CN207294636U - A kind of reaction unit of high efficiency methanol alkene - Google Patents
A kind of reaction unit of high efficiency methanol alkene Download PDFInfo
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- CN207294636U CN207294636U CN201720972787.7U CN201720972787U CN207294636U CN 207294636 U CN207294636 U CN 207294636U CN 201720972787 U CN201720972787 U CN 201720972787U CN 207294636 U CN207294636 U CN 207294636U
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Abstract
Coal-to-olefin, technical field of petrochemical industry are the utility model is related to, in particular to a kind of reaction unit of high efficiency methanol alkene.In the reaction unit, methanol gasifying device, methanol heater, preparing dimethyl ether from methanol reactor, methanol/dimethyl ether alkene main reactor are sequentially connected；The methanol/dimethyl ether alkene main reactor is bi-directionally connected by two pipelines of pipe to be generated and regenerating tube with catalyst regenerator.Methanol to olefins reaction is carried out using the reaction unit, mild condition, energy efficiency utilization rate are high.
Description
Technical field
Coal-to-olefin, technical field of petrochemical industry are the utility model is related to, in particular to a kind of high efficiency methanol alkene
The reaction unit of hydrocarbon.
Background technology
Traditional ethene, propylene produce route mainly by naphtha pyrolysis production, the drawback is that too relying on stone
Oil.It is the process route for being most hopeful to substitute that naphtha is raw material alkene by low-carbon alkenes such as methanol ethene, propylene, at present
Tend to be ripe.
Methanol-to-olefins (Methanol to Olefins, MTO) are important C1 chemical processes, are former with petrochemical industry
Material prepares the alternative route of ethene, is using coal or natural gas as primary raw material, is converted into methanol through synthesis gas, is then then converted to
The route of alkene, is completely independent of oil.It is expected to become the important route of production alkene in the 21 century of oil worsening shortages.
The development of methanol-to-olefins technology, opens by new process road of the coal through gasification production basic organic chemical raw material
Line, is conducive to optimize the product general layout of traditional Coal Industrial, improves the competitiveness in reply market, is to realize coal chemical industry to oil
The effective way of chemical extending development, while the contradiction to alleviating China's oil shortage has important strategy and realistic meaning.
The raw material resources such as China's naphtha and light diesel fuel shortage at present, if still produced only using them as low-carbon alkene
One raw material sources, to meet that volume increase demand of the China every year to low-carbon alkene is obviously not all right, it is necessary to walk out a new approach.If
In the area of rich coal resources in China, accelerate the industrial development of coal base MTO techniques, realize using ethene, propylene as the low of representative
Carbon olefin raw materials for production diversification, can yet be regarded as and solve China's oil resource anxiety, promote China's low-carbon alkene rapid industrial development
Most effective approach, be also beneficial to realize in China that the ground big province of producing coal realizes that coal resources advantage converts.On the other hand, it is near several
Year, China's methanol market long-term maintain a high position so that social great amount of investment methanol it is as warm as before, MTO technologies are also root
This solution methanol market outlet provides guarantee.
Mobil companies of last century the seventies U.S. research methanol using ZSM-5 catalyst be converted into it is other containing oxidation
During compound, it was found that preparing gasoline by methanol (Methanol to Gasoline, MTG) reacts.Analyzed from MTG reaction mechanisms, low-carbon
Alkene is the intermediate product of MTG reactions, thus MTG techniques succeed in developing the exploitation for promoting MTO techniques.
Mobil companies are studied methanol and are converted into ethene and other earliest based on the ZSM-5 catalyst that the said firm develops
The work of low-carbon alkene, however, make a breakthrough be two companies of UOP and Norsk Hydro cooperative development with UOP
MTO-100 is the MTO techniques of the UOP/Hydro of catalyst.
Domestic scientific research mechanism, such as Chinese Academy of Sciences Dalian Chemistry and Physics Institute, University of Petroleum, Sinopec Research Institute of Petro-Chemical Engineering
Also similar work has been carried out.Wherein process route (SDTO) of the synthesis gas through dimethyl ether low-carbon alkene of Dalian Chemistry and Physics Institute exploitation
Has originality, compared with MTO of the Conventional synthesis gas through preparing light olefins from methanol, CO high conversion rates, up to more than 90%, build and throw
Money and operating cost save 50%~80%.When using D0123 catalyst, product is catalyzed based on ethene when using D0300
Agent is product based on propylene.
In view of this, it is special to propose the utility model.
Utility model content
The purpose of this utility model is to provide a kind of reaction unit of high efficiency methanol alkene, and first is carried out using the device
Alcohol olefine reaction, reaction condition is gentle, energy efficiency utilization rate is high.
In order to realize the above-mentioned purpose of the utility model, spy uses following technical scheme：
A kind of reaction unit of high efficiency methanol alkene, in the reaction unit, methanol gasifying device, methanol heater,
Preparing dimethyl ether from methanol reactor, methanol/dimethyl ether alkene main reactor are sequentially connected；
The methanol/dimethyl ether alkene main reactor passes through two pipelines of pipe to be generated and regenerating tube and catalyst regenerator
It is bi-directionally connected.
Preferably, reaction unit as described above, is provided with methanol inlet on the methanol gasifying device.
Preferably, reaction unit as described above, is additionally provided with smoke stack emission mouth and regeneration on the catalyst regenerator
Medium inlet.
Preferably, reaction unit as described above, reaction production is provided with the methanol/dimethyl ether alkene main reactor
Thing exports.
Preferably, reaction unit as described above, the reaction unit further includes energy recovery unit, and the chimney is arranged
Put mouth and/or the reacting product outlet is connected with the energy recovery unit；
Preferably, reaction unit as described above, the energy recovery unit have two, the smoke stack emission mouth and first
Energy recovery unit is connected, and the reacting product outlet is connected with the second energy recovery unit.
Preferably, reaction unit as described above, the methanol gasifying device and/or methanol heater and the energy regenerating
Unit is contacted by heating equipment.
Preferably, reaction unit as described above, the reaction unit further include separation of olefins unit, and the reaction production
Thing outlet is connected with the separation of olefins unit.
Preferably, reaction unit as described above, the methanol/dimethyl ether alkene main reactor are fluidized-bed reaction
Device.
Preferably, reaction unit as described above, the top of the methanol/dimethyl ether alkene main reactor are additionally provided with
Cyclone separator.
The utility model further relates to a kind of method of the methanol-to-olefins based on above-mentioned reaction unit, including：
1) methanol feedstock is carried out condensation reaction into preparing dimethyl ether from methanol reactor after gasification and heating and obtains first by
The mixture of alcohol, dimethyl ether and water；
2) mixture is passed through methanol/dimethyl ether alkene main reactor by, and high temperature is carried out under the action of catalyst
Olefine reaction processed；
Wherein, the catalyst is regenerated into catalyst regenerator, and the catalyst regenerated enters back into the first
Alcohol/dimethyl ether alkene main reactor re-uses；
The methanol feedstock is in gasification and heating process institute's calorific requirement by the methanol/dimethyl ether alkene main reactor
The pre- heat supply in regenerated flue gas part that reaction product heat production and/or the catalyst regenerator produce.
Preferably, method as described above, in step 2), the catalyst is the catalysis for including SAPO-34 molecular sieves
Agent.
Preferably, method as described above, in step 2), the reaction temperature of the high temperature olefine reaction is 400 DEG C
~450 DEG C, reaction pressure is 0.1~0.5MPa；
It is furthermore preferred that in step 2), the reaction temperature of the high temperature olefine reaction is 420 DEG C~430 DEG C, reaction pressure
Power is 0.2~0.4MPa.
Preferably, method as described above, in step 2), the reaction of the methanol/dimethyl ether alkene main reactor
Air speed is controlled in 1h-1~4h-1；
It is furthermore preferred that in step 2), the reaction velocity of the methanol/dimethyl ether alkene main reactor is controlled in 2h-1
~3h-1。
Preferably, method as described above, in step 1), after the condensation reaction, 80vt%~85vt%'s
Methanol is converted into dimethyl ether；
It is furthermore preferred that in step 1), after the condensation reaction, the methanol of 82vt%~83vt% is converted into diformazan
Ether.
Compared with prior art, the beneficial effects of the utility model are：
1), material benzenemethanol gasification and heating process institute calorific requirement can be preheated by the part of reactor product logistics or regenerated flue gas
Supply, more environmental protection and energy saving；
2), for the ease of taking the regeneration of reaction heat and catalyst away, using fluidized-bed reactor, reaction, regenerative operation are made
Serialization, greatly improves reaction efficiency；
3), after dimethyl ether reactor, the reaction mechanism mechanism of reaction in a fluidized bed reactor shortens, anti-using fluidisation compared to complete
The technique for answering device, the size and catalyst circulation amount that can make alkene main reactor reduce, and reach lower catalyst consumption, from
And consume less conveying steam, supplying nitrogen and regeneration air.So the processing cost of alkene is relatively low；
4), since catalyst is cyclic regeneration, the utilization rate of waste heat of regenerated flue gas is better than fixed bed flow；
5) structure, is formed by controlling reaction temperature and catalyst, adjusts the output ratio of propylene and ethene, more than C5 products
It is seldom with branched chain isomer thing；
6), the modified SAPO-34 catalyst used shows prominent superiority in the reaction of preparing olefin by conversion of methanol,
Selectivity is good, and selectivity of light olefin is up to 90%, and physical strength is high, anti-to burn.
7), reaction condition is gentle, and temperature is 400 DEG C~450 DEG C, and pressure is 1~5Bar.
Brief description of the drawings
, below will be right in order to illustrate more clearly of the utility model embodiment or technical solution of the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, describe below
In attached drawing be the utility model some embodiments, for those of ordinary skill in the art, do not paying creativeness
On the premise of work, other attached drawings can also be obtained according to these attached drawings.
Fig. 1 is the schematic diagram of the reaction unit of high efficiency methanol alkene provided by the utility model.
Reference numeral：
Methanol gasifying device 1；
Methanol heater 2；
Preparing dimethyl ether from methanol reactor 3；
Methanol/dimethyl ether alkene main reactor 4；
Catalyst regenerator 5；
Methanol inlet 6；
Reacting product outlet 7；
Pipe 8 to be generated；
Regenerating tube 9；
Smoke stack emission mouth 10；
Regenerating medium entrance 11.
Embodiment
, it is necessary to explanation in the description of the utility model, term " " center ", " on ", " under ", it is "left", "right", " perpendicular
Directly ", the orientation of the instruction such as " level ", " interior ", " outer " or position relationship are based on orientation shown in the drawings or position relationship, are only
Described for the ease of description the utility model and simplifying, rather than instruction or imply signified device or element must have it is specific
Orientation, with specific azimuth configuration and operation, therefore it is not intended that limitation to the utility model.In addition, term " the
One ", " second ", " the 3rd " are only used for description purpose, and it is not intended that instruction or hint relative importance.
, it is necessary to which explanation, unless otherwise clearly defined and limited, term " are pacified in the description of the utility model
Dress ", " connected ", " connection " should be interpreted broadly, for example, it may be fixedly connected or be detachably connected, or integratedly
Connection；Can mechanically connect or be electrically connected；It can be directly connected, can also be indirectly connected by intermediary,
It can be the connection inside two elements.For the ordinary skill in the art, above-mentioned art can be understood with concrete condition
Concrete meaning of the language in the utility model.
As shown in Figure 1, the reaction unit of high efficiency methanol alkene provided by the utility model, including methanol gasifying device 1；First
Alcohol heater 2；Preparing dimethyl ether from methanol reactor 3；Methanol/dimethyl ether alkene main reactor 4 and catalyst regenerator 5.
The methanol gasifying device 1, methanol heater 2, preparing dimethyl ether from methanol reactor 3 and methanol/dimethyl ether alkene
Main reactor 4 is sequentially connected；
Methanol inlet 6 is provided with the methanol gasifying device 1；
Reacting product outlet 7 is provided with the methanol/dimethyl ether alkene main reactor 4；
The methanol/dimethyl ether alkene main reactor 4 by 9 two pipelines of pipe 8 to be generated and regenerating tube and catalyst again
Raw device 5 is bi-directionally connected；
Smoke stack emission mouth 10 and regenerating medium entrance 11 are additionally provided with the catalyst regenerator 5.
Wherein, it is preferred that the regenerating medium being passed through in the regenerating medium entrance 11 is air.
Preferably, reaction unit as described above, the reaction unit further includes energy recovery unit, and the chimney is arranged
Put mouth and/or the reacting product outlet is connected with the energy recovery unit；
It is furthermore preferred that the energy recovery unit has two, the smoke stack emission mouth is connected with the first energy recovery unit,
The reacting product outlet is connected with the second energy recovery unit.
Preferably, reaction unit as described above, the methanol gasifying device and/or methanol heater and the energy regenerating
Unit is contacted by heating equipment.
Preferably, reaction unit as described above, the reaction unit further include separation of olefins unit, and the reaction production
Thing outlet is connected with the separation of olefins unit.
The separation of olefins unit is mainly used for purification reaction product, it is final to the ethene of high-purity, propylene and other
Byproduct.
Preferably, reaction unit as described above, the methanol/dimethyl ether alkene main reactor are fluidized-bed reaction
Device.
Fluidized-bed reactor is that one kind is suspended using gas or liquid by granular solids layer be in solid particle
The reactor of motion state, promoting the circulation of qi solid phase reaction process of going forward side by side or liquid and solid phase reaction process.When for gas-solid system, also known as boil
Rise a reactor.Compared with fixed bed reactors, fluidized-bed reactor can realize that the continuous of solid material is output and input；Stream
The movement of body and particle makes bed have good heat transfer property, and bed internal temperature is uniform, and easily controllable, particularly suitable
In strong exothermal reaction；Cyclic regeneration and the circulate operation of catalyst are convenient for, suitable for the high process of catalyst deactivation rate
Carry out, petroleum distillate fluid catalytic cracking bed cracking develop rapidly be exactly this aspect exemplary.
Preferably, reaction unit as described above, the top of the methanol/dimethyl ether alkene main reactor are additionally provided with
Cyclone separator.The cyclone separator is used to collect and separate reaction product.
Technological process based on device provided by the utility model is as follows：
It is methanol saturated vapor that material benzenemethanol from tank field is injected into 1 heating and gasifying of methanol gasifying device through methanol inlet 6,
Enter preparing dimethyl ether from methanol reactor 3 after being heated to required temperature by methanol hot-air heater 2, about 75% methanol converts herein
For dimethyl ether and water.Methanol-dimethyl ether-aqueous mixtures of reactor outlet enter methanol/dimethyl ether alkene main reactor 4,
Mixed with the high temperature catalyst after regeneration and rise and occur exothermic reaction rapidly, reaction heat is by pipeline 7 by the steam zone of generation
Walk and recycle.After reactant flows through the cyclone separator separation of reactor top by reacting product outlet 7, after reaction product is sent to
Portion's energy regenerating and separative element it is final to the ethene of high-purity, propylene and other byproducts.The reclaimable catalyst isolated
Then delivered into through pipe 8 to be generated using nitrogen in catalyst regenerator 5, the regeneration air through being passed through is changed into regeneration catalyzing after burning
Agent, through regenerating tube 9, methanol/dimethyl ether alkene main reactor 4 is recycled back under steam conveying generation again is mixed with raw material instead
Should.Regenerated flue gas is after CO incinerators, waste heat boiler recycling heat from smoke stack emission.
Preferably, preparing dimethyl ether from methanol used catalyst is Cu/Al2O3, used in methanol/dimethyl ether alkene main reactor
Catalyst is modified small-porosity P-Si-Al (SAPO-34) molecular sieve catalyst.
The embodiment of the utility model is described in detail below in conjunction with embodiment, but those skilled in the art
It will be understood that the following example is merely to illustrate the utility model, and it is not construed as limitation the scope of the utility model.Embodiment
In the person that is not specified actual conditions, the condition suggested according to normal condition or manufacturer carries out.Life is not specified in agents useful for same or instrument
Manufacturer person is produced, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
The commercial methanol raw material of concentration about 100% heats up through gasification, enters methanol with 0.8MPa, 370 DEG C of reaction condition
Reaction of preparing dimethyl ether device, reactor outlet temperature are 430 DEG C, and about 80% methanol is converted into dimethyl ether.Gained methanol-dimethyl ether-
Aqueous mixtures enter fluidized-bed reactor with 0.5MPa, and reaction velocity is controlled in 4h-1, final methanol conversion is 100%.
The following olefin yields of gained C4 (being calculated with carbon atom molal quantity) are 61%, and wherein the yield of ethene+propylene is (with carbon
Atomic molar number calculates) it is 57%, ethene 31%, propylene 26%.
Embodiment 2
The commercial methanol raw material of concentration about 100% heats up through gasification, enters methanol with 0.8MPa, 380 DEG C of reaction condition
Reaction of preparing dimethyl ether device, reactor outlet temperature are 438 DEG C, and about 85% methanol is converted into dimethyl ether.Gained methanol-dimethyl ether-
Aqueous mixtures enter fluidized-bed reactor with 0.4MPa, and reaction velocity is controlled in 3h-1, final methanol conversion is 100%.
The following olefin yields of gained C4 (being calculated with carbon atom molal quantity) are 67%, and wherein the yield of ethene+propylene is (with carbon
Atomic molar number calculates) it is 63%, ethene 36%, propylene 27%.
Embodiment 3
The commercial methanol raw material of concentration about 100% heats up through gasification, enters methanol with 0.8MPa, 390 DEG C of reaction condition
Reaction of preparing dimethyl ether device, reactor outlet temperature are 450 DEG C, and about 83% methanol is converted into dimethyl ether.Gained methanol-dimethyl ether-
Aqueous mixtures enter fluidized-bed reactor with 0.3MPa, and reaction velocity is controlled in 2h-1, final methanol conversion is 100%.
The following olefin yields of gained C4 (being calculated with carbon atom molal quantity) are 74%, and wherein the yield of ethene+propylene is (with carbon
Atomic molar number calculates) it is 68%, ethene 39%, propylene 29%.
Embodiment 4
The commercial methanol raw material of concentration about 100% heats up through gasification, enters methanol with 0.8MPa, 390 DEG C of reaction condition
Reaction of preparing dimethyl ether device, reactor outlet temperature are 450 DEG C, and about 83% methanol is converted into dimethyl ether.Gained methanol-dimethyl ether-
Aqueous mixtures enter fluidized-bed reactor with 0.2MPa, and reaction velocity is controlled in 1h-1, final methanol conversion is 100%.
The following olefin yields of gained C4 (being calculated with carbon atom molal quantity) are 84%, and wherein the yield of ethene+propylene is (with carbon
Atomic molar number calculates) it is 73%, ethene 42%, propylene 31%.
Finally it should be noted that：Various embodiments above is only to illustrate the technical solution of the utility model, rather than it is limited
System；Although the utility model is described in detail with reference to foregoing embodiments, those of ordinary skill in the art should
Work as understanding：It can still modify the technical solution described in foregoing embodiments, either to which part or complete
Portion's technical characteristic carries out equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from this practicality
The scope of new each embodiment technical solution.
Claims (10)
- A kind of 1. reaction unit of high efficiency methanol alkene, it is characterised in that in the reaction unit, methanol gasifying device, first Alcohol heater, preparing dimethyl ether from methanol reactor, methanol/dimethyl ether alkene main reactor are sequentially connected；The methanol/dimethyl ether alkene main reactor is two-way by two pipelines of pipe to be generated and regenerating tube and catalyst regenerator Connection.
- 2. reaction unit according to claim 1, it is characterised in that be provided with methanol inlet on the methanol gasifying device.
- 3. reaction unit according to claim 1, it is characterised in that chimney row is additionally provided with the catalyst regenerator Put mouth and regenerating medium entrance.
- 4. reaction unit according to claim 3, it is characterised in that on the methanol/dimethyl ether alkene main reactor It is provided with reacting product outlet.
- 5. reaction unit according to claim 4, it is characterised in that the reaction unit further includes energy recovery unit, And the smoke stack emission mouth and/or the reacting product outlet are connected with the energy recovery unit.
- 6. reaction unit according to claim 5, it is characterised in that the energy recovery unit has two, the chimney Floss hole is connected with the first energy recovery unit, and the reacting product outlet is connected with the second energy recovery unit.
- 7. the reaction unit according to claim 5 or 6, it is characterised in that the methanol gasifying device and/or methanol heater Contacted with the energy recovery unit by heating equipment.
- 8. reaction unit according to claim 4, it is characterised in that the reaction unit further includes separation of olefins unit, And the reacting product outlet is connected with the separation of olefins unit.
- 9. reaction unit according to claim 1, it is characterised in that the methanol/dimethyl ether alkene main reactor is Fluidized-bed reactor.
- 10. reaction unit according to claim 1, it is characterised in that the methanol/dimethyl ether alkene main reactor Top is additionally provided with cyclone separator.
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| CN201720972787.7U CN207294636U (en) | 2017-08-04 | 2017-08-04 | A kind of reaction unit of high efficiency methanol alkene |
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| CN201720972787.7U CN207294636U (en) | 2017-08-04 | 2017-08-04 | A kind of reaction unit of high efficiency methanol alkene |
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