CN101279872B - Method for preparing low-carbon olefin hydrocarbon with oxocompound - Google Patents
Method for preparing low-carbon olefin hydrocarbon with oxocompound Download PDFInfo
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- CN101279872B CN101279872B CN2007100390835A CN200710039083A CN101279872B CN 101279872 B CN101279872 B CN 101279872B CN 2007100390835 A CN2007100390835 A CN 2007100390835A CN 200710039083 A CN200710039083 A CN 200710039083A CN 101279872 B CN101279872 B CN 101279872B
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
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- Y02P30/40—Ethylene production
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Abstract
The invention relates to a method for producing a low carbon olefin by an oxycompound, which mainly solves the problem that a regenerated catalyst carrying partial N2, O2, CO(X), NO(X) impurities to a reactor brings difficulties and even causes great harm to the product separation in the process of low carbon olefin production by oxycompound. The invention well solves the problem by adopting the technical proposal that the regenerated catalyst firstly passes a degassing tank to remove impurities and then returned to a fluidized bed reactor circularly, and the method can be used for the industrial production of producing the low carbon olefin by oxycompound.
Description
Technical field
The present invention relates to a kind of method of producing low-carbon alkene, relate in particular to a kind of method of using continuous catalyst regeneration fluidized-bed reaction and regeneration system rapidly to produce low-carbon alkene by oxycompound by oxycompound.
Background technology
Petrochemical complex is a mainstay industry important in the national economy, for industry, agricultural, departments such as traffic and national defence provide a large amount of industrial chemicals, is one of related and branch of industry that drive property is stronger in the national economy.Ethene and propylene then are to constitute modern petrochemical complex of paramount importance two big basic materials.
All the time; coal or Sweet natural gas preparing synthetic gas, synthesising gas systeming carbinol and alkene isolation technique have had the mass-producing mature experience; but the process by methanol to olefins is breakpoint and the difficult point of synthetic gas to this industrial chain of alkene, and this solution of key technology can be for providing a new raw material route by non-oil resource production basic organic ethene, propylene.Especially in the last few years, it is high that the demand of ethene and propylene continues, and under the deficient day by day situation of petroleum resources.How to hew out a non-oil resource and produce the Coal Chemical Industry variation route of propylene, for greatly alleviating China's oil situation in short supply, promote the great-leap-forward development of the heavy chemical industry of China and the structural adjustment of raw material route, have important strategic meaning and society, economic benefit.
Document US 6846405B2, a kind of circulating fluid bed reactor of being produced low-carbon alkenes such as ethene, propylene by oxygenatedchemicals is disclosed, oxygenatedchemicals contacts in riser reactor with molecular sieve catalyst and reacts, and oxygenate is a low-carbon alkene.Molecular sieve catalyst and low-carbon alkene are imported the disengaging zone separate, the molecular sieve catalyst after the separation is imported in the standpipe, and enters riser reactor through inclined tube, adopts riser reactor can effectively improve the utilising efficiency of device.US6166282 discloses the fast fluidized bed reactor of a kind of MTO of being applied to, and this reactor comprises emulsion zone and the zone of transition that extends to catalyst separation zone in the lower reaction zone.The part catalyzer is circulated to the emulsion zone of below from the disengaging zone, such layout can reduce the reserve of catalyzer.Above-mentioned two reactor assemblies have all increased substantially the processing power of raw material, but all do not consider to carry part N secretly behind the catalyst regeneration
2, O
2, CO
X, NO
XEnter reactor Deng impurity, to the influence of product composition.
When catalyst regeneration, can produce the NO of trace
X, the influence that the cryogenic system of ethylene unit is produced secure context.Regenerated catalyst is carried N secretly
2And O
2Enter the ethene separation system with product, enter in thick hydrogen and the methane hydrogen tail gas, can the operation of ice chest, methanator and burner be exerted an influence as rare gas element.CO
XExistence Deng sour gas is harmful to the further processing of low temperature separation process and alkene, and sour gas not only can make poisoning of catalyst, also can corrode and blocking pipe.Moisture content and carbonic acid gas can congeal into ice and the solid water compound at low temperatures, and occluding device influences lock out operation.Therefore should reduce N in the reactor outlet product as far as possible
2, O
2, CO
X, NO
XContent Deng impurity.
Summary of the invention
Technical problem to be solved by this invention is to be produced in the process of low-carbon alkene by oxycompound, and catalyzer inactivation ratio in reactor is very fast, in the process of cyclic regeneration, and catalyst entrainment part N
2, O
2, CO
X, NO
XEnter reactor Deng impurity, these impurity bring difficulty can for the separation of product even cause the problem of very big harm, and a kind of new method by oxycompound production low-carbon alkene is provided.This method has in the continuous catalyst regenerating process can effectively control N
2, O
2, CO
X, NO
XEnter reactor Deng impurity, thereby reduced the isolating difficulty of product, help obtaining purer target product ethene, the advantage of propylene.
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 being produced low-carbon alkene by oxycompound, may further comprise the steps: (a) be raw material with the oxycompound, in temperature of reaction is 400～600 ℃, reaction pressure is 0.02～0.5MPaG, and weight space velocity is 0.2～20 hour
-1Under the condition, fluidized-bed reactor and the SAPO-34 molecular sieve catalyst contact reacts effluent that generate the low-carbon alkene that contain ethene, propylene, butylene of raw material by the reaction-regeneration system of continuous catalyst regenerating, through separate ethene, propylene and butylene product; (b) reclaimable catalyst enters revivifier regeneration behind the stripper stripping; (c) through regenerated catalyst recirculation backflow fluidized bed reactor; The rear catalyst of wherein regenerating is earlier through pump around circuit fluidized bed reactor behind the degassing vessel; Degassing vessel has two stripped vapor sections, and to make the linear speed of bottom stripping stage be 0.05～0.2 meter per second, and the linear speed of top stripping stage is 0.25～0.5 meter per second.
In the technique scheme, the catalyzer after the regeneration enters reactor after deviating from small amount of nitrogen, oxygen, COx and the NOx of catalyst entrainment by degassing vessel; Oxycompound is selected from least a in methyl alcohol, ethanol or the dme.
Oxycompound is produced the reaction-regeneration system of the continuous catalyst regenerating in the low-carbon alkene technology, comprise fluidized-bed reactor (1), fluid bed regenerator (2), stripper (3), degassing vessel (4), cyclonic separator (5) and riser tube (6), catalyst recirculation pipe formations such as (7), see accompanying drawing 1.
Produce low-carbon alkene technology at oxycompound, the present invention proposes and will be connected by catalyst transport (8) between fluidized-bed reactor (1), fluid bed regenerator (2), stripper (3) and degassing vessel (4), has guaranteed carrying out continuously of reaction; Simultaneously degassing vessel (4) stripping stage is divided into two portions up and down, the linear speed that makes the bottom stripping stage is 0.05～0.2 meter per second, make regenerated catalyst be in loosening state, the linear speed of top stripping stage is 0.3～0.5 meter per second, make regenerated catalyst be in fluidized state, upper and lower two sections rational Match can improve steam stripping efficiency, has better avoided the part N of catalyst entrainment
2, O
2, CO
X, NO
XAfter impurity entered reactor, the influence to product separates and product purity is brought had obtained better technical effect.
Description of drawings
Fig. 1 is the reaction-regeneration system synoptic diagram of continuous catalyst regenerating of the present invention;
Fig. 2 is the stripping stage synoptic diagram of degassing vessel of the present invention.
In Fig. 1,1 is reactor; 2 is revivifier; 3 is stripper; 4 is degassing vessel; 5 is cyclonic separator; 6 is riser tube; 7 is the catalyst recirculation pipe; 8 is catalyst transport; 9 is feed-pipe; 10 are the product outlet; 11 is the regeneration air pipe; 12 is exhanst gas outlet.
In Fig. 2,13 is the bottom stripping stage; 14 is the top stripping stage; 15 is top stripping gas import; 16 is bottom stripping gas import; 17 is catalyst inlet; 18 is catalyst outlet; 19 are the stripping gas outlet.
The feed pipe (9) of raw material bottom fluid bed through preheating enters fluidized-bed reactor (1), contact with the regenerated catalyst of process degassing tank immediately and react, reacted product rises along dilute phase conveying pipe with catalyst, make by go out outspoken subsystem that catalyst and product separation are laggard to enter fluidized-bed reactor (1) top, do not have to separate lower catalyst and enter cyclone separator (5) with the product of rising. By cyclone separator with product and catalyst separation, separated catalyst enters fluidized-bed reactor (1) top, the partially catalyzed agent enters stripper (3), and regenerated catalyst enters regenerator (2) after deviating from a small amount of product gas through stripper. Reactor product leaves cyclone separator and enters top collection chamber (10), and multiparity property management line enters the chilling separating part. Main air regeneration air pipe (11) by the bottom after the heating of combustion chamber enters regenerator (2), contact and carry out the catalyst charcoal regeneration with the regenerated catalyst through stripper (3), the exhaust gas volumn that following minimizing regenerated catalyst carries, enter reactor (1) behind the regenerated catalyst process degassing tank (4), the flue gas that is gone out by stripping returns regenerator, the flue gas of the generation after burning and the catalyst that carries enter cyclone separator (5) through the dilute phase section, most catalyst are taken down return the close phase section in regenerator bottom. The seldom amount catalyst fines that leaves the flue gas of cyclone separator and carry enters atmosphere behind smoke energy recovering system.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
200,000 tons of/year preparing low carbon olefin hydrocarbon with methanol process using are the reaction-regeneration system of continuous catalyst regenerating and the stripping stage of degassing vessel shown in Figure 2 as shown in Figure 1.3100 millimeters of reactor diameters, 0.06MPaG, 450 ℃ of temperature of reaction, air speed 1.0 hours
-1, bottom stripping stage linear speed is 0.08 meter per second, and top stripping stage linear speed is 0.25 meter per second, adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is pure methyl alcohol, and the reactor outlet impurity concentration sees Table 1.
[embodiment 2]
300,000 tons of/year preparing low carbon olefin hydrocarbon with methanol process using are the reaction-regeneration system of continuous catalyst regenerating and the stripping stage of degassing vessel shown in Figure 2 as shown in Figure 1.3900 millimeters of reactor diameters, 0.06MPaG, 450 ℃ of temperature of reaction, air speed 5.0 hours
-1, bottom stripping stage linear speed is 0.12 meter per second, and top stripping stage linear speed is 0.3 meter per second, adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is pure methyl alcohol, and the reactor outlet impurity concentration sees Table 1.
[embodiment 3]
400,000 tons of/year preparing low carbon olefin hydrocarbon with methanol process using are the reaction-regeneration system of continuous catalyst regenerating and the stripping stage of degassing vessel shown in Figure 2 as shown in Figure 1.4300 millimeters of reactor diameters, 0.06MPaG, 470 ℃ of temperature of reaction, air speed 3.0 hours
-1, bottom stripping stage linear speed is 0.17 meter per second, and top stripping stage linear speed is 0.35 meter per second, adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is pure methyl alcohol, and the reactor outlet impurity concentration sees Table 1.
[embodiment 4]
200,000 tons of/year preparing low carbon olefin hydrocarbon with methanol process using are the reaction-regeneration system of continuous catalyst regenerating and the stripping stage of degassing vessel shown in Figure 2 as shown in Figure 1.3100 millimeters of reactor diameters, 0.06MPaG, 530 ℃ of temperature of reaction, air speed 0.5 hour
-1, bottom stripping stage linear speed is 0.08 meter per second, and top stripping stage linear speed is 0.25 meter per second, adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is pure methyl alcohol, and the reactor outlet impurity concentration sees Table 2.
[embodiment 5]
200,000 tons of/year preparing low carbon olefin hydrocarbon with methanol process using are the reaction-regeneration system of continuous catalyst regenerating and the stripping stage of degassing vessel shown in Figure 2 as shown in Figure 1.3100 millimeters of reactor diameters, 0.2MPaG, 550 ℃ of temperature of reaction, air speed 9 hours
-1, bottom stripping stage linear speed is 0.08 meter per second, and top stripping stage linear speed is 0.25 meter per second, adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is pure methyl alcohol, and the reactor outlet impurity concentration sees Table 2.
[embodiment 6]
200,000 tons of/year preparing low carbon olefin hydrocarbon with methanol process using are the reaction-regeneration system of continuous catalyst regenerating and the stripping stage of degassing vessel shown in Figure 2 as shown in Figure 1.3100 millimeters of reactor diameters, 0.4MPaG, 570 ℃ of temperature of reaction, air speed 15 hours
-1, bottom stripping stage linear speed is 0.08 meter per second, and top stripping stage linear speed is 0.25 meter per second, adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is pure methyl alcohol, and the reactor outlet impurity concentration sees Table 2.
[embodiment 7]
200,000 tons of/year dme are produced low-carbon alkene the process using reaction-regeneration system of continuous catalyst regenerating and the stripping stage of degassing vessel shown in Figure 2 as shown in Figure 1.3100 millimeters of reactor diameters, 0.1MPaG, 450 ℃ of temperature of reaction, air speed 1.5 hours
-1, bottom stripping stage linear speed is 0.08 meter per second, and top stripping stage linear speed is 0.25 meter per second, adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is a pure Dimethyl ether, and the reactor outlet impurity concentration sees Table 2.
[embodiment 8]
200,000 tons of/year methyl alcohol and dme are the raw material production low-carbon alkene process using reaction-regeneration system of continuous catalyst regenerating and the stripping stage of degassing vessel shown in Figure 2 as shown in Figure 1.3100 millimeters of reactor diameters, 0.1MPaG, 470 ℃ of temperature of reaction, air speed 3.6 hours
-1, bottom stripping stage linear speed is 0.08 meter per second, and top stripping stage linear speed is 0.25 meter per second, adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is methyl alcohol and dme, and its weight ratio is 10: 1, the reactor outlet impurity concentration sees Table 2.
[embodiment 9]
200,000 tons of/year methyl alcohol and ethanol are the raw material production low-carbon alkene process using reaction-regeneration system of continuous catalyst regenerating and the stripping stage of degassing vessel shown in Figure 2 as shown in Figure 1.3100 millimeters of reactor diameters, 0.1MPaG, 470 ℃ of temperature of reaction, air speed 4.0 hours
-1, bottom stripping stage linear speed is 0.08 meter per second, and top stripping stage linear speed is 0.25 meter per second, adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is methyl alcohol and ethanol, and its weight ratio is 10: 1, the reactor outlet impurity concentration sees Table 2.
[comparative example 1]
300,000 tons of/year preparing low carbon olefin hydrocarbon with methanol process using are the reaction-regeneration system of continuous catalyst regenerating and degassing vessel shown in Figure 1 as shown in Figure 1.3900 millimeters of reactor diameters, 0.06MPaG, 450 ℃ of temperature of reaction, air speed 1.0 hours
-1, no stripping stage adopts the SAPO-34 molecular sieve catalyst, and reaction raw materials is pure methyl alcohol, and the reactor outlet impurity concentration sees Table 1.
Table 1 reactor outlet impurity concentration
Table 2 reactor outlet impurity concentration
Claims (3)
1. method of producing low-carbon alkene by oxycompound, may further comprise the steps: (a) being raw material with the oxycompound, is 400～600 ℃ in temperature of reaction, and reaction pressure is 0.02～0.5MPaG, and weight space velocity is 0.2～20 hour
-1Under the condition, fluidized-bed reactor and the SAPO-34 molecular sieve catalyst contact reacts effluent that generate the low-carbon alkene that contain ethene, propylene, butylene of raw material by the reaction-regeneration system of continuous catalyst regenerating, through separate ethene, propylene and butylene product; (b) reclaimable catalyst enters revivifier regeneration behind the stripper stripping; (c) through regenerated catalyst recirculation backflow fluidized bed reactor; The rear catalyst of wherein regenerating is earlier through pump around circuit fluidized bed reactor behind the degassing vessel; Degassing vessel has two stripped vapor sections, and to make the linear speed of bottom stripping stage be 0.05～0.2 meter per second, and the linear speed of top stripping stage is 0.25～0.5 meter per second.
2. according to the described method of producing low-carbon alkene by oxycompound of claim 1, the catalyzer after it is characterized in that regenerating enters reactor after deviating from small amount of nitrogen, oxygen, COx and the NOx of catalyst entrainment by degassing vessel.
3. according to the described method of producing low-carbon alkene of claim 1, it is characterized in that oxycompound is selected from least a in methyl alcohol, ethanol or the dme by oxycompound.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102274661B (en) * | 2010-06-11 | 2016-02-10 | 中国石油化工股份有限公司 | The removal methods of catalyst in methanol-to-olefins regenerator flue gas |
| CN102295507B (en) * | 2010-06-24 | 2014-01-22 | 中国石油化工股份有限公司 | Method for converting methanol or dimethyl ether into low-carbon olefin |
| CN102463085B (en) * | 2010-11-17 | 2014-01-22 | 中国石油化工股份有限公司 | Reaction device for producing dimethylbenzene from methanol or dimethyl ether and methylbenzene |
| CN102463084B (en) * | 2010-11-17 | 2015-02-11 | 中国石油化工股份有限公司 | Reaction device for preparing dimethylbenzene from methanol or dimethyl ether and methylbenzene |
| CN103372460B (en) * | 2012-04-19 | 2015-09-30 | 正大能源材料(大连)有限公司 | A kind of method utilizing the gaseous mixture regenerated methanol alkene catalyst of oxygen and carbon dioxide |
| CN104557365B (en) * | 2013-10-28 | 2016-09-07 | 中国石油化工股份有限公司 | The coaxial-type fluidized bed reaction system of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons and reaction method thereof |
| CN104557366B (en) * | 2013-10-28 | 2017-01-18 | 中国石油化工股份有限公司 | System and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether |
| CN104557370B (en) * | 2013-10-28 | 2016-07-13 | 中国石油化工股份有限公司 | The double-fluidized-bed response system of methanol and/or dimethyl ether conversion ethylene, propylene and aromatic hydrocarbons and method thereof |
| CN113493365B (en) * | 2020-03-19 | 2022-11-04 | 中国石油化工股份有限公司 | Method for reducing catalyst loss in methanol to olefin conversion processes |
| CN114479914A (en) * | 2021-12-31 | 2022-05-13 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for removing oxygen-containing compounds in Fischer-Tropsch synthetic oil |
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