CN107961745A - A kind of turbulent fluid bed reactor, device and method that propylene and C4 hydro carbons are prepared by oxygenatedchemicals - Google Patents
A kind of turbulent fluid bed reactor, device and method that propylene and C4 hydro carbons are prepared by oxygenatedchemicals Download PDFInfo
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- CN107961745A CN107961745A CN201610913355.9A CN201610913355A CN107961745A CN 107961745 A CN107961745 A CN 107961745A CN 201610913355 A CN201610913355 A CN 201610913355A CN 107961745 A CN107961745 A CN 107961745A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/30—Treating with free oxygen-containing gas in gaseous suspension, e.g. fluidised bed
- B01J38/32—Indirectly heating or cooling material within regeneration zone or prior to entry into regeneration zone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/2402—Monolithic-type reactors
- B01J2219/2418—Feeding means
- B01J2219/2419—Feeding means for the reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/2402—Monolithic-type reactors
- B01J2219/2418—Feeding means
- B01J2219/242—Feeding means for the catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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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
- Y02P30/20—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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to prepare propylene, the turbulent fluid bed reactor of C4 hydro carbons, device and method by oxygenatedchemicals.The device includes turbulent fluid bed reactor and the fluid bed regenerator for regenerated catalyst.This method includes：A) raw material containing oxygenatedchemicals is passed through to the reaction zone of turbulent fluid bed reactor from n reactor feed distributor, contacted with catalyst, generates the logistics containing target product and carbon containing reclaimable catalyst；B) product separation system is sent into the logistics containing target product flowed out by turbulent fluid bed reactor, separate to obtain the component such as propylene, C4 hydro carbons, light component, the light component of more than 70wt.% is returned to the reaction zone of turbulent fluid bed reactor by the reactor feed distributor of turbulent fluid bed reactor bottom, the product such as alkylated reaction, generation propylene occurs under the action of catalyst for ethene and oxygenatedchemicals.It is high that method and apparatus of the present invention improve ethylene alkylation speed, reactor unit volume production capacity.
Description
Technical field
The present invention relates to chemical catalysis field, more particularly to a kind of method that propylene, C4 hydro carbons are prepared by oxygenatedchemicals
And its device.
Background technology
Propylene, butadiene are important industrial chemicals, are usually obtained from naphtha pyrolysis and steam cracking.Propylene
Main source is ethene propylene simultaneously and refinery's by-product propylene, and butadiene main source is the C4 produced to cracking of ethylene technique
Accessory substance is processed further and obtains.Recent years, methanol-to-olefins (MTO) technology, methanol prepare propylene (MTP) technology, second
Alkane dehydrogenation technique for producing ethylene, preparing propylene by dehydrogenating propane technology obtain faster development, global olefin feedstock lighting trend
Substantially, this will cause C4 resource provisionings nervous, it is therefore desirable to develop it is a kind of can be with highly-selective preparation of propylene and the work of C4 alkene
Skill, so as to meet the market demand.
German Lucci corporation develops fixed bed methanol-to-olefins technology (WO2004/018089), which utilizes south
The ZSM-5 molecular sieve catalyst of chemical company, carries out methanol to olefins reaction in fixed bed reactors, and Propylene Selectivity approaches
70%, accessory substance is ethene, liquefied petroleum gas and gasoline.
The DMTO technologies of Dalian Chemistry and Physics Institute exploitation, using SAPO molecular sieve as catalyst, use dense-phase circulating fluidized bed reaction
Device, using methanol aqueous solution as raw material, the yield about 80% of ethene, propylene, the C4 hydro carbons of by-product more than 10% in product.
Patent CN104098429A discloses a kind of method for preparing propylene, C4 hydro carbons by methanol using recirculating fluidized bed,
This method uses ZSM-5 catalyst, and process characteristic is that most of C1, C2, C5 hydro carbons in material benzenemethanol and product enters jointly
Circulating fluid bed reactor, propylene, C4 hydro carbons, more than C6 hydro carbons and accessory substance are recycled as final product.
Patent CN101177374B discloses a kind of method by methanol or dimethyl ether for alkene.This method includes methanol
Or dimethyl ether conversion reaction, ethene and methanol alkylation reaction and more than C4 heavy component catalytic cracking reactions.Methanol or diformazan
Ether conversion reaction, ethene and methanol alkylation reaction use catalyst 1, and reaction is completed in same reactor；More than C4 weights
Component catalyst cracking reaction completes reaction using catalyst 2 in another reactor.
Patent CN104098429A and CN101177374B disclose method have the characteristics that one it is common, i.e. by light
Component (carbon number is not more than 2 hydro carbons) freshening, the selectivity of increase target product (propylene and C4).Above-mentioned light component freshening reaction
Main reaction be ethene and methanol alkylated reaction.
MTO reacts and olefin alkylation reaction can all use acid molecular sieve catalyst, but MTO reaction rates are far above alkene
Hydrocarbon alkyl reaction.We have found that fresh SAPO catalyst activities are high, are more advantageous to olefin alkylation reaction, urge by studying
After agent carbon distribution, olefin alkylation reaction speed will reduce rapidly.
Methanol is both the raw material of olefin alkylation reaction, and the raw material of MTO reactions, so, olefin alkylation reaction must
So reacted with MTO.MTO reactions can cause catalyst carbon deposit, activity to reduce, and can thus suppress olefin alkylation reaction.
The content of light component in product gas can be reduced by improving olefin alkylation reaction speed, therefore can improve reactor unit volume
Production capacity.
The method that patent CN104098429A and CN101177374B are disclosed is not directed to structure of reactor, is also not known anti-
Answer the catalyst type of flow in device, material flow mode, product distribution mode etc..The method that patent CN101177374B is disclosed is adopted
With SAPO catalyst, case study on implementation shows that the mass ratio of methanol and light component is 1:10-20, it can be seen that, light component content pole
Height, the production capacity of reactor unit volume are extremely low.The method that patent CN104098429A is disclosed uses ZSM-5 catalyst, in product
More than C6 hydrocarbon contents are higher, and the content of light component in product gas is not disclosed in this method.
From the above analysis, it is MTO reactions and alkene alkane by the main reaction that raw material prepares propylene and C4 hydro carbons of methanol
Glycosylation reaction, therefore, the key for improving propylene and C4 hydrocarbon selectives are Catalyst Design and reactor design.Pass through reaction
It is to improve the economy that methanol prepares propylene and C4 hydro carbons processes that device optimization design, which avoids MTO response inhabitation olefin alkylation reactions,
One of important method.
The content of the invention
The present invention prepares the problem of ethylene alkylation speed during propylene and C4 hydro carbons is low for methanol, there is provided one
The method and its device of the new raising ethylene alkylation speed of kind.This method prepares propylene and C4 hydrocarbon for oxygenatedchemicals
In the production of class, there is propylene and C4 hydro carbons yields are higher, process economics are good.
To achieve the above object, on the one hand, prepare propylene and C4 hydro carbons for oxygenatedchemicals the present invention provides one kind
Turbulent fluid bed reactor, the turbulent fluid bed reactor includes：Reactor shell (2), n reactor feed distributor
(3-1~3-n), reactor gas-solid separator 1 (4), reactor gas-solid separator 2 (5), reactor heat collector (6), product gas go out
Mouthful (7) and reactor stripper (8), the lower part of wherein turbulent fluid bed reactor (1) are reaction zones, turbulent fluid bed reactor
(1) top is decanting zone, and n reactor feed distributor (3-1~3-n) arranges be placed in reaction zone, reactor from the bottom to top
Heat collector (6) is placed in reaction zone, and reactor gas-solid separator 1 (4) and reactor gas-solid separator 2 (5) are placed in decanting zone or anti-
Answer device housing (2) exterior, reactor gas-solid separator 1 (4) is equipped with regenerated catalyst inlet, reactor gas-solid separator 1 (4)
Catalyst outlet is placed in the bottom of reaction zone, and the gas vent of reactor gas-solid separator 1 (4) is placed in decanting zone, reactor gas
The entrance of solid separator 2 (5) is placed in decanting zone, and the catalyst outlet of reactor gas-solid separator 2 (5) is placed in reaction zone, reaction
The gas vent of device gas-solid separator 2 (5) is connected to product gas outlet (7), and reactor stripper (8) is reacted in turbulent fluidized bed
The bottom ecto-entad of device is through reactor shell and is opened in the reaction zone of turbulent fluid bed reactor (1), reactor
The bottom of stripper (8) is equipped with reactor stripping gas entrance (9), and the bottom of reactor stripper goes out equipped with reclaimable catalyst
Mouthful.
In a preferred embodiment, n reactor feed distributor (3-1~3- of fast fluidized bed reactor (1)
N) it is placed in reaction zone from the bottom to top, 0<n<10.
In a preferred embodiment, reactor stripper (8) is high in the level of the internal opening of reactor shell (2)
Degree is directly entered reactor stripper higher than the height of 1/10 reaction zone to avoid fresh catalyst.
In a preferred embodiment, reactor gas-solid separator 1 (4) and reactor gas-solid separator 2 (5) are whirlwind
Separator.
Invention further provides a kind of device that propylene and C4 hydro carbons are prepared for oxygenatedchemicals, described device bag
Fluid bed regenerator (14) containing above-mentioned turbulent fluid bed reactor (1) and for regenerated catalyst.
In a preferred embodiment, fluid bed regenerator (14) is turbulent fluidized bed regenerator.
In a preferred embodiment, fluid bed regenerator (14) includes regenerator housing (15), regenerator feed point
Cloth device (16), regenerator gas-solid separator (17), regenerator heat collector (18), exhanst gas outlet (19) and regenerator stripper
(20), the lower part of wherein fluid bed regenerator (14) is renewing zone, and the top of fluid bed regenerator (14) is decanting zone, regenerator
Feed distributor (16) is placed in the bottom of renewing zone, and regenerator heat collector (18) is placed in renewing zone, regenerator gas-solid separator
(17) it is placed in decanting zone or regenerator housing (15) is exterior, the entrance of regenerator gas-solid separator (17) is placed in decanting zone, regenerates
The catalyst outlet of device gas-solid separator (17) is placed in renewing zone, and the gas vent of regenerator gas-solid separator (17) is connected to cigarette
Gas exports (19), and the entrance of regenerator stripper (20) is connected to the bottom of regenerator housing (15)；
The reclaimable catalyst outlet of reactor stripper (8) is connected to the entrance of inclined tube to be generated (10), inclined tube (10) to be generated
In be equipped with guiding valve to be generated (11), the outlet of inclined tube (10) to be generated is connected to the entrance of riser to be generated (12), riser to be generated
(12) bottom is equipped with lifting gas entrance (13) to be generated, and the outlet of riser (12) to be generated is connected to fluid bed regenerator (14)
Decanting zone；And
The bottom of regenerator stripper (20) is equipped with regenerator stripping gas entrance (21), the bottom of regenerator stripper (20)
The entrance of regenerator sloped tube (22) is connected to, regeneration guiding valve (23) is equipped with regenerator sloped tube (22), the outlet of regenerator sloped tube (22) connects
The entrance of regeneration riser (24) is connected to, the bottom of regeneration riser (24) is equipped with regeneration lifting gas entrance (25), regeneration lifting
The outlet of pipe (24) is connected to the entrance of reactor gas-solid separator 1 (4).
On the other hand, the present invention provides a kind of method that oxygenatedchemicals prepares propylene and C4 hydro carbons, including：
It is anti-that raw material containing oxygenatedchemicals from n reactor feed distributor (3-1~3-n) is passed through turbulent fluidized bed
The reaction zone of device (1) is answered, is contacted with catalyst, generates the logistics containing propylene and C4 hydrocarbon products and carbon containing catalysis to be generated
Agent；
Product segregative line is sent into the logistics containing propylene and C4 hydrocarbon products that will be flowed out by turbulent fluid bed reactor (1)
System, propylene, C4 hydro carbons, light component, propane, more than C5 hydro carbons are obtained through separation, and light component comprises more than the ethene of 90wt%, also
Include a small amount of methane, ethane, hydrogen, CO and CO2, the light component of more than 70wt.% is most lower by turbulent fluid bed reactor (1)
The reactor feed distributor (3-1) of side returns to the reaction zone of turbulent fluid bed reactor (1), and ethene and oxygenatedchemicals are being urged
Alkylated reaction occurs under the action of agent, generation includes the product of propylene；
Reclaimable catalyst is regenerated through fluid bed regenerator (14), the gas of the reacted device gas-solid separator 1 (4) of regenerated catalyst
Gu after separation, the bottom of reaction zone into turbulent fluid bed reactor (1).
In a preferred embodiment, method of the present invention using it is above-mentioned for oxygenatedchemicals prepare propylene and
The device of C4 hydro carbons carries out.
In a preferred embodiment, reclaimable catalyst is by reactor stripper (8), inclined tube to be generated (10), to be generated
Guiding valve (11) and riser to be generated (12) enter the decanting zone of fluid bed regenerator (14)；
Regenerating medium is passed through the renewing zone of fluid bed regenerator (14), and catalysis to be generated from regenerator feed distributor (16)
Agent is made charcoal reaction, and generation contains CO, CO2Flue gas and regenerated catalyst, flue gas pass through regenerator gas-solid separator (17)
Discharged after dedusting；
Regenerated catalyst is by regenerator stripper (20), regenerator sloped tube (22), regeneration guiding valve (23) and regeneration riser
(24) reactor gas-solid separator 1 (4) entrance is entered, after gas solid separation, regenerated catalyst enters turbulent fluid bed reactor (1)
The bottom of middle reaction zone；
Reactor stripping gas enters reactor stripper (8) and reclaimable catalyst adverse current by reactor stripping gas entrance (9)
Contact, subsequently into turbulent fluid bed reactor (1)；Lifting gas to be generated enters riser to be generated by lifting gas entrance (13) to be generated
(12) and reclaimable catalyst co-current contact, subsequently into the decanting zone of fluid bed regenerator (14)；
Regenerator stripping gas enters regenerator stripper (20) by regenerator stripping gas entrance (21) and regenerated catalyst is inverse
Stream contact, subsequently into fluid bed regenerator (14)；Regeneration lifting gas enters regeneration riser by regeneration lifting gas entrance (25)
(24) and regenerated catalyst co-current contact, subsequently into the entrance of reactor gas-solid separator 1 (4).
Turbulent fluid bed reactor in the present invention is characterized mainly in that reactor feed point of the light component by bottom
Cloth device enters, and oxygenatedchemicals is respectively enterd by n reactor feed distributor, and regenerated catalyst is directly entered reaction zone bottom
Portion.On the one hand, in the lower part of reaction zone, catalyst activity is high, is conducive to the alkylated reaction of ethene, propylene and methanol；It is another
Aspect, due to by the way of oxygenatedchemicals multistage feeding, avoiding sub-fraction of the oxygenatedchemicals below reaction zone
Most conversion reaction is completed in region, in this way, oxygenate concentration is more uniform in most of conversion zone, is weakened
MTO reacts the suppression to olefin alkylation reaction.Therefore, the turbulent fluid bed reactor in the present invention can effectively improve alkene
Hydrocarbon alkyl reaction speed, reactor unit volume production capacity are high.
Oxygenatedchemicals of the present invention is prepared in the method for propylene and C4 hydro carbons, MTO reactions generation ethene and propylene
High Deng product, olefin alkylation reaction consumption of ethylene and propylene etc., ethylene alkylation speed, then light component contains in product gas
Measure that low, light component internal circulating load is low.Method of the present invention, light component internal circulating load are the 5- of oxygen compound feedstock amount
40wt.%.
Method of the present invention, the light component of more than 70wt.% circulate in systems, and the release rate of light component affects
The composition of product gas under equilibrium state.In the state of the equilibrium, the composition of product gas is 20-50wt.% propylene, 15-40wt.%C4
Hydro carbons, 10-45wt.% light components, 0-5wt.% propane and more than 5-20wt.%C5 hydro carbons.Contain in light component and have more than
90wt.%, such as>The ethene of 95wt.%, other components are methane, ethane, hydrogen, CO and CO2Deng.
In a preferred embodiment, the catalyst contains SAPO molecular sieve, which has methanol system at the same time
The function of alkene, olefin alkylation.
In a preferred embodiment, the regenerated catalyst carbon content<2wt.%, it is further preferred that regeneration is urged
Agent carbon content<0.5wt.%.
In a preferred embodiment, the reclaimable catalyst carbon content is 5-12wt.%, it is further preferred that treating
Raw coke on regenerated catalyst is 5-10wt.%.
In a preferred embodiment, turbulent fluid bed reactor (1) the reaction zone reaction condition is：Gas superficial
Linear velocity is 0.1-2m/s, and reaction temperature is 300-550 DEG C, reaction pressure 100-500kPa, bed density 200-
1200kg/m3。
In a preferred embodiment, fluid bed regenerator (14) renewing zone reaction condition is：Gas superficial line
Speed is 0.1-2m/s, and regeneration temperature is 500-750 DEG C, regeneration pressure 100-500kPa, bed density 200-1200kg/
m3。
In a preferred embodiment, the oxygenatedchemicals is methanol and/or dimethyl ether；The regenerating medium is sky
Any one in gas, oxygen denuded air or vapor or any several mixture；The reactor stripping gas, regenerator stripping
Gas, lifting gas to be generated and regeneration lifting gas are vapor or nitrogen.
Brief description of the drawings
Fig. 1 is the device letter that the oxygenatedchemicals of the present invention according to an embodiment of the invention prepares propylene and C4 hydro carbons
Figure.
The reference numerals are as follows in attached drawing：
1- turbulent fluid bed reactors；2- reactor shells；3- reactor feeds distributor (3-1~3-n)；4- reactors
Gas-solid separator 1；5- reactors gas-solid separator 2；6- reactor heat collectors；7- product gas outlets；8- reactor strippers；9-
Reactor stripping gas entrance；10- inclined tubes to be generated；11- guiding valves to be generated；12- risers to be generated；13- lifting gas entrances to be generated；14-
Fluid bed regenerator；15- regenerator housings；16- regenerator feed distributors；17- regenerator gas-solid separators；18- regenerators
Heat collector；19- exhanst gas outlets；20- regenerator strippers；21- regenerator stripping gas entrances；22- regenerator sloped tubes；23- regeneration is slided
Valve；24- regenerates riser；25- regeneration lifting gas entrances.
Embodiment
In a specific embodiment, it is of the present invention propylene is prepared by oxygenatedchemicals, the device of C4 hydro carbons shows
It is intended to as shown in Figure 1, the device includes：
A) turbulent fluid bed reactor (1), it includes reactor shell (2), n reactor feed distributor (3-1~3-
N), reactor gas-solid separator 1 (4), reactor gas-solid separator 2 (5), reactor heat collector (6), product gas outlet (7) and
Reactor stripper (8), the lower part of wherein turbulent fluid bed reactor (1) are reaction zones, turbulent fluid bed reactor (1) it is upper
Portion is decanting zone, and n reactor feed distributor (3-1~3-n) arranges be placed in reaction zone from the bottom to top, 0<n<10, reactor
Heat collector (6) is placed in reaction zone, and reactor gas-solid separator 1 (4) and reactor gas-solid separator 2 (5) are placed in decanting zone or anti-
Answer device housing (2) exterior, the entrance of reactor gas-solid separator 1 (4) is connected to regeneration riser (24), reactor gas solid separation
The catalyst outlet of device 1 (4) is placed in the bottom of reaction zone, and the gas vent of reactor gas-solid separator 1 (4) is placed in decanting zone,
The entrance of reactor gas-solid separator 2 (5) is placed in decanting zone, and the catalyst outlet of reactor gas-solid separator 2 (5) is placed in reaction
Area, the gas vent of reactor gas-solid separator 2 (5) are connected to product gas outlet (7), and the entrance of reactor stripper (8) exists
In the reaction zone of turbulent fluid bed reactor (1), its level height is higher than the height of 1/10 reaction zone；
B) fluid bed regenerator (14), it includes regenerator housing (15), regenerator feed distributor (16), regenerator gas
Solid separator (17), regenerator heat collector (18), exhanst gas outlet (19) and regenerator stripper (20), wherein fluid bed regenerator
(14) lower part is renewing zone, and the top of fluid bed regenerator (14) is decanting zone, and regenerator feed distributor (16) is placed in again
The bottom in raw area, regenerator heat collector (18) are placed in renewing zone, and regenerator gas-solid separator (17) is placed in decanting zone or regenerator
Housing (15) is exterior, and the entrance of regenerator gas-solid separator (17) is placed in decanting zone, the catalysis of regenerator gas-solid separator (17)
Agent outlet is placed in renewing zone, and the gas vent of regenerator gas-solid separator (17) is connected to exhanst gas outlet (19), regenerator stripping
The entrance of device (20) is connected to the bottom of regenerator housing (15)；
C) bottom of reactor stripper (8) is equipped with reactor stripping gas entrance (9), the bottom of reactor stripper (8)
The entrance of inclined tube to be generated (10) is connected to, guiding valve to be generated (11) is equipped with inclined tube (10) to be generated, the outlet of inclined tube (10) to be generated connects
The entrance of riser to be generated (12) is connected to, the bottom of riser (12) to be generated is equipped with lifting gas entrance (13) to be generated, lifting to be generated
The outlet of pipe (12) is connected to the decanting zone of fluid bed regenerator (14)；
D) bottom of regenerator stripper (20) is equipped with regenerator stripping gas entrance (21), the bottom of regenerator stripper (20)
Portion is connected to the entrance of regenerator sloped tube (22), and regeneration guiding valve (23), the outlet of regenerator sloped tube (22) are equipped with regenerator sloped tube (22)
The entrance of regeneration riser (24) is connected to, the bottom of regeneration riser (24) is equipped with regeneration lifting gas entrance (25), and regeneration carries
The outlet of riser (24) is connected to the entrance of reactor gas-solid separator 1 (4).
In the above-described embodiment, fluid bed regenerator (14) can be turbulent fluidized bed regenerator；Reactor gas-solid point
Can be cyclone separator from device 1 (4), reactor gas-solid separator 2 (5) and regenerator gas-solid separator (17).
In a specific embodiment, the method bag of the present invention that propylene, C4 hydro carbons are prepared by oxygenatedchemicals
Include：
A) raw material containing oxygenatedchemicals is passed through turbulent fluidized bed from n reactor feed distributor (3-1~3-n)
The reaction zone of reactor (1), contacts with catalyst, generates the logistics containing propylene and C4 hydrocarbon products and carbon containing catalysis to be generated
Agent；
B) product separation is sent into the logistics containing propylene and C4 hydrocarbon products that will be flowed out by turbulent fluid bed reactor (1)
System, obtains propylene, C4 hydro carbons, light component, propane, more than C5 hydro carbons, the main component of light component is ethene, is also wrapped through separation
Containing a small amount of methane, ethane, hydrogen, CO and CO2, the light component of more than 70wt.% is by turbulent fluid bed reactor (1) bottom
Reactor feed distributor (3-1) return turbulent fluid bed reactor (1) reaction zone, ethene and oxygenatedchemicals are being catalyzed
Product, the light component less than 30wt.% such as alkylated reaction, generation propylene occur under the action of agent to be recovered as accessory substance；
C) reclaimable catalyst passes through reactor stripper (8), inclined tube to be generated (10), guiding valve to be generated (11) and riser to be generated
(12) decanting zone of fluid bed regenerator (14) is entered；
D) regenerating medium is passed through to the renewing zone of fluid bed regenerator (14) from regenerator feed distributor (16), regeneration is situated between
Matter and reclaimable catalyst are made charcoal reaction, and generation contains CO, CO2Flue gas and regenerated catalyst, flue gas pass through regenerator gas
Discharged after solid separator (17) dedusting；
E) regenerated catalyst is by regenerator stripper (20), regenerator sloped tube (22), regeneration guiding valve (23) and regeneration lifting
Pipe (24) enters reactor gas-solid separator 1 (4) entrance, and after gas solid separation, regenerated catalyst enters turbulent fluid bed reactor
(1) bottom of reaction zone in；
F) reactor stripping gas enters reactor stripper (8) by reactor stripping gas entrance (9) and reclaimable catalyst is inverse
Stream contact, subsequently into turbulent fluid bed reactor (1)；Lifting gas to be generated enters lifting to be generated by lifting gas entrance (13) to be generated
(12) and reclaimable catalyst co-current contact are managed, subsequently into the decanting zone of fluid bed regenerator (14)；
G) regenerator stripping gas enters regenerator stripper (20) and regenerated catalyst by regenerator stripping gas entrance (21)
Counter current contacting, subsequently into fluid bed regenerator (14)；Regeneration lifting gas enters regeneration by regeneration lifting gas entrance (25) and is lifted
(24) and regenerated catalyst co-current contact are managed, subsequently into the entrance of reactor gas-solid separator 1 (4).
For the present invention is better described, readily appreciate technical scheme, the typical case of contrast case and the present invention but
Non-limiting embodiment is as follows：
Embodiment 1
Present case is contrast case, using the device shown in Fig. 1, but does not include reaction in turbulent fluid bed reactor (1)
Device gas-solid separator 1 (4), regeneration riser (24) are directly connected in the decanting zone of turbulent fluid bed reactor (1).
Turbulent fluid bed reactor (1) contains 3 reactor feed distributors (3-1~3-3), reactor gas-solid separator
1 (4) are placed in reactor shell (2) outside, and the level height of the entrance of reactor stripper (8) is in the height of 1/2 reaction zone.
Turbulent fluid bed reactor (1) reaction zone reaction condition is：Gas superficial linear velocity is about 1.0m/s, and reaction temperature is about 450
DEG C, reaction pressure is about 150kPa, and bed density is about 350kg/m3。
Fluid bed regenerator (14) renewing zone reaction condition is：Gas superficial linear velocity is about 1.0m/s, and regeneration temperature is about
For 650 DEG C, regeneration pressure is about 150kPa, and bed density is about 350kg/m3。
Catalyst contains SAPO molecular sieve, and reclaimable catalyst carbon content is about 7%, and regenerated catalyst carbon content is about
0.2wt.%.
Oxygenatedchemicals is methanol, and regenerating medium is air；Reactor stripping gas, regenerator stripping gas, lifting gas to be generated
It is vapor with regeneration lifting gas.
Light component internal circulating load is the 20wt.% of methanol inlet amount, and the light component of 83wt.% circulates in systems.
By turbulent fluid bed reactor (1) discharge forming for product gas be：34wt.% propylene, 20wt.%C4 hydro carbons,
35wt.% light components, 1wt.% propane and more than 10wt.%C5 hydro carbons.Ethene containing 99wt.% in light component, and
Methane, ethane, hydrogen, CO, CO of 1wt.%2Deng.
By piece-rate system discharge forming for product gas be：48wt.% propylene, 28wt.%C4 hydro carbons, light group of 9wt.%
Point, 1wt.% propane and more than 14wt.%C5 hydro carbons.
Embodiment 2
Using the device shown in Fig. 1, turbulent fluid bed reactor (1) contains 3 reactor feed distributor (3-1~3-
3), reactor gas-solid separator 1 (4) is placed in reactor shell (2) outside, the level height of the entrance of reactor stripper (8)
Height in 1/2 reaction zone.Turbulent fluid bed reactor (1) reaction zone reaction condition is：Gas superficial linear velocity is about
1.0m/s, reaction temperature are about 450 DEG C, and reaction pressure is about 150kPa, and bed density is about 350kg/m3。
Fluid bed regenerator (14) renewing zone reaction condition is：Gas superficial linear velocity is about 1.0m/s, and regeneration temperature is about
For 650 DEG C, regeneration pressure is about 150kPa, and bed density is about 350kg/m3。
Catalyst contains SAPO molecular sieve, and reclaimable catalyst carbon content is about 7%, and regenerated catalyst carbon content is about
0.2wt.%.
Oxygenatedchemicals is methanol, and regenerating medium is air；Reactor stripping gas, regenerator stripping gas, lifting gas to be generated
It is vapor with regeneration lifting gas.
Light component internal circulating load is the 20wt.% of methanol inlet amount, and the light component of 98wt.% circulates in systems.
By turbulent fluid bed reactor (1) discharge forming for product gas be：32wt.% propylene, 24wt.%C4 hydro carbons,
31wt.% light components, 2wt.% propane and more than 11wt.%C5 hydro carbons.Ethene containing 97wt.% in light component, and
Methane, ethane, hydrogen, CO, CO of 3wt.%2Deng.
By piece-rate system discharge forming for product gas be：46wt.% propylene, 34wt.%C4 hydro carbons, light group of 1wt.%
Point, 3wt.% propane and more than 16wt.%C5 hydro carbons.
The regenerated catalyst that differs only in of present case and embodiment 1 (contrast case) enters turbulent fluid bed reactor
Bottom, contacts with light component first, and regenerated catalyst enters the decanting zone of turbulent fluid bed reactor in embodiment 1.Contrast
Present case and embodiment 1 understand, catalyst contacts light component first can increase substantially the conversion ratio of light component, present case by
The light component of piece-rate system discharge is only contrast case 11%, and therefore, device of the present invention effectively raises ethene
Alkylated reaction speed.
Embodiment 3
Using the device shown in Fig. 1, turbulent fluid bed reactor (1) contains 4 reactor feed distributor (3-1~3-
4), reactor gas-solid separator 1 (4) is placed in decanting zone, and the level height of the entrance of reactor stripper (8) is in 3/4 reaction
The height in area.Turbulent fluid bed reactor (1) reaction zone reaction condition is：Gas superficial linear velocity is about 1.2m/s, reaction temperature
About 360 DEG C of degree, reaction pressure is about 200kPa, and bed density is about 300kg/m3。
Fluid bed regenerator (14) renewing zone reaction condition is：Gas superficial linear velocity is about 1.2m/s, and regeneration temperature is about
For 700 DEG C, regeneration pressure is about 200kPa, and bed density is about 300kg/m3。
Catalyst contains SAPO molecular sieve, and reclaimable catalyst carbon content is about 8%, and regenerated catalyst carbon content is about
0.1wt.%.
Oxygenatedchemicals is methanol, and regenerating medium is air；Reactor stripping gas, regenerator stripping gas, lifting gas to be generated
It is vapor with regeneration lifting gas.
Light component internal circulating load is the 16wt.% of methanol inlet amount, and the light component of 90wt.% circulates in systems.
By turbulent fluid bed reactor (1) discharge forming for product gas be：34wt.% propylene, 25wt.%C4 hydro carbons,
29wt.% light components, 2wt.% propane and more than 10wt.%C5 hydro carbons.Ethene containing 98wt.% in light component, and
Methane, ethane, hydrogen, CO, CO of 2wt.%2Deng.
By piece-rate system discharge forming for product gas be：46wt.% propylene, 34wt.%C4 hydro carbons, light group of 4wt.%
Point, 3wt.% propane and more than 13wt.%C5 hydro carbons.
Embodiment 4
Using the device shown in Fig. 1, turbulent fluid bed reactor (1) contains 6 reactor feed distributor (3-1~3-
6), reactor gas-solid separator 1 (4) is placed in decanting zone, and the level height of the entrance of reactor stripper (8) is in 5/6 reaction
The height in area.Turbulent fluid bed reactor (1) reaction zone reaction condition is：Gas superficial linear velocity is about 1.5m/s, reaction temperature
About 420 DEG C of degree, reaction pressure is about 250kPa, and bed density is about 250kg/m3。
Fluid bed regenerator (14) renewing zone reaction condition is：Gas superficial linear velocity is about 1.5m/s, and regeneration temperature is about
For 700 DEG C, regeneration pressure is about 250kPa, and bed density is about 250kg/m3。
Catalyst contains SAPO molecular sieve, and reclaimable catalyst carbon content is about 9%, and regenerated catalyst carbon content is about
0.05wt.%.
Oxygenatedchemicals is dimethyl ether, and regenerating medium is oxygen denuded air；It is reactor stripping gas, regenerator stripping gas, to be generated
It is nitrogen to lift gas and regeneration lifting gas.
Light component internal circulating load is the 14wt.% of dimethyl ether inlet amount, and the light component of 85wt.% circulates in systems.
By turbulent fluid bed reactor (1) discharge forming for product gas be：38wt.% propylene, 30wt.%C4 hydro carbons,
21wt.% light components, 2wt.% propane and more than 9wt.%C5 hydro carbons.Ethene containing 98wt.% in light component, and
Methane, ethane, hydrogen, CO, CO of 2wt.%2Deng.
By piece-rate system discharge forming for product gas be：46wt.% propylene, 37wt.%C4 hydro carbons, light group of 4wt.%
Point, 2wt.% propane and more than 11wt.%C5 hydro carbons.
Above to the present invention have been described in detail, but the invention is not limited in specific embodiment party described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and deformation can be made.This hair
Bright scope is defined by the following claims.
Claims (15)
1. a kind of turbulent fluid bed reactor that propylene and C4 hydro carbons are prepared for oxygenatedchemicals, the turbulent fluidized bed reaction
Device includes：It is reactor shell, n reactor feed distributor, reactor gas-solid separator 1, reactor gas-solid separator 2, anti-
Answer device heat collector, product gas outlet and reactor stripper, the lower part of wherein turbulent fluid bed reactor is reaction zone, turbulence stream
The top of fluidized bed reactor is decanting zone, and n reactor feed distributor is placed in reaction zone, and reactor heat collector is placed in reactor
Reaction zone, reactor gas-solid separator 1 and reactor gas-solid separator 2 are placed in outside decanting zone or reactor shell, instead
Device gas-solid separator 1 is answered to be equipped with regenerated catalyst inlet, the catalyst outlet of reactor gas-solid separator 1 is placed in the bottom of reaction zone
Portion, the gas vent of reactor gas-solid separator 1 are placed in decanting zone, and the entrance of reactor gas-solid separator 2 is placed in decanting zone, instead
The catalyst outlet of device gas-solid separator 2 is answered to be placed in reaction zone, the gas vent of reactor gas-solid separator 2 is connected to product gas
Outlet, reactor stripper through reactor shell and are opened on turbulence in the bottom ecto-entad of turbulent fluid bed reactor
In the reaction zone of fluidized-bed reactor, the bottom of reactor stripper is equipped with reactor stripping gas entrance, and reactor strips
The bottom of device is exported equipped with reclaimable catalyst.
2. turbulent fluid bed reactor according to claim 1, wherein the n reactor feed distributor is from the bottom to top
It is placed in reaction zone, 0<n<10.
3. turbulent fluid bed reactor according to claim 1 or 2, wherein the reactor stripper is in reactor shell
The level height of internal opening is higher than the height of 1/10 reaction zone.
4. turbulent fluid bed reactor according to claim 1 or 2, wherein reactor gas-solid separator 1 and reactor gas
Solid separator 2 is cyclone separator.
5. a kind of device that propylene and C4 hydro carbons are prepared for oxygenatedchemicals, described device include any in claim 1-3
Turbulent fluid bed reactor described in and the fluid bed regenerator for regenerated catalyst.
6. device according to claim 5, wherein the fluid bed regenerator is turbulent fluidized bed regenerator.
7. device according to claim 5, wherein the fluid bed regenerator includes regenerator housing, regenerator feed point
Cloth device, regenerator gas-solid separator, regenerator heat collector, exhanst gas outlet and regenerator stripper, wherein fluid bed regenerator
Lower part is renewing zone, and the top of fluid bed regenerator is decanting zone, and regenerator feed distributor is placed in the bottom of renewing zone, regeneration
Device heat collector is placed in renewing zone, and regenerator gas-solid separator is placed in decanting zone or regenerator hull outside, regenerator gas solid separation
The entrance of device is placed in decanting zone, and the catalyst outlet of regenerator gas-solid separator is placed in renewing zone, regenerator gas-solid separator
Gas vent is connected to exhanst gas outlet, and regenerator stripper is opened on the bottom of regenerator housing；
The reclaimable catalyst outlet of the reactor stripper is connected to the entrance of inclined tube to be generated, and cunning to be generated is equipped with inclined tube to be generated
Valve, the outlet of inclined tube to be generated are connected to the entrance of riser to be generated, and the bottom of riser to be generated is equipped with lifting gas entrance to be generated, treats
The outlet of raw riser is connected to the decanting zone of fluid bed regenerator；And
The bottom of the regenerator stripper is equipped with regenerator stripping gas entrance, and the bottom of regenerator stripper is connected to regeneration tiltedly
The entrance of pipe, regeneration guiding valve is equipped with regenerator sloped tube, and the outlet of regenerator sloped tube is connected to the entrance of regeneration riser, and regeneration is lifted
The bottom of pipe is equipped with regeneration lifting gas entrance, and the outlet for regenerating riser is connected to the regeneration catalyzing of reactor gas-solid separator 1
Agent entrance.
8. a kind of method that oxygenatedchemicals prepares propylene and C4 hydro carbons, including：
Raw material containing oxygenatedchemicals is passed through to the reaction zone of turbulent fluid bed reactor from n reactor feed distributor,
Contacted with catalyst, generate the logistics containing propylene and C4 hydrocarbon products and carbon containing reclaimable catalyst；
Product separation system is sent into the logistics containing propylene and C4 hydrocarbon products flowed out by turbulent fluid bed reactor, through dividing
From propylene, C4 hydro carbons, light component, propane, more than C5 hydro carbons is obtained, wherein light component comprises more than the ethene of 90wt%, also wraps
Containing a small amount of methane, ethane, hydrogen, CO and CO2, the light component of more than 70wt.% is by turbulent fluid bed reactor bottom
Reactor feed distributor returns to the reaction zone of turbulent fluid bed reactor, and ethene and oxygenatedchemicals are under the action of catalyst
Generation alkylated reaction, generation include the product of propylene；
Reclaimable catalyst is regenerated through fluid bed regenerator, after the gas solid separation of the reacted device gas-solid separator 1 of regenerated catalyst, into
Enter the bottom of reaction zone in turbulent fluid bed reactor.
9. according to the method described in claim 8, it is carried out using device according to any one of claims 5 to 7.
10. according to the method described in claim 9, wherein
Reclaimable catalyst enters fluid bed regenerator by reactor stripper, inclined tube to be generated, guiding valve to be generated and riser to be generated
Decanting zone；
Regenerating medium is passed through the renewing zone of fluid bed regenerator, and reclaimable catalyst is made charcoal reaction, and generation contains CO, CO2's
Flue gas and regenerated catalyst, flue gas discharge after regenerator gas-solid separator dedusting；
Regenerated catalyst is divided by regenerator stripper, regenerator sloped tube, regeneration guiding valve and regeneration riser into reactor gas-solid
From 1 entrance of device, after gas solid separation, regenerated catalyst enters the bottom of reaction zone in turbulent fluid bed reactor；
Reactor stripping gas enters reactor stripper and reclaimable catalyst counter current contacting, Ran Houjin by reactor stripping gas entrance
Enter turbulent fluid bed reactor；Lifting gas to be generated enters riser to be generated by lifting gas entrance to be generated and reclaimable catalyst following current connects
Touch, subsequently into the decanting zone of fluid bed regenerator；
Regenerator stripping gas enters regenerator stripper and regenerated catalyst counter current contacting, Ran Houjin by regenerator stripping gas entrance
Fluidized bed regenerator；Regeneration lifting gas enters regeneration riser and regenerated catalyst co-current contact by regeneration lifting gas entrance,
Subsequently into the entrance of reactor gas-solid separator 1.
11. according to the method described in claim 8, wherein light component internal circulating load is the 5-40wt.% of oxygen compound feedstock amount.
12. according to the method described in claim 8, wherein described reclaimable catalyst carbon content is 5-12wt.%, and it is described again
Raw coke on regenerated catalyst<2wt.%.
13. according to the method described in claim 10, wherein described oxygenatedchemicals is methanol and/or dimethyl ether；It is and/or described
Regenerating medium is any one or any several mixture in air, oxygen denuded air or vapor；And/or the reactor
Stripping gas, regenerator stripping gas, lifting gas to be generated and regeneration lifting gas are vapor or nitrogen.
14. the according to the method described in claim 8, it is characterized in that, turbulent fluid bed reactor reaction zone reaction condition
For：Gas superficial linear velocity is 0.1-2m/s, and reaction temperature is 300-550 DEG C, reaction pressure 100-500kPa, bed density
For 200-1200kg/m3。
15. according to the method described in claim 8, it is characterized in that, fluid bed regenerator renewing zone reaction condition is：Gas
Body superficial linear vilocity is 0.1-2m/s, and regeneration temperature is 500-750 DEG C, regeneration pressure 100-500kPa, and bed density is
200-1200kg/m3。
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| WO2020227849A1 (en) * | 2019-05-10 | 2020-11-19 | 中国科学院大连化学物理研究所 | Method for partially regenerating catalyst for methanol and/or dimethyl ether-to-olefin and method for methanol and/or dimethyl ether-to-olefin |
| RU2787876C1 (en) * | 2019-05-10 | 2023-01-13 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайэнс | Method for partial regeneration of a catalyst for converting methanol and/or dimethyl ether into olefins and method for converting methanol and/or dimethyl ether into olefins |
| CN112552136A (en) * | 2019-09-26 | 2021-03-26 | 中国石油化工股份有限公司 | Method for converting byproduct mixed oxygen-containing compound in process of preparing olefin from methanol |
| CN112552136B (en) * | 2019-09-26 | 2023-05-02 | 中国石油化工股份有限公司 | Method for converting byproduct mixed oxygen-containing compound in process of preparing olefin from methanol |
| RU2719490C1 (en) * | 2019-10-28 | 2020-04-17 | Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" | Device for preparation of catalyst in processes of dehydrogenation of paraffin hydrocarbons c3-c5 |
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