature of reaction is 460 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 6 meter per seconds.Methyl alcohol and naphtha feed weight ratio are 2: 1.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 62.19% weight.
[embodiment 4]
According to the condition described in embodiment 1 and step, the catalyzer in described settling vessel is divided into two portions after stripping, and 50% weight enters revivifier regeneration, and 50% weight enters riser tube III.ZSM-5 molecular sieve SiO
2/ Al
2o
3mol ratio is 70, and regenerated catalyst coke content massfraction is 0.12%, also comprises water vapour in riser tube I charging, and the weight ratio of water vapour and petroleum naphtha is 0.5: 1.In riser tube I, reaction conditions is: temperature of reaction is 650 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and gas phase linear speed is 6 meter per seconds; In riser tube II, reaction conditions is: temperature of reaction is 640 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and gas phase linear speed is 5 meter per seconds; In riser tube III, reaction conditions is: temperature of reaction is 460 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and gas phase linear speed is 5 meter per seconds.Methyl alcohol and naphtha feed weight ratio are 2: 1.Keep the stability of catalyst flow control, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 56.24% weight.
[comparative example 1]
According to the condition described in embodiment 3 and step, just do not arrange riser tube II, low-carbon alkene carbon base absorption rate is 51.49% weight.
[comparative example 2]
According to the condition described in embodiment 3 and step, just do not arrange riser tube II and riser tube III, low-carbon alkene carbon base absorption rate is 37.14% weight.
Obviously, adopt method of the present invention, the object improving yield of light olefins can be reached, there is larger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (2)
1. prepare a method for low-carbon alkene with methyl alcohol and petroleum naphtha, reaction unit comprises: regenerating medium source line (1); Plug valve to be generated (2); Methanol feed line (3); Riser tube III lower lift section (4); Degas zone, riser tube I bottom (5); Naphtha feed pipeline (6); Riser tube I (7); Riser tube III (8); Catalyzer enters the pipeline (9) of riser tube III from settling vessel; Revivifier (10); Regeneration standpipe (11); Riser tube II (12); Degassed medium inlet pipeline (13); Stripping fluid source line (14); Revivifier gas-solid cyclone separator (15); Exhanst gas outlet (16); Settling vessel (17); Stripping zone (18); Gas-solid cyclone separator (19); Riser tube III exports and slightly revolves (20); Products export pipeline (21); More than C4 hydrocarbon feeding line (22); Degassed medium inlet pipeline (23); Overflow weir (24); Degas zone, riser tube II bottom (25);
Mainly comprise the following steps:
(1) raw material comprising petroleum naphtha enters riser tube I, contact with regenerated catalyst, generate the product stream comprising low-carbon alkene and enter settling vessel together with catalyzer, after gas solid separation, product stream enters centrifugal station, and be separated and obtain low-carbon alkene product, isolated more than C4 hydrocarbon enters riser tube II, contact with regenerated catalyst, generate the product stream comprising low-carbon alkene and enter described settling vessel together with catalyzer;
(2) catalyzer in described settling vessel is at least divided into two portions after stripping, a part enters revivifier regeneration, the described regenerated catalyst formed enters riser tube I and II, a part enters riser tube III, with the contact raw comprising methyl alcohol, generate the product stream comprising low-carbon alkene and enter described settling vessel together with catalyzer;
Wherein, settling vessel and revivifier coaxially arranged, settling vessel is positioned at revivifier top, and the entrance end of riser tube I and II is positioned at revivifier, and exit end is positioned at settling vessel;
Regenerated catalyst coke content massfraction is 0.01 ~ 0.5%;
Also comprise water vapour in riser tube I charging, the weight ratio of water vapour and petroleum naphtha is 0.05 ~ 1.5:1;
Petroleum naphtha boiling range is between 20 DEG C ~ 220 DEG C;
In riser tube I, reaction conditions is: temperature of reaction is 580 ~ 690 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In riser tube II, reaction conditions is: temperature of reaction is 560 ~ 660 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds; In riser tube III, reaction conditions is: temperature of reaction is 425 ~ 500 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and gas phase linear speed is 4 ~ 10 meter per seconds;
Catalyzer in settling vessel is at least divided into two portions after stripping, and 40 ~ 70% weight enter revivifier regeneration, and 30 ~ 60% weight enter riser tube III;
Riser tube III outlet is arranged slightly revolves.
2. prepare the method for low-carbon alkene according to claim 1 with methyl alcohol and petroleum naphtha, it is characterized in that described catalyzer comprises ZSM-5 molecular sieve, SiO
2/ Al
2o
3mol ratio is 10 ~ 100.
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| CN101417911A (en) * | 2007-10-26 | 2009-04-29 | 中国石油化工股份有限公司 | Method for preparing light olefins from methanol using hydrocarbons as part material |
| CN101367699A (en) * | 2007-10-31 | 2009-02-18 | 中国科学院大连化学物理研究所 | Preparation of propylene |
| CN101362668A (en) * | 2007-11-15 | 2009-02-11 | 中国科学院大连化学物理研究所 | Preparation of propane |
| CN101955406A (en) * | 2009-07-20 | 2011-01-26 | 中国科学院大连化学物理研究所 | Method for producing propylene and ethylene byproduct |
| CN101992046A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Parallel combined riser circular reaction-regeneration device |
| CN102050691A (en) * | 2009-11-10 | 2011-05-11 | 中国石油大学(北京) | Method for preparing low carbon olefin by use of coupling between methanol and C4 hydrocarbon |
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