CN101698629A - Device for preparing low-carbon olefin by adopting methanol or dimethyl ether - Google Patents
Device for preparing low-carbon olefin by adopting methanol or dimethyl ether Download PDFInfo
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- CN101698629A CN101698629A CN200910210636A CN200910210636A CN101698629A CN 101698629 A CN101698629 A CN 101698629A CN 200910210636 A CN200910210636 A CN 200910210636A CN 200910210636 A CN200910210636 A CN 200910210636A CN 101698629 A CN101698629 A CN 101698629A
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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
- 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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- 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
- B01J8/38—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 fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
- B01J8/384—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 fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only
- B01J8/388—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 fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only externally, i.e. the particles leaving the vessel and subsequently re-entering it
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective 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
- 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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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A device for preparing low-carbon olefin by adopting methanol or dimethyl ether comprises a catalyst pre-processor besides a reactor and a catalyst regenerator. A gas inlet and a gas distributor is arranged on the bottom of the catalyst pre-processor, and the upper part of the catalyst pre-processor is connected with the main body of the reactor. The catalyst pre-processor adopts riser pre-processor, dense-phase fluidized bed pre-processor, moving bed pre-processor, or fixed bed pre-processor. The catalyst is used in a cyclic way of traveling through the reactor, the regenerator and the catalyst pre-processor in sequence, and returning to the reactor. In the invention, the catalyst pre-processor is arranged between the reactor and the regenerator to pre-process the regenerated catalyst, so that the catalyst can skim the early stage of the induction period with lower selectivity so as to ensure that the catalyst can be in the high selectivity operation area when beginning to take part in the reaction for preparing low-carbon olefin by adopting methanol or dimethyl ether, thus the technique can obtain higher yields of ethylene and propylene.
Description
Technical field
The present invention relates to a kind of device for preparing low-carbon alkene, particularly a kind of device that adopts methyl alcohol or dimethyl ether production low-carbon alkene belongs to technical field of chemical.
Background technology
Low-carbon alkene such as ethene, propylene is an important chemical material, and the important channel of producing low-carbon alkenes such as ethene, propylene at present is to obtain by lightweight oils such as cracking naphtha, solar oils, and petroleum naphtha, solar oil are mainly derived from oil.Scarcity gradually along with petroleum resources adopts raw materials such as abundant coal, Sweet natural gas to produce the technological line of ethene, propylene, more and more is subjected to attention both domestic and external.
Early 1980s, UCC company has successfully developed SAPO series molecular sieve, wherein the SAPO-34 molecular sieve catalyst shows excellent catalytic performance when being used for methanol-to-olefins (MTO) reaction, has very high selectivity of light olefin, and activity is very high, but catalyzer loses activity owing to catalyst surface area has coke in use for some time.
CN116478A discloses a kind of method of being produced low-carbon alkenes such as ethene, propylene by methyl alcohol or dme, catalyzer uses and regenerates at the ciculation fluidized reaction unit of upstriker dense bed, catalyzer is after regeneration, coke long-pending on the surface is by burn off, activity is replied, thereby realize that catalyzer recycles in reactor and revivifier, can produce low-carbon alkenes such as ethene, propylene by successive, ethene and the propylene selectivity sum of utilizing the method and apparatus described in the invention to obtain are 81.01%.
In use there is tangible inductive phase in the SAPO-34 molecular sieve catalyst, in inductive phase, the selectivity of alkene is lower, the selectivity of alkane is higher, and along with the increase in reaction times, selectivity of light olefin rises gradually, after inductive phase, catalyzer keeps high selectivity and high activity within a certain period of time, and continuation in time prolongs, and activity of such catalysts descends rapidly.
WO01/66497A1 discloses a kind of device of methanol-to-olefins, in reactor, be provided with two reaction zones, be provided with first reaction zone at reactor lower part, reaction is mainly at first reactor, finish the reaction of methanol to olefins, be provided with second reaction zone on reactor top, the heavy components such as C4 alkene that contain from the gas that first reactor comes out continue reaction at second reaction zone, to increase the productive rate of alkene, on catalyzer, form simultaneously coke, the catalyzer that has coke enters first reaction zone, the selectivity of low-carbon alkene in the time of can improving methanol conversion.
Methyl alcohol or dme system olefin hydrocarbon, the part of device and revivifier all responds in the pilot plant that has built up at present, the overwhelming majority is to adopt the dense fluidized bed bioreactor, in order to obtain higher selectivity of light olefin, the new reaction unit of exploitation has very important meaning in the process of methyl alcohol or dme system alkene.
Summary of the invention
The objective of the invention is to propose a kind of device that adopts methyl alcohol or dimethyl ether production low-carbon alkene, device also comprises the catalyst pretreatment device except that comprising reactor and catalyst regenerator.In the catalyst pretreatment device, can adopt the by-product gas that product gas separating technology returns or adopt partial raw gas or adopt other gas can be fresh or the regenerated catalyzer carry out pre-treatment, make catalyzer contain certain coke in advance, to eliminate or to reduce the inductive phase of catalyzer, reduce the generation of alkane and higher olefins, thereby increase the selectivity of ethene and propylene; Because pretreated catalyzer is in the optimal operations state in the reactor, therefore can obtain the higher ethene and the yield of propylene;
To achieve these goals, the invention provides a kind of device that adopts methyl alcohol or dimethyl ether production low-carbon alkene, concrete technical scheme is as follows:
A kind of device that adopts methyl alcohol or dimethyl ether production low-carbon alkene, this device comprises reactor body, be arranged on the gas distributor of reactor bottom, be arranged on the cyclonic separator of reactor head, the catalyst regenerator main body, be arranged on the gas distributor of catalyst regenerator bottom, be arranged on the cyclonic separator at catalyst regenerator top, described reactor body and catalyst regenerator main body are arranged in juxtaposition, pipe connection is passed through in the bottom of described reactor body and catalyst regenerator main body, this device also comprises the catalyst pretreatment device, be provided with gas feed and gas distributor in the bottom of described catalyst pretreatment device, the top of catalyst pretreatment device is connected with reactor body.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, described catalyst pretreatment device adopts the riser tube pretreater, riser tube pretreater and reactor body and revivifier are arranged in juxtaposition, and the top of riser tube pretreater is connected with the middle and upper part of reactor body or bottom.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, be provided with catalyzer fast separation device, cyclonic separator and pneumatic outlet at the top of described riser tube pretreater, the outlet of described catalyzer fast separation device is connected with the reactor middle and upper part.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, described catalyst pretreatment device adopts the riser tube pretreater, described riser tube pretreater and reactor body coaxial arrangement, the top of riser tube pretreater is connected with the bottom of reactor body.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, the dense-phase bed of reactor is passed on the top of riser tube pretreater, is provided with the catalyzer fast separation device at the top of riser tube pretreater.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, it is characterized in that: the top of described reactor body also is provided with the cyclonic separator of using for pretreater, and the pneumatic outlet of this catalyzer fast separation device is connected with the described cyclonic separator of using for pretreater.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, described catalyst pretreatment device adopts the dense phase fluidized bed pretreater, be provided with cyclonic separator at described dense phase fluidized bed pretreater top, dense phase fluidized bed pretreater and reactor body and revivifier are arranged in juxtaposition, and the middle and lower part of dense phase fluidized bed pretreater is connected with the middle and upper part of reactor body or bottom.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, described catalyst pretreatment device adopts the moving-bed pretreater, be provided with cyclonic separator at described moving-bed pretreater top, moving-bed pretreater and reactor body and revivifier are arranged in juxtaposition, and the bottom of moving-bed pretreater is connected with the middle and upper part of reactor body or bottom.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, described catalyst pretreatment device adopts the fixed bed pretreater, fixed bed pretreater and reactor body and revivifier are arranged in juxtaposition, and the bottom of fixed bed pretreater is connected with the middle and upper part of reactor body or bottom.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, reactor adopts fluidized-bed, moving-bed or fixed-bed reactor, and reactor preferably adopts fluidized-bed; Catalyst regenerator adopts fluidized-bed, moving-bed or fixed bed revivifier, and revivifier preferably adopts fluidized-bed; Reactor, catalyst regenerator, catalyst pretreatment device adopt different reactors separately, or the same reactor of wherein two or more employings.
The device of described employing methyl alcohol or dimethyl ether production low-carbon alkene, between described reactor and revivifier, also has stripper, be provided with gas distributor in described stripper bottom, the top is provided with cyclonic separator, and stripper is connected by pipeline with the bottom of reactor and revivifier.
The present invention compared with prior art, have the following advantages and the high-lighting effect: in the middle of revivifier and reactor, add pretreater, catalyzer after the regeneration is carried out pre-treatment earlier, make catalyzer skip selectivity early stage lower inductive phase, the reaction that makes catalyzer just participate in methyl alcohol or dme producing light olefins just can be in the highly selective operating area, therefore can make technology obtain higher ethene and propene yield.
Description of drawings
Fig. 1 is a kind of structural representation that adopts the device of methyl alcohol or dimethyl ether production low-carbon alkene provided by the invention, and wherein the catalyst pretreatment device adopts riser tube, and the riser tube outlet links to each other with the reactor middle and upper part, and catalyst pretreatment device and reactor are arranged in juxtaposition.
Fig. 2 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, and wherein the catalyst pretreatment device adopts riser tube, and the riser tube outlet links to each other with reactor lower part, and catalyst pretreatment device and reactor are arranged in juxtaposition.
Fig. 3 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, wherein the catalyst pretreatment device adopts riser tube, catalyzer fast separation device and cyclonic separator are arranged at catalyst pretreatment device top, and catalyst pretreatment device and reactor are arranged in juxtaposition.
Fig. 4 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, and wherein the catalyst pretreatment device adopts riser tube, catalyst pretreatment device and reactor coaxial arrangement.
Fig. 5 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, wherein the catalyst pretreatment device adopts riser tube, riser tube passes beds, the riser tube top is provided with the catalyzer fast separation device, catalyst pretreatment device and reactor coaxial arrangement.
Fig. 6 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, wherein the catalyst pretreatment device adopts riser tube, riser tube passes beds, the riser tube top is provided with the catalyzer fast separation device, reactor head also is provided with cyclonic separator, catalyst pretreatment device and the reactor coaxial arrangement of using for the catalyst pretreatment device.
Fig. 7 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, wherein the catalyst pretreatment device adopts dense phase fluidized bed, the dense phase fluidized bed top is provided with cyclonic separator, catalyst pretreatment device and reactor coaxial arrangement.
Fig. 8 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, and wherein the catalyst pretreatment device adopts moving-bed, and the moving-bed top is provided with cyclonic separator, catalyst pretreatment device and reactor coaxial arrangement.
Fig. 9 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, and wherein the catalyst pretreatment device adopts fixed bed, and the fixed bed top is provided with cyclonic separator, catalyst pretreatment device and reactor coaxial arrangement.
Among the figure: the 1-reactor; The 2-catalyst regenerator; 3-catalyst pretreatment device; 4-first gas distributor; 5-first cyclonic separator; 6-second gas distributor; The 7-second cyclonic separator b; 8-the 3rd gas distributor; 9-catalyzer fast separation device 10-the 3rd cyclonic separator;
Embodiment
The invention provides a kind of device that adopts methyl alcohol or dimethyl ether production low-carbon alkene, this device comprises reactor body, be arranged on the gas distributor of reactor bottom, be arranged on the cyclonic separator of reactor head, the catalyst regenerator main body, be arranged on the gas distributor of catalyst regenerator bottom, be arranged on the cyclonic separator at catalyst regenerator top, described reactor body and catalyst regenerator main body are arranged in juxtaposition, pipe connection is passed through in the bottom of described reactor body and catalyst regenerator main body, this device also comprises the catalyst pretreatment device, be provided with gas feed and gas distributor in the bottom of described catalyst pretreatment device, the outlet of catalyst pretreatment device is connected with reactor body.
Described reactor and catalyst regenerator, purpose provide the container that unstripped gas or resurgent gases contact with catalyzer, and the reactor that can provide gas to contact with catalyzer all can be realized the reactor in this device and the effect of revivifier.Therefore, reactor among the present invention and revivifier all can be selected conventional fixed bed, fluidized-bed or moving-bed for use, and preferred reactor of the present invention and revivifier are fluidized-beds.
Described catalyst pretreatment device, purpose provides the container that unstripped gas or resurgent gases contact with catalyzer, the reactor that can provide gas to contact with catalyzer all can be realized the effect of catalyst pretreatment in this device, therefore, catalyst pretreatment device among the present invention can be selected conventional fixed bed, fluidized-bed or moving-bed for use, and the preferred pretreater of the present invention is riser tube fluidized-bed reactor or dense fluidized bed bioreactor.
Described reactor, catalyst regenerator and catalyst pretreatment device according to the difference of operating method, can adopt different reactors respectively, also can the same reactor of wherein two or more employings; Promptly can adopt different reactors in series to carry out cyclical operation, also can adopt same reactor to carry out periodical operation.
For described pretreatment reaction device, finish rear catalyst and reaction end gas will be discharged pretreater at preprocessing process, catalyzer can enter reactor without separating together with pre-treatment tail gas, also can be through separating, tripping device can be selected different devices as required for use, the preferred tripping device of the present invention is that the catalyzer fast separation device is or/and cyclone separator, catalyzer after the separation enters reactor, pre-treatment tail gas after the separation can enter reactor, also can not enter reactor, discharge by the pretreater pneumatic outlet.
Described pretreatment reaction device, finish rear catalyst and pre-treatment tail gas will be discharged pretreater at preprocessing process, catalyzer and pre-treatment tail gas can enter the emulsion zone of reactor, pre-treatment tail gas is continued and the catalyzer contact reacts, also can enter the freeboard of fluidized bed of reactor, together discharge reactor with product gas.
For technical scheme of the present invention and technique effect better are described, engage description of drawings the specific embodiment of the present invention below:
Fig. 1 is a kind of structural representation that adopts the device of methyl alcohol or dimethyl ether production low-carbon alkene provided by the invention, and wherein the catalyst pretreatment device adopts riser tube, and the riser tube outlet links to each other with the reactor middle and upper part, and catalyst pretreatment device and reactor are arranged in juxtaposition.Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2, pretreatment gas enters riser tube pretreater 3 through gas distributor 8, carrying pending catalyzer rises, in uphill process, catalyzer is carried out pre-treatment, enter reactor 1 freeboard of fluidized bed together at pretreater 3 tops and catalyzer; Unstripped gas enters reactor 1 through gas distributor 4, with the catalyzer contact reacts after cyclonic separator 5 back outflow reactors 1; Reclaimable catalyst is delivered to catalyst regenerator 2 from reactor 1, and regeneration gas enters revivifier through gas distributor 6, contact the coke in the burn off catalyzer with catalyzer after, outflow reactor 2 behind cyclonic separator 7; Catalyzer after the regeneration enters riser tube pretreater 3 by catalyst regenerator 2 and circulates.
Fig. 2 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, and wherein the catalyst pretreatment device adopts riser tube, and the riser tube outlet links to each other with reactor lower part, and catalyst pretreatment device and reactor are arranged in juxtaposition.Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2, pretreatment gas enters riser tube pretreater 3 through gas distributor 8, carrying pending catalyzer rises, in uphill process, catalyzer is carried out pre-treatment, enter the emulsion zone of reactor 1 at pretreater 3 top gas and catalyzer; Unstripped gas enters reactor 1 through gas distributor 4, with the catalyzer contact reacts after cyclonic separator 5 back outflow reactors 1; Reclaimable catalyst is delivered to catalyst regenerator 2 from reactor 1, and regeneration gas enters revivifier through gas distributor 6, contact the coke in the burn off catalyzer with catalyzer after, outflow reactor 2 behind cyclonic separator 7; Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2 and circulates.
Fig. 3 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, wherein the catalyst pretreatment device adopts riser tube, catalyzer fast separation device and cyclonic separator are arranged at catalyst pretreatment device top, and catalyst pretreatment device and reactor are arranged in juxtaposition.Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2, pretreatment gas enters riser tube pretreater 3 through gas distributor 8, carrying pending catalyzer rises, in uphill process, catalyzer is carried out pre-treatment, at pretreater 3 top gas and catalyzer after catalyzer fast separation device 9 and catalyst separating, gas flows out pretreater 3 behind cyclonic separator 10, catalyzer enters reactor 1 freeboard of fluidized bed; Unstripped gas enters reactor 1 through gas distributor 4, with the catalyzer contact reacts after cyclonic separator 5 back outflow reactors 1; Reclaimable catalyst is delivered to catalyst regenerator 2 from reactor 1, and regeneration gas enters revivifier through gas distributor 6, contact the coke in the burn off catalyzer with catalyzer after, outflow reactor 2 behind cyclonic separator 7; Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2 and circulates.
Fig. 4 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, and wherein the catalyst pretreatment device adopts riser tube, catalyst pretreatment device and reactor coaxial arrangement.Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2, pretreatment gas enters riser tube pretreater 3 through gas distributor 8, carrying pending catalyzer rises, in uphill process, catalyzer is carried out pre-treatment, enter the emulsion zone of reactor 1 at pretreater 3 top gas and catalyzer; Unstripped gas enters reactor 1 through gas distributor 4, with the catalyzer contact reacts after cyclonic separator 5 back outflow reactors 1; Reclaimable catalyst is delivered to catalyst regenerator 2 from reactor 1, and regeneration gas enters revivifier through gas distributor 6, contact the coke in the burn off catalyzer with catalyzer after, outflow reactor 2 behind cyclonic separator 7; Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2 and circulates.
Fig. 5 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, wherein the catalyst pretreatment device adopts riser tube, riser tube passes beds, the riser tube top is provided with the catalyzer fast separation device, catalyst pretreatment device and reactor coaxial arrangement.Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2, pretreatment gas enters riser tube pretreater 3 through gas distributor 8, carrying pending catalyzer rises, in uphill process, catalyzer is carried out pre-treatment, at pretreater 3 top gas and catalyzer after catalyzer fast separation device 9 and catalyst separating, catalyzer enters the emulsion zone of reactor 1, and gas mixes with gas in the reactor; Unstripped gas enters reactor 1 through gas distributor 4, after the catalyzer contact reacts with tail gas outflow reactor 1 behind cyclonic separator 5 of pretreater; Reclaimable catalyst is delivered to catalyst regenerator 2 from reactor 1, and regeneration gas enters revivifier through gas distributor 6, contact the coke in the burn off catalyzer with catalyzer after, outflow reactor 2 behind cyclonic separator 7; Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2 and circulates.
Fig. 6 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, wherein the catalyst pretreatment device adopts riser tube, riser tube passes beds, the riser tube top is provided with the catalyzer fast separation device, reactor head also is provided with cyclonic separator, catalyst pretreatment device and the reactor coaxial arrangement of using for the catalyst pretreatment device.Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2, pretreatment gas enters riser tube pretreater 3 through gas distributor 8, carrying pending catalyzer rises, in uphill process, catalyzer is carried out pre-treatment, at pretreater 3 top gas and catalyzer after catalyzer fast separation device 9 and catalyst separating, gas flows out pretreater 3 behind cyclonic separator 10, catalyzer enters reactor 1 emulsion zone; Unstripped gas enters reactor 1 through gas distributor 4, with the catalyzer contact reacts after cyclonic separator 5 back outflow reactors 1; Reclaimable catalyst is delivered to catalyst regenerator 2 from reactor 1, and regeneration gas enters revivifier through gas distributor 6, contact the coke in the burn off catalyzer with catalyzer after, outflow reactor 2 behind cyclonic separator 7; Pending catalyzer enters riser tube pretreater 3 by catalyst regenerator 2 and circulates.
Fig. 7 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, wherein the catalyst pretreatment device adopts dense phase fluidized bed, the dense phase fluidized bed top is provided with cyclonic separator, catalyst pretreatment device and reactor coaxial arrangement.Pending catalyzer enters dense phase fluidized bed pretreater 3 by catalyst regenerator 2, pretreatment gas enters dense phase fluidized bed pretreater 3 through gas distributor 8, pending catalyzer is carried out pre-treatment, flow out pretreater 3 through cyclonic separator 10 then; Catalyzer after the processing enters reactor 1 by dense phase fluidized bed pretreater 3, and unstripped gas enters reactor 1 through gas distributor 4, with the catalyzer contact reacts after cyclonic separator 5 back outflow reactors 1; Reclaimable catalyst is delivered to catalyst regenerator 2 from reactor 1, and regeneration gas enters revivifier through gas distributor 6, contact the coke in the burn off catalyzer with catalyzer after, outflow reactor 2 behind cyclonic separator 7; Pending catalyzer enters dense phase fluidized bed pretreater 11 by catalyst regenerator 2 and circulates.
Fig. 8 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, and wherein the catalyst pretreatment device adopts moving-bed, and the moving-bed top is provided with cyclonic separator, catalyst pretreatment device and reactor coaxial arrangement.Pending catalyzer enters moving-bed pretreater 3 by catalyst regenerator 2, and pretreatment gas enters moving-bed pretreater 3 through gas distributor 8, and pending catalyzer is carried out pre-treatment, flows out pretreater 3 through cyclonic separator 10 then; Catalyzer after the processing enters reactor 1 by moving-bed pretreater 3, and unstripped gas enters reactor 1 through gas distributor 4, with the catalyzer contact reacts after cyclonic separator 5 back outflow reactors 1; Reclaimable catalyst is delivered to catalyst regenerator 2 from reactor 1, and regeneration gas enters revivifier through gas distributor 6, contact the coke in the burn off catalyzer with catalyzer after, outflow reactor 2 behind cyclonic separator 7; Pending catalyzer enters moving-bed pretreater 14 by catalyst regenerator 2 and circulates.
Fig. 9 is the structural representation of the device of another employing methyl alcohol provided by the invention or dimethyl ether production low-carbon alkene, and wherein the catalyst pretreatment device adopts fixed bed, and the fixed bed top is provided with cyclonic separator, catalyst pretreatment device and reactor coaxial arrangement.Pending catalyzer enters fixed bed pretreater 3 by catalyst regenerator 2, and pretreatment gas is fed fixed bed pretreater 3, and pending catalyzer is carried out pre-treatment, flows out pretreater 3 then; Catalyzer after the processing enters reactor 1 by pretreater 3, and unstripped gas enters reactor 1 through gas distributor 4, with the catalyzer contact reacts after cyclonic separator 5 back outflow reactors 1; Reclaimable catalyst is delivered to catalyst regenerator 2 from reactor 1, and regeneration gas enters revivifier through gas distributor 6, contact the coke in the burn off catalyzer with catalyzer after, outflow reactor 2 behind cyclonic separator 7; Fixed bed pretreater 3 can be made up of two or more fixed beds, and each fixed bed is used alternatingly and can makes whole process cyclical operation.
Embodiment 1:
Catalyst pretreatment: it is in the fluidized-bed reactor of 50mm that the SAPO-34 catalyzer after the 100g regeneration is added internal diameter, weight in catalyzer is benchmark, the initial carbon content of catalyzer is 0.1-0.3%, pretreatment temperature is 450 ℃, absolute pressure is 0.15MPa, purge 30min with high-purity N 2 earlier, nitrogen flow is 60L/h, pre-treatment gas is added from reactor bottom, the composition of pre-treatment gas is a methyl alcohol again, and its mass space velocity is 1/h, feed time remaining 10min, purging 30min with high-purity N 2 again, is benchmark in the weight of catalyzer, and the catalyzer carbon content after the processing is 3.1-3.7%.
MTO reaction: use the employed reactor of catalyst pretreatment device, keeping temperature of reaction is 500 ℃, absolute pressure is 0.15MPa, material benzenemethanol feeds in the reactor after the preheater gasification, methyl alcohol is 3/h with respect to the mass space velocity of catalyzer, reactor outlet product condensing tube condensation, collect with air collector through condensed reactant gases, liquid carries out online methanol concentration analysis, reaction reaches 4% o'clock stopped reaction until outlet liquid phase methanol quality concentration, get that gas carries out the analysis of hydrocarbon content in the air collector with gas-chromatography, the selectivity sum of ethene and propylene is 81.7-82.8% in the gaseous products, weight in catalyzer is benchmark, and coke content is 7.2-7.6% in the catalyzer after using.
Catalyst regeneration: use the employed reactor of catalyst pretreatment device, keeping regeneration temperature is 600 ℃, absolute pressure is 0.15MPa, use air as regeneration gas, air flow quantity is 60L/h, the feeding time is 1h, is benchmark in the weight of catalyzer, and the catalyzer after the regeneration on average contains the coke of 0.1-0.3%.
Embodiment 2: adopt the reaction unit among the embodiment 5, pretreatment gas adopts 1-butylene in the catalyst pretreatment device, pretreatment temperature is controlled at 580-600 ℃, absolute pressure is 0.14-0.16MPa, the pretreatment gas mass space velocity is 1.5/h, weight in catalyzer is benchmark, and average coke level is 2.1-2.5% in the riser tube outlet catalyzer; Reactant gases adopts methyl alcohol in the reactor, and temperature of reaction is controlled at 470-480 ℃, and absolute pressure is 0.14-0.16MPa, and the methanol quality air speed is 4/h, is benchmark in the weight of catalyzer, and average coke level is 7.3-7.8% in the catalyzer; Regeneration gas adopts air in the catalyst regenerator, and regeneration temperature is controlled at 650-660 ℃, and absolute pressure is 0.14-0.16MPa, is benchmark in the weight of catalyzer, and average coke level is 0.1-0.3% in the catalyzer.Under the aforesaid operations condition, the selectivity sum of ethene and propylene can reach 83.2-83.7% in the reactor outlet gas phase hydro carbons.
Embodiment 3: adopt the reaction unit among the embodiment 6, pretreatment gas employing volume content is 50%, 50% propylene and propane mixed gas in the catalyst pretreatment device, pretreatment temperature is controlled at 540-560 ℃, absolute pressure is 0.14-0.16MPa, the pretreatment gas mass space velocity is 2/h, weight in catalyzer is benchmark, and average coke level is 3-3.5% in the catalyzer; Reactant gases adopts methyl alcohol in the reactor, and temperature of reaction is controlled at 500-510 ℃, and absolute pressure is 0.14-0.16MPa, and the methanol quality air speed is 2/h, is benchmark in the weight of catalyzer, and average coke level is 7.1-7.6% in the catalyzer; Regeneration gas adopts air in the catalyst regenerator, and regeneration temperature is controlled at 650-660 ℃, and absolute pressure is 0.14-0.16MPa, is benchmark in the weight of catalyzer, and average coke level is 0.1-0.3% in the catalyzer.Under the aforesaid operations condition, the selectivity sum of ethene and propylene can reach 82.3-83.3% in the reactor outlet gas phase hydro carbons.
Utilize this device can realize the process of methyl alcohol or dimethyl ether production low-carbon alkene, owing to add the catalyst pretreatment device, reaction result is better than existing result as device as described in the CN1166478A, reaches the optionally purpose that increases ethene and propylene.
Claims (11)
1. device that adopts methyl alcohol or dimethyl ether production low-carbon alkene, this device comprises reactor body (1), be arranged on the gas distributor (4) of reactor bottom, be arranged on the cyclonic separator (5) of reactor head, catalyst regenerator main body (2), be arranged on the gas distributor (6) of catalyst regenerator bottom, be arranged on the cyclonic separator (7) at catalyst regenerator top, described reactor body and catalyst regenerator main body are arranged in juxtaposition, pipe connection is passed through in the bottom of described reactor body and catalyst regenerator main body, it is characterized in that: this device also comprises catalyst pretreatment device (3), be provided with gas feed and gas distributor (8) in the bottom of described catalyst pretreatment device, the top of catalyst pretreatment device is connected with reactor body.
2. according to the device of described employing methyl alcohol of claim 1 or dimethyl ether production low-carbon alkene, it is characterized in that: described catalyst pretreatment device adopts the riser tube pretreater, riser tube pretreater and reactor body and revivifier are arranged in juxtaposition, and the top of riser tube pretreater is connected with the middle and upper part of reactor body or bottom.
3. according to the device of described employing methyl alcohol of claim 2 or dimethyl ether production low-carbon alkene, it is characterized in that: be provided with catalyzer fast separation device (9), cyclonic separator (10) and pneumatic outlet at the top of described riser tube pretreater, the outlet of described catalyzer fast separation device is connected with the reactor middle and upper part.
4. according to the device of described employing methyl alcohol of claim 1 or dimethyl ether production low-carbon alkene, it is characterized in that: described catalyst pretreatment device adopts the riser tube pretreater, described riser tube pretreater and reactor body coaxial arrangement, the top of riser tube pretreater is connected with the bottom of reactor body.
5. according to the device of described employing methyl alcohol of claim 4 or dimethyl ether production low-carbon alkene, it is characterized in that: the dense-phase bed of reactor is passed on the top of riser tube pretreater, is provided with catalyzer fast separation device (9) at the top of riser tube pretreater.
6. according to the device of described employing methyl alcohol of claim 5 or dimethyl ether production low-carbon alkene, it is characterized in that: the top of described reactor body also is provided with the cyclonic separator of using for pretreater (10), and the pneumatic outlet of this catalyzer fast separation device is connected with the described cyclonic separator of using for pretreater.
7. according to the device of described employing methyl alcohol of claim 1 or dimethyl ether production low-carbon alkene, it is characterized in that: described catalyst pretreatment device adopts the dense phase fluidized bed pretreater, be provided with cyclonic separator (10) at described dense phase fluidized bed pretreater top, dense phase fluidized bed pretreater and reactor body and catalyst regenerator are arranged in juxtaposition, and the middle and lower part of dense phase fluidized bed pretreater is connected with the middle and upper part of reactor body or bottom.
8. according to the device of described employing methyl alcohol of claim 1 or dimethyl ether production low-carbon alkene, it is characterized in that: described catalyst pretreatment device adopts the moving-bed pretreater, be provided with cyclonic separator (10) at described moving-bed pretreater top, moving-bed pretreater and reactor body and catalyst regenerator are arranged in juxtaposition, and the bottom of moving-bed pretreater is connected with the middle and upper part of reactor body or bottom.
9. according to the device of described employing methyl alcohol of claim 1 or dimethyl ether production low-carbon alkene, it is characterized in that: described catalyst pretreatment device adopts the fixed bed pretreater, described fixed bed pretreater and reactor body and catalyst regenerator are arranged in juxtaposition, and the bottom of fixed bed pretreater is connected with the middle and upper part of reactor body or bottom.
10. according to the device of arbitrary described employing methyl alcohol of claim 1-9 or dimethyl ether production low-carbon alkene, it is characterized in that: reactor adopts fluidized-bed, moving-bed or fixed-bed reactor, and reactor preferably adopts fluidized-bed; Catalyst regenerator adopts fluidized-bed, moving-bed or fixed bed revivifier, and revivifier preferably adopts fluidized-bed; Reactor, catalyst regenerator, catalyst pretreatment device adopt different reactors separately, or the same reactor of wherein two or more employings.
11. device according to arbitrary described employing methyl alcohol of claim 1-9 or dimethyl ether production low-carbon alkene, it is characterized in that: between described reactor and catalyst regenerator, also be provided with stripper, be provided with gas distributor in described stripper bottom, the top is provided with cyclonic separator, and stripper is connected by pipeline with the bottom of reactor and catalyst regenerator.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102106368A CN101698629B (en) | 2009-11-04 | 2009-11-04 | Device for preparing low-carbon olefin by adopting methanol or dimethyl ether |
| PCT/CN2010/074459 WO2011054205A1 (en) | 2009-11-04 | 2010-06-25 | Device for preparing lower alkenes with methanol or dimethyl ether |
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| CN2009102106368A CN101698629B (en) | 2009-11-04 | 2009-11-04 | Device for preparing low-carbon olefin by adopting methanol or dimethyl ether |
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| WO2011054205A1 (en) * | 2009-11-04 | 2011-05-12 | 兆威兴业有限公司 | Device for preparing lower alkenes with methanol or dimethyl ether |
| CN102633246A (en) * | 2011-05-27 | 2012-08-15 | 天津市贝特瑞新能源材料有限责任公司 | Complete equipment for preparing intermediate phase carbon microball as well as catalyst pretreatment device and preparation method |
| CN104117328A (en) * | 2014-08-04 | 2014-10-29 | 陕西延长石油(集团)有限责任公司研究院 | Continuous reaction-generation catalytic conversion system and method |
| CN104672045A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院大连化学物理研究所 | Reaction device for preparing low-carbon olefin by employing methyl alcohol and/or dimethyl ether |
| WO2021180195A1 (en) * | 2020-03-13 | 2021-09-16 | 中国石油化工股份有限公司 | Method for converting methanol in fluidized bed reactor |
| WO2022057805A1 (en) * | 2020-09-15 | 2022-03-24 | 中国石油化工股份有限公司 | Catalyst mixing device |
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| US6023005A (en) * | 1997-07-03 | 2000-02-08 | Exxon Chemicals Patents Inc. | Process for converting oxygenates to olefins using molecular sieve catalysts comprising desirable carbonaceous deposits |
| CN101270023B (en) * | 2008-04-11 | 2011-04-27 | 中国石油化工股份有限公司 | Method for improving yield of light olefin hydrocarbon |
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| CN102633246A (en) * | 2011-05-27 | 2012-08-15 | 天津市贝特瑞新能源材料有限责任公司 | Complete equipment for preparing intermediate phase carbon microball as well as catalyst pretreatment device and preparation method |
| CN104672045A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院大连化学物理研究所 | Reaction device for preparing low-carbon olefin by employing methyl alcohol and/or dimethyl ether |
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| WO2022057805A1 (en) * | 2020-09-15 | 2022-03-24 | 中国石油化工股份有限公司 | Catalyst mixing device |
| US20230125888A1 (en) * | 2020-10-16 | 2023-04-27 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Regeneration device, device for preparing low-carbon olefins, and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101698629B (en) | 2013-07-17 |
| WO2011054205A1 (en) | 2011-05-12 |
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