CN103420750A - Method for preparing olefin from low-carbon alkane - Google Patents
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Abstract
The present invention relates to a method for preparing olefin from low-carbon alkane, wherein problems of low low-carbon olefin yield and high investment cost in the prior art are mainly solved with the present invention. The technical scheme comprises that: low-carbon alkane having a carbon atom number of 2-5 is subjected to a dehydrogenation reaction at a reaction temperature of 500-650 DEG C under reaction pressure of 0-0.5 MPa through a reactor filled with a platinum base dehydrogenation catalyst or a chromium base dehydrogenation catalyst to obtain a mixing stream containing hydrogen, low-carbon olefin and unconverted low-carbon alkane, the mixing stream is subjected to gas-liquid separation at a temperature of -60 to -165 DEG C under pressure 2.0-4.0 MPa, the gas phase contains hydrogen and methane, the partial gas phase is recycled to the reactor, the liquid phase is subjected to rectification separation to obtain the product low-carbon olefin, and the unconverted low-carbon carbon alkane is recycled to the reactor. With the technical scheme, the problems are well solved, and the method can be used for industrial production of preparation of low-carbon olefin from low-carbon alkane.
Description
Technical field
The present invention relates to a kind of preparation method of low-carbon alkene.
Background technology
Low-carbon alkene is (as ethene, propylene, divinyl, iso-butylene etc.) be one of important basic organic chemical industry raw material, ethene and propylene are two kinds of important foundation organic raw material of consumption maximum in petrochemical industry, ethene is synthon, synthetic rubber, synthetic plastics (polyethylene and polyvinyl chloride), the basic chemical raw materials of synthesizing alcohol (alcohol), also for the manufacture of vinylchlorid, vinylbenzene, oxyethane, acetic acid, acetaldehyde, ethanol and explosive etc., propylene is mainly for the production of PP, isopropyl benzene, vinyl cyanide, all multi-products such as vinylformic acid, divinyl can be used for manufacturing synthetic rubber (styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, paracril, chloroprene rubber), iso-butylene is mainly used in the synthetic of methyl tertiary butyl ether (MTBE), also can be for the production of isoprene-isobutylene rubber, polyisoprene rubber, the elastomericss such as polyisoamylene rubber, can also be for the production of various fine chemicals.
At present the production method of low-carbon alkene is generally petroleum hydrocarbon steam cracking method, according to statistics, at present in the world about 90% ethene and 50% above propylene by the method production.Industrial naphtha cracking temperature has been brought up to 840～860 ℃, and one way minor diameter boiler tube cracking temperature is brought up to more than 900 ℃ the sixth of the twelve Earthly Branches, and the naphtha cracking once through ethylene yield is 28%～35%.Because the steam cracking law technology becomes better and approaching perfection day by day, improvable leeway is also little, add high, the used high temperature alloy material expensive of this method temperature of reaction, high, easy coking and ingredient requirement harsh (lightweight material oil) consume energy, so in recent years, the catalysis worker turns to more attention the research of producing low-carbon alkene by other new technologies, comprises catalytic pyrolysis preparing ethylene technology, methane oxidation coupling technology, oxidative dehydrogenation of ethane technology, oil refinery dry gas selective oxidation technology, natural gas via methyl alcohol or dme producing light olefins technology etc.The purpose of these technology is the material optimization for ethylene production resource distribution, and from the Sweet natural gas to heavy oil, (residual oil) various hydro carbons all are fully used, and energy-saving and cost-reducing, reduces production costs.
Low-carbon alkanes (as ethane, propane, Trimethylmethane, pentane etc.) dehydrogenation is a competitive production low-carbon alkene operational path, is one of important channel increased in the alkene source, is also the key of low-carbon alkanes comprehensive utilization of resources.Low-carbon alkanes mainly contains following three kinds of sources: 1, oil production: in the oil production process, oil and associated gas spray simultaneously, utilize and are installed in the gas and oil separating plant above oil well, and oil is separated with associated gas.2, Natural gas extraction: Sweet natural gas is two kinds of dry gas and moistures.Methane content in moisture is below 90%, and the Determination of Alkane Contents such as ethane, propane, butane, more than 10%, if the components such as the propane in moisture, butane are separated, just obtain required liquefied petroleum gas (LPG).3, the refining of petroleum course of processing: the plant catalytic reacted gas is removed C2 and C 4 fraction through distillation, obtains propylene, propane fraction, then obtains respectively propane, propylene through rectifying.
The report of at present existing manufacturing olefin by low-carbon alkane dehydrogenation, as the preparing propylene by dehydrogenating propane Catofin technique of U.S. Lummus, the preparing isobutene through dehydrogenation of iso-butane Oleflex technique of UOP, gondola preparing propylene by dehydrogenating propane FBD-4 technique etc., its key problem in technology is good catalyzer.Concrete document is shown in Chinese patent ZL9110898.X, ZL96117222.3, ZL96121452.X, ZL92111388.9, U.S. Pat 4996387.China does not also have dehydrogenating low-carbon alkane to produce the report of low-carbon alkene suitability for industrialized production at present.
Summary of the invention
Technical problem to be solved by this invention is that the yield of light olefins in the past existed in conventional art is low, the problem that cost of investment is high.A kind of method of new manufacturing olefin by low-carbon alkane dehydrogenation is provided, and the method has the advantages that yield of light olefins is high, cost of investment is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of low-carbon alkanes producing light olefins, by the low-carbon alkanes of carbon atoms 2～5, in temperature of reaction, it is 500 ~ 650 ℃, reaction pressure is under 0 ~ 0.5MPa condition, by platinum group or chromium are housed, be that the reactor of dehydrogenation catalyst carries out dehydrogenation reaction, obtain comprising hydrogen, low-carbon alkene, the mixture flow of unconverted low-carbon alkanes, by this mixture flow, at pressure, be 2.0 ~ 4.0MPa, under the condition that temperature is-60 ~-165 ℃, carry out gas-liquid separation, gas phase after separation comprises hydrogen, liquid phase comprises the hydro carbons such as low-carbon alkene and low-carbon alkanes, hydrogen partial loops back reactor, liquid phase goes out the product low-carbon alkene by rectifying separation, unconverted low-carbon alkanes loops back reactor.
In technique scheme, dehydrogenation catalyst is platinum group catalyst, in catalyst weight per-cent, composed of the following components: as a) to be selected from least one in ruthenium in platinum metals, rhodium, palladium, osmium, iridium or platinum, with simple substance, to count 0.01 ~ 1.2% of catalyst weight; B) be selected from least one in IV A compound in the periodic table of elements, with simple substance, count 0.01 ~ 5.0% of catalyst weight; C) be selected from least one in I A in the periodic table of elements or II A compound, with simple substance, count 0.01 ~ 3.0% of catalyst weight; D) 90.8 ~ 99.97% carrier; That dehydrogenation reactor adopts is insulation fix bed, a kind of in isothermal fixed bed, moving-bed or fluidized-bed, and preferred version is insulation fix bed reactor, is at least two-stage series connection; The dehydrogenation reactor inter-stage adopts process furnace to carry out the inter-stage heating to reaction gas, and after heating, the gas temperature preferable range is 520 ~ 620 ℃; Dehydrogenation reactor at least comprises 2 classes, and at least one class is for reaction, another kind of for catalyst regeneration; 520 ~ 620 ℃ of temperature of reaction preferable range, the reaction pressure preferable range is 0.1 ~ 0.2MPaA, low-carbon alkanes weight space velocity preferable range is 2 ~ 6 hours
-1Low-carbon alkanes is introduced dehydrogenation reactor together with heating medium, and the mol ratio preferable range of low-carbon alkanes and heating medium is 0.1 ~ 5; Heating medium is at least one in hydrogen or water vapour; Adopt air, hydrogen, nitrogen as resurgent gases, 400 ~ 550 ℃ of regeneration temperature preferable range, regeneration pressure preferable range 0 ~ 0.15MPa, regeneration period preferable range 12 ~ 120 hours, regeneration required time preferable range 2 ~ 24 hours; After low-carbon alkanes reaction, gas is compressed ℃ carries out gas-liquid separation to preferable range 3.0 ~ 3.5MPaG, deep cooling to preferable range-100 ~-160, and gas phase partly loops back reactive system, and liquid phase enters the rectifying separation part; The compression process preferred version is 1 grade ~ 3 grades compressions, and compressor can be radial compressor, reciprocation compressor or spiral-lobe compressor, and deep cooling medium is ethene, ethane or methane; Liquid phase after the compression low temperature separation process is separated by knockout tower, and tower top is isolated the product low-carbon alkene, and tower reactor is that unconverted low-carbon alkanes loops back reactor; Knockout tower is single or multiple, and knockout tower is tray column or packing tower.
The present invention is heated to 500 ~ 650 ℃ of temperature of reaction by the low-carbon alkanes by carbon atoms 2～5, under pressure 0 ~ 0.5MPaA condition, passing into platinum group or chromium are housed is that the reactor of dehydrogenation catalyst carries out dehydrogenation reaction, obtain comprising hydrogen, the mixture flow of alkene and unconverted low-carbon alkanes, dehydrogenation reaction low-carbon alkanes transformation efficiency is 40% ~ 70%, olefine selective reaches 85% ~ 95%, unreacted low-carbon alkanes Returning reacting system after separating in resultant of reaction, overall yield of reaction can reach more than 80%, apparently higher than petroleum hydrocarbon steam cracking method, as the naphtha cracking yield of ethene is only 28%～35%.Reduced production cost; Simultaneously, dehydrogenation reaction temperature of the present invention is 500 ~ 650 ℃, lower than petroleum hydrocarbon steam cracking method, as the naphtha cracking temperature has been brought up to 840～860 ℃, one way minor diameter boiler tube cracking temperature is brought up to 900 ℃ the sixth of the twelve Earthly Branches even more than 1000 ℃, has greatly saved facility investment and energy consumption.
In the present invention, the compressed machine of products of dehydrogenation reactions is compressed to 2.0 ~ 4.0MPaG, and to adopt methane be the cryogen deep cooling carries out gas-liquid separation to-100 ~-165 ℃, under this pressure and temperature condition, and the C in reaction product
2And C
2Above hydro carbons all is condensed, gaseous stream except comprising hydrogen and methane, C
2And the content<1ppm of above hydrocarbon, hydrogen volume content can reach more than 98%, part loops back reactive moieties, fully recycled the hydrogen that reaction generates, part is delivered to out-of-bounds, by-product the hydrogen be worth for usury, in the hydrogen of reuse simultaneously, the content of alkene has seldom effectively reduced the carbon distribution of catalyst surface, improve the utilization ratio of raw material, extended regeneration period and the work-ing life of dehydrogenation catalyst.In the present invention, the liquid phase that compressed low temperature separation process obtains enters the rectifying separation part, and the knockout tower tower top is isolated the product low-carbon alkene, and tower reactor is that unconverted low-carbon alkanes loops back reactor; Knockout tower is single or multiple tray columns or packing tower, and tower top is isolated the product low-carbon alkene, and tower reactor is that unconverted low-carbon alkanes loops back reactor.This scheme has improved the low-carbon alkanes utilization ratio, has reduced facility investment and energy consumption simultaneously.Adopt technical solution of the present invention, increased a kind of to low-carbon alkanes the new method of utilizing, enlarged the source of low-carbon alkene, the low-carbon alkene total recovery of dehydrogenation reaction is high, temperature is low, investment and energy consumption are low, compress after deep cooling the hydrogen purity in gas phase high simultaneously, but the by-product usury is with being worth hydrogen, improved raw material availability simultaneously, regeneration period and the work-ing life of catalyzer have been extended, this device propane one way total conversion rate can reach 62%, Propylene Selectivity can reach 90.5%, the propylene total recovery reaches 89%, propylene product purity reaches 99.7%, plant investment cost savings 50% left and right, obtained technique effect significantly.
The accompanying drawing explanation
Fig. 1 is that dehydrogenating low-carbon alkane prepares the low-carbon alkene process flow diagram.
In Fig. 1,1 is dehydrogenation reactor system, and 2 is the compression cryogenic system, and 3 is the rectifying separation system, 101 is the low-carbon alkanes raw material, and 102 is products of dehydrogenation reactions, and 103 is compression deep cooling liquid phase stream, and 104 is circulating hydrogen, 105 is the circulation low-carbon alkanes, and 106 is by-product hydrogen, and 107 is the product low-carbon alkene.
In Fig. 1, raw material low-carbon alkanes 101 mixes by being heated to feeding temperature with circulating hydrogen 104, enter dehydrogenation reactor system 1 and carry out dehydrogenation reaction, the laggard promoting the circulation of qi liquid of the compressed deep cooling of dehydrogenation reactor discharging 102 separates, and the gas phase part is as circulating hydrogen 104 Returning reacting systems 1, and part is delivered to out-of-bounds as by-product hydrogen 106, liquid phase enters rectifying separation system 3, after separating, tower top obtains product low-carbon alkene 107, and the tower reactor low-carbon alkanes 105 that obtains circulating, loop back dehydrogenation reactor system 1.
Below by embodiment and comparative example, invention is further elaborated.
Embodiment
[embodiment 1]
Certain 200,000 ton/years of preparing propylene by dehydrogenating propane device (year operation hours 8000 hours), adopt the Technology of Fig. 1, raw material propane, recycled propane and circulating hydrogen pass into the insulation fix bed dehydrogenation reactor that platinum-Xi dehydrogenation catalyst is housed after mixing, this catalyst component is (weight): platinum 0.4%, tin 1.1%, Na/Ca 0.44%, Al
2O
398.06%, propane and hydrogen mol ratio are 3, and dehydrogenation reactor adopts 2 groups of 2 series connection, the first 615 ℃ of reactor inlet temperatures, and the second 620 ℃ of reactor inlet temperatures, reaction pressure is 0.1MPa, the propane weight space velocity is 3.5 hours
-1, process furnace is set between reactor the first reactor outlet gas is heated.One group reaction device is for dehydrogenation reaction, and one group is used for catalyst regeneration, and catalyst regeneration adopts air, hydrogen, nitrogen as regenerator, 540 ℃ of regeneration temperatures, regeneration pressure 0.1MPa.After reaction, gas is compressed to 3.5MPaG, adopts methane that to be the cryogen deep cooling carry out gas-liquid separation to-160 ℃ through three grades of radial compressors, gas phase partly loops back reactive system, liquid phase enters propane propylene separation tower and separates, this tower is the float valve tray column, tower top working pressure 3.0MPa, 40 ℃ of tower top temperatures, 52 ℃ of tower reactor temperature, tower top is isolated the product propylene, and tower reactor is that unconverted propane cycles is returned reactor.
This device propane one way total conversion rate 50%, Propylene Selectivity 92%, propylene total recovery 90%, 24 hours catalyst regeneration cycles, regeneration required time 8 hours, propylene product purity 99.7%, approximately 800,000,000 yuans of plant investments.
[embodiment 2]
Certain 200,000 ton/years of preparing propylene by dehydrogenating propane device (year operation hours 8000 hours), adopt the Technology of Fig. 1, raw material propane and hydrogen mol ratio are 2, dehydrogenation reactor adopts 2 groups of 3 series connection, the first 615 ℃ of reactor inlet temperatures, the second 620 ℃ of reactor inlet temperatures, the 3rd 625 ℃ of reactor inlet temperatures, after reaction, gas is compressed to 4.0MPaG through three grades of radial compressors, and other conditions are with embodiment 1.
This device propane one way total conversion rate 60%, Propylene Selectivity 90%, propylene total recovery 88%, 24 hours catalyst regeneration cycles, regeneration required time 8 hours, propylene product purity 99.7%, approximately 8.5 hundred million yuans of plant investments.
[embodiment 3]
Certain 200,000 ton/years of preparing propylene by dehydrogenating propane device (year operation hours 8000 hours), adopt the Technology of Fig. 1, dehydrogenation catalyst is chromium-based catalysts, and heating medium adopts water vapour, the mol ratio of raw material propane and water vapour is 0.5, and other conditions are with embodiment 2.
This device propane one way total conversion rate 62%, Propylene Selectivity 90.5%, propylene total recovery 89%, 48 hours catalyst regeneration cycles, regeneration required time 8 hours, propylene product purity 99.7%, approximately 800,000,000 yuans of plant investments.
[embodiment 4]
Certain 100,000 ton/years of preparing isobutene through dehydrogenation of iso-butane device (year operation hours 8000 hours), adopt the Technology of Fig. 1, raw material Trimethylmethane, recycle isobutane and circulating hydrogen pass into the insulation fix bed dehydrogenation reactor that platinum-Xi dehydrogenation catalyst is housed after mixing, Trimethylmethane and hydrogen mol ratio are 2.5, dehydrogenation reactor adopts 2 groups of 3 series connection, the first 615 ℃ of reactor inlet temperatures, the second 620 ℃ of reactor inlet temperatures, the 3rd 625 ℃ of reactor inlet temperatures, reaction pressure is 0.1MPa, and the Trimethylmethane weight space velocity is 4 hours
-1, process furnace is set between reactor the first reactor outlet gas is heated.One group reaction device is for dehydrogenation reaction, and one group is used for catalyst regeneration, and catalyst regeneration adopts air, hydrogen, nitrogen as regenerator, 520 ℃ of regeneration temperatures, regeneration pressure 0.1MPa.After reaction, gas is compressed to 3.5MPaG, adopts methane that to be the cryogen deep cooling carry out gas-liquid separation to-160 ℃ through three grades of radial compressors, gas phase partly loops back reactive system, liquid phase enters methyl tertiary butyl ether (MTBE) ether-based device, iso-butylene reacts with methyl alcohol as raw material of etherification produces MTBE, and unreacted Trimethylmethane loops back reactor.
This device Trimethylmethane one way total conversion rate 40%, selective isobutene 90%, iso-butylene total recovery 88%, 24 hours catalyst regeneration cycles, regeneration required time 12 hours, approximately 500,000,000 yuans of plant investments.
[embodiment 5]
Certain 100,000 ton/years of preparing isobutene through dehydrogenation of iso-butane device (year operation hours 8000 hours), adopt the Technology of Fig. 1, raw material Trimethylmethane, recycle isobutane and circulating hydrogen pass into the fluidized-bed dehydrogenation reactor that chromium is dehydrogenation catalyst are housed after mixing, this fluidized-bed reactor inside is provided with heating unit, temperature of reaction is 580 ℃, reaction pressure is 0.1MPa, and other conditions are with embodiment 4.
This device Trimethylmethane one way total conversion rate 45%, selective isobutene 88%, iso-butylene total recovery 85%, approximately 4.5 hundred million yuans of plant investments.
[comparative example 1]
Certain 200,000 ton/years of alkene (ethene, propylene) production equipment, adopt petroleum hydrocarbon steam cracking technique, 850 ℃ of naphtha cracking temperature, and 920 ℃ of boiler tube cracking temperatures, adopt the high temperature alloy material.Naphtha cracking one way low-carbon alkene (ethene, propylene) yield is 30%.Approximately 1,200,000,000 yuans of plant investments.
Claims (10)
1. the method for a low-carbon alkanes producing light olefins, by the low-carbon alkanes of carbon atoms 2～5, in temperature of reaction, it is 500 ~ 650 ℃, reaction pressure is under 0 ~ 0.5MPa condition, by platinum group or chromium are housed, be that the reactor of dehydrogenation catalyst carries out dehydrogenation reaction, obtain comprising hydrogen, low-carbon alkene, the mixture flow of unconverted low-carbon alkanes, by this mixture flow, at pressure, be 2.0 ~ 4.0MPa, under the condition that temperature is-60 ~-165 ℃, carry out gas-liquid separation, gas phase after separation comprises hydrogen, liquid phase comprises the hydro carbons such as low-carbon alkene and low-carbon alkanes, hydrogen partial loops back reactor, liquid phase goes out the product low-carbon alkene by rectifying separation, unconverted low-carbon alkanes loops back reactor.
2. low-carbon alkanes producing light olefins method according to claim 1 is characterized in that dehydrogenation catalyst is platinum group catalyst, in catalyst weight per-cent, comprises following component:
A) be selected from least one in ruthenium in platinum metals, rhodium, palladium, osmium, iridium or platinum, with simple substance, count 0.01 ~ 1.2% of catalyst weight;
B) be selected from least one in IV A compound in the periodic table of elements, with simple substance, count 0.01 ~ 5.0% of catalyst weight;
C) be selected from least one in I A in the periodic table of elements or II A compound, with simple substance, count 0.01 ~ 3.0% of catalyst weight;
D) 90.8 ~ 99.97% carrier.
3. low-carbon alkanes producing light olefins method according to claim 1, is characterized in that dehydrogenation reactor adopts a kind of in insulation fix bed, isothermal fixed bed, moving-bed or fluidized-bed.
4. low-carbon alkanes producing light olefins method according to claim 3, is characterized in that dehydrogenation reactor is insulation fix bed reactor, is at least two-stage series connection.
5. the method for low-carbon alkanes producing light olefins according to claim 3, is characterized in that the dehydrogenation reactor inter-stage adopts process furnace to carry out the inter-stage heating to reaction gas, and after heating, gas temperature is 520 ~ 620 ℃.
6. low-carbon alkanes producing light olefins method according to claim 3, is characterized in that dehydrogenation reactor at least comprises 2 classes, and at least one class is for reaction, another kind of for catalyst regeneration.
7. low-carbon alkanes producing light olefins method according to claim 1, is characterized in that 520 ~ 620 ℃ of temperature of reaction, and reaction pressure is 0.1 ~ 0.2MPaA, and the low-carbon alkanes weight space velocity is 2 ~ 6 hours
-1Low-carbon alkanes is introduced dehydrogenation reactor together with heating medium, and the mol ratio of low-carbon alkanes and heating medium is 0.1 ~ 5; Heating medium is at least one in hydrogen or water vapour.
8. the method for low-carbon alkanes producing light olefins according to claim 6, it is characterized in that adopting air, hydrogen, nitrogen as resurgent gases, 400 ~ 550 ℃ of regeneration temperatures, regeneration pressure 0-0.15MPa, 12 ~ 120 hours regeneration periods, regeneration required time 2 ~ 24 hours.
9. the method for low-carbon alkanes producing light olefins according to claim 1, it is characterized in that after low-carbon alkanes reaction that gas is that 3.0 ~ 3.5MPaG, temperature are-100 ~-160 ℃ and carry out gas-liquid separation at pressure, gas phase partly loops back reactive system, and liquid phase enters the rectifying separation part; Compression process is 1 grade ~ 3 grades compressions, and compressor can be radial compressor, reciprocation compressor or spiral-lobe compressor, and deep cooling medium is ethene, ethane or methane.
10. the method for low-carbon alkanes producing light olefins according to claim 1, the liquid phase that it is characterized in that compressing after low temperature separation process is separated by knockout tower, and tower top is isolated the product low-carbon alkene, and tower reactor is that unconverted low-carbon alkanes loops back reactor; Knockout tower is single or multiple, and knockout tower is tray column or packing tower.
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| CN105585400A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing light olefin from light alkane |
| CN106140226A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of catalyst of alkene processed and preparation method and application |
| CN106687429A (en) * | 2014-09-12 | 2017-05-17 | 沙特基础工业全球技术有限公司 | Embedded alkane dehydrogenation systems and processes |
| CN106140274B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of catalyst of the highly selective preparing isobutene of bromomethane and preparation method thereof |
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| CN106687429A (en) * | 2014-09-12 | 2017-05-17 | 沙特基础工业全球技术有限公司 | Embedded alkane dehydrogenation systems and processes |
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| CN108349837A (en) * | 2015-11-06 | 2018-07-31 | 环球油品公司 | Reactor effluent is washed to remove aromatic compounds |
| CN111433174A (en) * | 2017-11-02 | 2020-07-17 | 环球油品有限责任公司 | Dehydrogenation process at reduced hydrogen to hydrocarbon ratio |
| CN111433174B (en) * | 2017-11-02 | 2023-03-24 | 环球油品有限责任公司 | Dehydrogenation process with reduced hydrogen to hydrocarbon ratio |
| CN110452085A (en) * | 2018-05-07 | 2019-11-15 | 淄博众森石化工程技术有限公司 | A kind of moving bed C3/C4 alkane dehydrogenation process |
| CN110452085B (en) * | 2018-05-07 | 2023-08-18 | 淄博链科工程材料有限公司 | Moving bed C3/C4 alkane dehydrogenation process |
| CN112745188A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for improving conversion rate of dehydrogenation reaction of low-carbon alkane |
| CN112745188B (en) * | 2019-10-30 | 2022-11-15 | 中国石油化工股份有限公司 | Method for improving conversion rate of dehydrogenation reaction of low-carbon alkane |
| CN112569872A (en) * | 2020-11-24 | 2021-03-30 | 西南化工研究设计院有限公司 | Moving bed system for preparing low-carbon olefin by dehydrogenating low-carbon alkane |
| CN114736095A (en) * | 2022-05-12 | 2022-07-12 | 中海石油气电集团有限责任公司 | Method for preparing hydrogen and olefin by catalytic oxidation of natural gas |
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