CN105617948A - Methanol conversion reactor and reaction system and methanol conversion method - Google Patents
Methanol conversion reactor and reaction system and methanol conversion method Download PDFInfo
- Publication number
- CN105617948A CN105617948A CN201410592192.XA CN201410592192A CN105617948A CN 105617948 A CN105617948 A CN 105617948A CN 201410592192 A CN201410592192 A CN 201410592192A CN 105617948 A CN105617948 A CN 105617948A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- housing
- methanol
- support plate
- catalyst support
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a methanol conversion reactor, a reaction system and a methanol conversion method. The reactor comprises a housing 2, a reaction gas outlet 4 arranged at the top of the housing 2, a feed gas inlet 1 arranged at the bottom of the housing 2, a catalyst inlet arranged in a side face of the top of the housing 2 and a spent agent outlet arranged in a side face of the bottom of the housing 2, wherein multiple catalyst support plates 3 which slantly extend to pass through cross section of the housing 2, are spaced from each other and are used for making a catalyst to slip down from the top of the housing 2 to the bottom of the housing 2 are also arranged inside the housing 2; lower ends of the catalyst support plates 3 are provided with gaps used as slipping channels of the catalyst; and the catalyst support plates 3 are provided with multiple small holes used for allowing reaction gas to flow upwards. According to the invention, contact efficiency can be raised, side reaction is reduced, and conversion rate of raw materials and selectivity of a target product are enhanced.
Description
Technical field
The present invention relates to a kind of methanol conversion and response system and the method for methanol conversion. In particular it relates to a kind of gas-solid circulated in countercurrent moving-burden bed reactor, the reaction of methanol conversion system containing this reactor and adopt the method that this response system carries out methanol-to-olefins reaction or gasoline.
Background technology
Methanol-to-olefins reaction or gasoline are important " carbon one " chemical processes, it is possible to for solving the purposes of methanol and increasing low-carbon alkene or gasoline products. The reaction of methanol conversion mostly is heterogeneous catalytic reaction process, and the reaction that catalyst occurs is parallel and the complex reaction of consecutive reaction mixing, and differential responses are different to the Active pharmaceutical of catalyst, and products distribution is also different. Therefore industrial to have expected that suitable yield and selective target product need course of reaction is had rational control, take the way of contact of suitable catalyst and reaction mass.
Exxon Mobil adopts fixed bed reactors to carry out preparing gasoline by methanol production, and five fixed bed reactors are arranged side by side, and four-in-one is standby, and each reactor runs regeneration in 14 days once. Inert gas purge reactor must be used before regeneration, question response device combustable gas concentration is down to certain value, blowing air or oxygen-containing gas carry out coke burning regeneration, make renewing catalyst activity, after burning end, more logical inert gas purge reactor, the oxygen concentration to reactor is lower than certain value, logical methanol steam, about needs 2.5 days again. Owing to each reactor needs frequent regeneration, and regenerative process is complicated, this considerably increases the complexity of operation and running cost, and reactor is high-pressure reactor, and regenerative process is normal pressure process, which increases equipment investment, improve the costs of production and operation of enterprise.
LURGI adopts fixed bed reactors to carry out preparing propylene from methanol process, similar with the preparing gasoline by methanol process of Exxon Mobil, three open one standby, switching regeneration between different reactor. But each reactor is all almost atmospheric operation, it is not necessary to boosting frequently, pressure reduction, relatively easy compared with preparing gasoline by methanol process, but frequently purging, regeneration still considerably increase running cost and complexity.
UOP and bigization institute employing fluid bed MTO technology, but bed back-mixing is serious, and the catalyst of different coke contents is blended together, approximate in continuous stir reactor. But in fluid bed, presenting the spatial distribution of gas with various concentration vertically, catalyst characteristics required when different gas concentration also differs, and the catalyst of complete mixed state cannot meet these requirements, affecting catalytic effect, the products distribution and the conversion ratio that obtain are undesirable.
Device complicated operation in prior art, and catalytic reaction weak effect. Accordingly, it would be desirable to one is capable of methanol conversion better effect, obtains low-carbon alkene or gasoline as much as possible, and obtain the methanol conversion process of the little molecule alkane products such as methane, ethane, propane as little as possible.
Summary of the invention
It is an object of the invention to overcome the defect of prior art methanol changing effect difference, it is provided that a kind of method that methanol conversion and response system and methanol convert.
To achieve these goals, the present invention provides a kind of methanol conversion, and this reactor includes: the spent agent outlet that housing 2, the reaction gas outlet 4 offered on the top of housing 2, the unstripped gas entrance 1 offered in the bottom of housing 2, the catalyst inlet offered in the top-side of housing 2 and the bottom sides at housing 2 are offered; Wherein, in housing 2, also set up multiple cross section extending obliquely through housing 2 and catalyst support plate 3 spaced apart each other, for making catalyst be slipped to the bottom of housing 2 from the top of housing 2; Low side at catalyst support plate 3 offers breach, as the landing passage of catalyst; Catalyst support plate 3 is offered multiple aperture, flows up for reacting gas.
Present invention also offers the response system that a kind of methanol converts, this system includes: methanol conversion, stripper 9 and regenerator 12; The catalyst inlet of methanol conversion is communicated to regenerator 12 by catalyst transport pipeline 5; The spent agent outlet of methanol conversion is to stripper 9; The bottom of stripper 9 is communicated to the bottom of regenerator 12 by spent agent feed-line 17; Described methanol conversion is reactor provided by the invention.
Present invention also offers a kind of methanol convert method, the method includes: when methanol converts, methanol is introduced methanol conversion response system from bottom to top with catalyst counter current contacting, carry out the reaction of methanol conversion; The response system that described methanol converts is the response system that methanol provided by the invention converts.
Reactor provided by the invention arranges the catalyst support plate of inclination, catalyst is made to move in baffling from top to bottom between gripper shoe, and reactant feed methanol vertically moves from bottom to top, gas-particle two-phase material is all approximate in laminar flow, due to gas-solid adverse current, and gas linear velocity is less than the terminal velocity of solid particle, decrease solid back-mixing, the contacting efficiency of methanol and catalyst can be improved, methanol is made to combine with reaction characteristics with the way of contact of catalyst, reduce side reaction, improve the conversion ratio of raw material and the selectivity of purpose product.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below. In the accompanying drawings:
Fig. 1 is the schematic diagram of the response system that methanol provided by the invention converts.
Description of reference numerals
1, unstripped gas entrance 2, housing 3, catalyst support plate
4, reaction gas outlet 5, catalyst transport pipeline 6, regenerative agent transfer valve
7, gas entrance 8, stripping gas outlet 9, stripper are loosened
10, stripping gas entrance 11, regeneration gas outlet 12, regenerator
13, regeneration gas inlet 14, spent agent transfer valve 15, conveying gas entrance
16, sieve plate 17, spent agent feed-line 18, fresh dose of entrance
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
In the present invention, methanol conversion is for erectting vertical placement, when not making contrary explanation, the noun of locality used typically refers to the direction of the reaction gas outlet 4 to reactor such as " upper, top, top ", and " under, bottom, bottom " typically refers to the direction of the unstripped gas entrance 1 to reactor.
The invention provides a kind of methanol conversion, as it is shown in figure 1, this reactor includes: the spent agent outlet that housing 2, the reaction gas outlet 4 offered on the top of housing 2, the unstripped gas entrance 1 offered in the bottom of housing 2, the catalyst inlet offered in the top-side of housing 2 and the bottom sides at housing 2 are offered; Wherein, in housing 2, also offer multiple cross section extending obliquely through housing 2 and catalyst support plate 3 spaced apart each other, for making catalyst be slipped to the bottom of housing 2 from the top of housing 2; Low side at catalyst support plate 3 offers breach, as the landing passage of catalyst; Catalyst support plate 3 is offered multiple aperture, flows up for reacting gas.
According to the present invention, having certain angle between catalyst support plate 3 and horizontal plane, this angle can ensure that catalyst landing on catalyst support plate 3, it is possible to more than or equal to the catalyst granules static landing angle on catalyst support plate 3. Under preferable case, catalyst support plate 3 is tilted the angle �� formed with horizontal plane and is 10-45 ��.
According to the present invention, in reactor, from top to bottom, the inclination conditions of multiple catalyst support plate 3 can be constant or change. Under preferable case, in housing 2, the angle �� of multiple catalyst support plate 3 is identical; Or along the top of housing 2 to the direction of the bottom of housing 2, the angle �� of multiple catalyst support plate 3 is gradually increased. The change of this angle specifically can set according to the cycle rate of the different fluidization properties of catalyst of carbon distribution, catalyst, such as can be from top to bottom, multiple catalyst support plate 3 increase the angle of angle �� successively, in two adjacent catalyst support plate, one piece of catalyst support plate of lower section increases 0-10 �� than the angle �� of one piece of catalyst support plate of top.
According to the present invention, reactor is generally pylindrical, and the level cross-sectionn of reactor is circular. catalyst support plate 3 extends obliquely through the cross section of housing 2, is not exclusively circular, but because catalyst support plate 3 is less big with the angle �� of horizontal plane, the true form deviation circle of catalyst support plate 3 is not serious. under preferable case, the shape of catalyst support plate 3 is approximately circular, and the breach of catalyst support plate 3 is the arch that central angle is not more than 90 ��, and the breach of adjacent catalyst support plate 3 is that dislocation is offered. in the present invention, the catalyst support plate 3 only central angle part more than 270 �� is connected with housing 2, and forming catalyst between straight line portion and the housing 2 of the breach of catalyst support plate 3 can the passage of landing. be opened in during the breach difference of adjacent catalyst support plate 3 up and down just to position, namely by the breach not directly to the lower catalyst support plate 3 by lower section of the catalyst under the breach landing of the catalyst support plate 3 of top, now, the breach of catalyst support plate 3 of lower section is opened in the position that the breach of the catalyst support plate 3 with top is relative, it is that baffling moves during the from top to bottom landing of such catalyst, the longest distance can be moved on the catalyst support plate 3 of lower section when breach from above is to the breach of lower section, can ensure that the catalyst time of staying in reactor.
In the present invention, catalyst support plate 3, for tilting, has the high-end of top towards housing 2 and the low side of the bottom towards housing 2. the breach of each catalyst support plate 3 is all opened in the low side of this catalyst support plate 3. as previously mentioned, the breach of adjacent catalyst support plate 3 is opened in relative position, therefore, in the reactor, multiple catalyst support plate 3 be arranged as from top to bottom, in adjacent catalyst support plate 3, the low side jaggy of the catalyst support plate 3 of top is unnotched high-end relative and close with the catalyst support plate 3 of lower section, the low side jaggy of catalyst support plate 3 of the unnotched high-end and lower section of the catalyst support plate 3 of top relative and away from, thus, catalyst can move from the top of reactor baffling from top to bottom on multiple catalyst support plate 3.
According to the invention it is preferred in situation, described breach straight line portion be connected below baffle plate, this baffle plate extends towards the bottom direction of housing 2, for forming the landing passage of catalyst with housing 2. The lower edge of this baffle plate and the catalyst support plate 3 of lower section high-end between have certain space, this space can be determined according to feed throughput, catalyst circulating load, and specifically the height in such as this space can be 0.05-0.5 times of the diameter of reactor.
According to the present invention, the aperture that catalyst support plate 3 is arranged does not allow catalyst granules to fall, it is preferable that in situation, the diameter of the aperture of catalyst support plate 3 is less than the particle diameter of catalyst granules. The diameter of aperture can be set smaller than 1-3cm according to the particle diameter of catalyst granules. Porosity on catalyst support plate 3 is 1-30 hole/cm2��
In the present invention, multiple catalyst support plate 3 are interval placement each other from top to bottom in the reactor, wherein spaced apart may determine that in adjacent catalyst support plate 3 top catalyst support plate 3 breach end and lower section catalyst support plate 3 high-end between air line distance, specifically, diameter 0.5-3 times for reactor spaced apart.
According to the present invention, the unstripped gas entrance 1 in the bottom of housing 2 is only used for passing into reaction raw materials gas, i.e. methanol gas, and catalyst is without falling into unstripped gas entrance 1. Under preferable case, all catalyst support plate 3 be arranged below extend obliquely through the cross section of housing 2 and unnotched sieve plate 16, the low side of sieve plate 16 connects the outlet of described spent agent, and multiple diameter aperture less than catalyst granules particle diameter offered by sieve plate 16. Sieve plate 16 can make the catalyst of landing finally discharge reactor from spent agent outlet, separates with product. The angle of sieve plate 16 and horizontal plane can more than the angle �� of its catalyst support plate 3 immediately above. Sieve plate 16 high-end relative with the low side jaggy of its catalyst support plate 3 immediately above. The diameter of the aperture on sieve plate 16 can be identical with the diameter of the aperture of catalyst support plate 3 and porosity with porosity.
Present invention also offers the response system that a kind of methanol converts, as it is shown in figure 1, this system includes: methanol conversion, stripper 9 and regenerator 12; The catalyst inlet of methanol conversion is communicated to regenerator 12 by catalyst transport pipeline 5; The spent agent outlet of methanol conversion is to stripper 9; The bottom of stripper 9 is communicated to the bottom of regenerator 12 by spent agent feed-line 17; Described methanol conversion is reactor provided by the invention.
In the present invention, the sectional area of spent agent feed-line 17 is less than the breach area of catalyst support plate 3.
According to the invention it is preferred in situation, this system also includes: the stripping gas outlet 8 offered on the top of stripper 9, the regeneration gas outlet 11 offered on the top of regenerator 12.
According to the invention it is preferred in situation, this system also includes: fresh dose of entrance 18, regenerative agent transfer valve 6 and the loosening gas entrance 7 offered on catalyst transport pipeline 5; And, stripping gas entrance 10, conveying gas entrance 15, spent agent transfer valve 14 and the regeneration gas inlet 13 offered on spent agent feed-line 17.
In the present invention, stripping gas entrance 10 can pass into stripping gas, washes the Remaining Oil And Gas on catalyst off, also has the effect of loosening catalyst, it is to avoid dead bed. Stripping gas can be steam can also be other noble gases. Stripper 9 is also used as the catalyst relief area between reaction-regeneration system, it is to avoid catalyst circulation rate does not move the fluctuation of the catalyst inventory causing reaction-regeneration system, normal, the even running of holding means.
In the present invention, spent agent transfer valve 14 can be L-shaped valve or U-shaped valve, has the effect of lock pressure, separates reaction environment and regenerative environ-ment. Pressure reduction according to reaction-regenerative environ-ment, it is possible to the structure of spent agent transfer valve 14 is adjusted, improves its lock pressure energy power.
The conveying tolerance of conveying gas entrance 15 is decided by the catalytic amount of regenerator 12. Spent agent feed-line 17 can horizontal by certain angle, and angle depends on catalyst angle of repose and the length of spent agent feed-line 17. If spent agent feed-line 17 is inclined upwardly, then can improve the lock pressure effect of spent agent transfer valve 14; If spent agent feed-line 17 is downward-sloping, then should be less than granule landing angle in pipeline with horizontal plane angle. If response system is high pressure or faces hydrogen environment, and regenerative system is normal pressure aerobic environment, it is also possible to installing valve on spent agent feed-line 17, valve can be ball valve or stop valve, cuts off reaction-regenerative environ-ment further, improves the safety of system. And owing to valve is contained in low-pressure end, not only reduce the seal request of valve, but also ensure that the lock pressure effect of spent agent transfer valve 14.
Under the effect of the conveying gas of conveying gas entrance 15 input, in stripper 9, the reclaimable catalyst after stripping is transported to the bottom of regenerator 12, regeneration gas inlet 13 regeneration gas inputted brings to regenerator 12. Conveying gas can for nitrogen that oxygen concentration is 0-22 volume %.
Can be the regeneration of close phase in regenerator 12 can also be dilute phase regeneration, regeneration gas can be pure oxygen, air or Poor oxygen gas, concentration for oxygen controls regenerator bed temperature, and ensures that the carbon deposit on catalyst is completely burned off, heavily causes catalysqt deactivation to avoid carbon deposit to become gradually.
There is overfall the middle and upper part of regenerator 12, connects with catalyst transport 5. Separating reaction-regeneration system with regenerative agent transfer valve 6, regenerative agent transfer valve 6 can be L-shaped valve or U-shaped valve. Regenerative agent transfer valve 6 has conveying gas entrance, enters the amount of reactor with conveying gas control preparation, regeneration catalyst, and mate with between spent agent transfer valve 14. Catalyzed dose of feed-line 5 of regeneration catalyzing agent enters reactor and completes a circulation of catalyst. Regenerative agent transfer valve 6 to reactor head has vertical pipeline section, depends highly on the difference of reaction-regeneration and the requirement of safety. If reaction environment is high pressure or faces hydrogen environment, and regenerative environ-ment is low pressure aerobic environment, then also at the low-pressure end of regenerative agent transfer valve 6 equipped with valve, need to increase the lock pressure effect of regenerative agent transfer valve 6 further. If during conveying catalyst granules, the lock pressure effect of regenerative agent transfer valve 6 reduces, the gas of response system can to regenerative system anti-channeling, then the close phase particles fall of vertical pipeline section. Therefore improve the lock pressure effect of regenerative agent transfer valve 6, it is possible to effectively prevent the reacting gas anti-channeling to regenerative system, improve the safety of device. Loosen gas entrance 7 for loosening the granule of this upstream, place, it is to avoid catalyst buildup is crossed and cannot normally be carried in fact.
Fresh dose of entrance 18 can carry fresh catalyst to reactor. When proceeding by the reaction of methanol conversion, it is possible to first carry fresh catalyst from fresh dose of entrance 18 to reactor. Carrying out along with reaction, it is possible to have the catalyst of regeneration to carry to reactor. The addition of fresh dose can be adjusted.
Present invention also offers a kind of method that methanol converts, the method includes: when methanol converts, and the response system that methanol introduces methanol conversion contacts with under catalyst the flow direction from bottom to top, carries out the reaction of methanol conversion; The response system that described methanol converts is the response system that methanol provided by the invention converts.
In the present invention, in the reactor, methanol from bottom to top flows, and catalyst from top to bottom flows, both counter current contacting, and methanol carries out catalytic conversion reaction.
According to the present invention, described the reaction of methanol conversion can be preparing gasoline by methanol and preparing propylene from methanol. Under preferable case, described the reaction of methanol conversion is preparing gasoline by methanol, and the temperature of reaction is 350-500 DEG C, and the pressure of reaction is 0.1-4MPa, and the weight (hourly) space velocity (WHSV) of methanol feeding is 0.5-8h-1, the one way time of staying of described catalyst is 14-240h.
Described the reaction of methanol conversion is preparing propylene from methanol, and the temperature of reaction is 380-420 DEG C, and the pressure of reaction is 1-3MPa, and the weight (hourly) space velocity (WHSV) of methanol feeding is 0.5-8h-1, the one way time of staying of described catalyst is 14-240h.
In the present invention, the flow velocity of methanol feeding does not affect flowing downward of catalyst, and specifically, methanol flows up but do not make catalyst that suspension phenomenon occurs in reactor.
According to the present invention, described catalyst can be the commonly used in the art catalyst realizing methanol conversion, it is possible to there is no particular limitation. Under preferable case, described catalyst is at least one in ZSM-5 molecular sieve, phosphorous modified ZSM-5 molecular sieve or rare-earth metal modified ZSM-5 molecular sieve. Can be such as SRM-8 (Research Institute of Petro-Chemical Engineering).
In the present invention, regenerative process is oxygen deprivation regeneration, and the temperature of regeneration is 500-650 DEG C, and the regeneration gas oxygen concentration of regenerator entrance is 5-21 volume %, and the regeneration gas oxygen concentration of regenerator outlet is 0-10 volume %.
With reference to shown in Fig. 1, in methanol conversion provided by the invention and the reaction of methanol conversion system, the process carrying out methanol conversion is as follows.
Methanol enters reactor from the unstripped gas entrance 1 of reactor bottom, and the aperture on catalyst support plate 3 arranged in reactor moves upward, and successively contacts with the catalyst on catalyst support plate 3 and react. Catalyst is fresh dose added by fresh dose of entrance 18 and/or regeneration catalyzing agent from regenerator 12, catalyst on catalyst support plate 3 by move obliquely, and be slipped to following catalyst support plate 3 from the breach of catalyst support plate 3. Catalyzer coke content is gradually lowered from bottom to top, and product leaves reactor from the outlet 4 at top. Wherein, due to gas-solid adverse current, not making catalyst be entrained, gas linear velocity is less than the terminal velocity of granule.
In the bottom of reactor, catalyst is slipped to sieve plate 16 and discharges from spent agent outlet, enters stripper 9 through spent agent feed-line 17. Reacting gas enters reactor through the aperture on sieve plate 16.
Pass into, from stripping gas entrance 10, the Remaining Oil And Gas that stripping gas is washed off catalyst, export 8 discharge stripping gases from stripping gas. By carrying gas entrance 15 to pass into conveying gas, the spent agent after stripping is delivered into regenerator 12. Spent agent transfer valve 14 operation makes reaction-regeneration system isolate. Pass into regeneration gas from regeneration gas inlet 13 to regenerator 12, make spent agent regenerate. Regeneration gas outlet 11 discharge regeneration gas. Catalyzed dose of feed-line 5 of regenerative agent is admitted to reactor, wherein regenerative agent transfer valve 6 operation makes reaction-regeneration system isolate, the operation loosening gas entrance 7 is the granule loosening this upstream, place, it is to avoid catalyst buildup is crossed and cannot normally be carried in fact, completes the reaction-regeneration cycle of catalyst.
Hereinafter will be described the present invention by embodiment.
In the following Examples and Comparative Examples, there is following relation in the condition of the method carrying out methanol conversion:
Air speed (h-1)=methanol feeding amount �� catalyst inventory
The time of staying (h)=catalyst inventory �� catalyst circulating load
Embodiment 1
The method that the present embodiment converts for methanol provided by the invention is described produces propylene product.
Reactor diameter is 0.2m, is highly 2m, wherein arranges 9 catalyst support plate 3, and angle �� is 15 ��, and from top to bottom, the catalyst support plate 3 of lower section increases by 1 �� than the angle �� of the catalyst support plate 3 of top. The porosity of the aperture on catalyst support plate 3 and sieve plate 16 is 10 holes/cm2, the diameter of aperture is 0.5cm. The height of the baffle plate that the indentation, there of catalyst support plate 3 connects is 13cm, is 4cm with the gap of the catalyst support plate 3 of lower section. Between catalyst support plate 3 spaced apart for 17cm.
Catalyst is ZSM-5 Type Zeolites agent (Research Institute of Petro-Chemical Engineering, SRM-8), and mean particle size is 2mm. Stripping gas is steam, and regeneration gas is air.
With the methanol of concentration 95% for raw material, entering reactor after vaporization, be simultaneously introduced catalyst, methanol contacts in the reactor from top to bottom with catalyst stream. The temperature of reaction is 500 DEG C, the pressure of reaction is 0.2MPa, and methanol feeding amount is 10kg/h, catalyst inventory 5kg, and catalyst circulating load is 35g/h. The nitrogen of conveying gas to be oxygen concentration be 5 volume %. The temperature of regenerator is 600 DEG C, carries out oxygen deprivation regeneration, and the oxygen concentration of entrance is 10 volume %, and the oxygen concentration of outlet controls lower than 3 volume %.
Obtaining gas products after the cooled separation of product that reactor head is collected, product slates is as shown in table 1.
Embodiment 2
The method that the present embodiment converts for methanol provided by the invention is described produces gasoline products.
Reactor diameter is 0.2m, is highly 2m, wherein arranges 9 catalyst support plate 3, and angle �� is 15 ��, and from top to bottom, the catalyst support plate 3 of lower section increases by 0.5 �� than the angle �� of the catalyst support plate 3 of top. The porosity of the aperture on catalyst support plate 3 and sieve plate 16 is 10 holes/cm2, the diameter of aperture is 0.5mm. The height of the baffle plate that the indentation, there of catalyst support plate 3 connects is 13cm, is 4cm with the gap of the catalyst support plate 3 of lower section. Between catalyst support plate 3 spaced apart for 17cm.
Catalyst is ZSM-5 Type Zeolites agent (Research Institute of Petro-Chemical Engineering, SRM-8), and mean particle size is 2mm. Stripping gas is steam, and regeneration gas is air.
With the methanol of concentration 95% for raw material, entering reactor after vaporization, be simultaneously introduced catalyst, methanol contacts in the reactor from top to bottom with catalyst stream. The temperature of reaction is 410 DEG C, the pressure of reaction is 2MPa, and methanol feeding amount is 10kg/h, catalyst inventory 5kg, and catalyst circulating load is 35g/h. The nitrogen of conveying gas to be oxygen concentration be 5 volume %. The temperature of regenerator is 630 DEG C, carries out oxygen deprivation regeneration, and the oxygen concentration of entrance is 10 volume %, and the oxygen concentration of outlet controls lower than 3 volume %.
Obtaining gas and gasoline products after the cooled separation of product that reactor bottom is collected, product slates is as shown in table 1.
Embodiment 3
The method that the present embodiment converts for methanol provided by the invention is described produces propylene product.
Reactor diameter is 0.2m, is highly 2m, wherein arranges 9 catalyst support plate 3, and angle �� is 15 ��, and from top to bottom, the catalyst support plate 3 of lower section increases by 1 �� than the angle �� of the catalyst support plate 3 of top. The porosity of the aperture on catalyst support plate 3 and sieve plate 16 is 10 holes/cm2, the diameter of aperture is 1mm. The height of the baffle plate that the indentation, there of catalyst support plate 3 connects is 14cm, is 5cm with the gap of the catalyst support plate 3 of lower section. Between catalyst support plate 3 spaced apart for 20cm.
Catalyst is ZSM-5 Type Zeolites agent (Research Institute of Petro-Chemical Engineering, SRM-8), and mean particle size is 2mm. Stripping gas is steam, and regeneration gas is air.
With the methanol of concentration 95% for raw material, entering reactor after vaporization, be simultaneously introduced catalyst, methanol contacts in the reactor from top to bottom with catalyst stream. The temperature of reaction is 480 DEG C, the pressure of reaction is 0.2MPa, and methanol feeding amount is 10kg/h, catalyst inventory 5kg, and catalyst circulating load is 35g/h. The nitrogen of conveying gas to be oxygen concentration be 5 volume %. The temperature of regenerator is 600 DEG C, carries out oxygen deprivation regeneration, and the oxygen concentration of entrance is 10 volume %, and the oxygen concentration of outlet controls lower than 3 volume %.
Obtaining gas and gasoline products after the cooled separation of product that reactor bottom is collected, product slates is as shown in table 1.
Comparative example 1
According to the method for embodiment 1, the difference is that, with " fixed fluidized-bed reactor " replacement " reactor ". Fixed fluidized-bed reactor is the taper fixed fluidized-bed reactor of internal diameter 114mm.
Obtaining gas products after the cooled separation of product of fixed fluidized-bed reactor bottom collection, product slates is as shown in table 1.
Comparative example 2
According to the method for embodiment 1, the difference is that, with " fixed-bed micro-reactor " replacement " reactor ". Fixed-bed micro-reactor is the fixed bed reactors of internal diameter 50mm, high 1200mm.
Obtaining gas and gasoline products after the cooled separation of product that fixed-bed micro-reactor material outlet is collected, product slates is as shown in table 1.
Table 1
Can be seen that from the result of embodiment 1-3, prior art compared to comparative example 1-2, technical scheme provided by the invention is adopted to improve the contacting efficiency of methanol and catalyst, the alcohol agent way of contact combines with reaction characteristics, making methanol conversion process reduce side reaction, the conversion ratio of methanol and the selectivity of purpose product gasoline or propane are obtained for raising.
Claims (14)
1. a methanol conversion, this reactor includes: the spent agent outlet that housing (2), the reaction gas outlet (4) offered on the top of housing (2), the unstripped gas entrance (1) offered in the bottom of housing (2), the catalyst inlet offered in the top-side of housing (2) and the bottom sides at housing (2) are offered; It is characterized in that, in housing (2), also set up multiple cross section extending obliquely through housing (2) and catalyst support plate (3) spaced apart each other, be used for making catalyst be slipped to the bottom of housing (2) from the top of housing (2); Low side at catalyst support plate (3) offers breach, as the landing passage of catalyst; Catalyst support plate offers multiple aperture on (3), flows up for reacting gas.
2. reactor according to claim 1, wherein, tilts catalyst support plate (3) angle �� formed with horizontal plane and is 10-45 ��.
3. reactor according to claim 2, wherein, in housing (2), the angle �� of multiple catalyst support plate (3) is identical; Or along the top of housing (2) to the direction of the bottom of housing (2), the angle �� of multiple catalyst support plate (3) is gradually increased.
4. the reactor according to any one in claim 1-3, wherein, the shape of catalyst support plate (3) is approximately circular, breach on catalyst support plate (3) is the arch that central angle is not more than 90 ��, and the breach dislocation on adjacent catalyst support plate (3) is offered.
5. reactor according to claim 4, wherein, described breach straight line portion be connected below baffle plate, this baffle plate extends towards the bottom direction of housing (2), for and housing (2) formed catalyst landing passage.
6. the reactor according to any one in claim 1-3, wherein, the diameter of the aperture on catalyst support plate (3) is less than the particle diameter of catalyst granules.
7. the reactor according to any one in claim 1-3, wherein, whole catalyst support plate (3) be arranged below extend obliquely through the cross section of housing (2) and unnotched sieve plate (16), the low side of sieve plate (16) connects the outlet of described spent agent, and sieve plate (16) is offered multiple diameter aperture less than catalyst granules particle diameter.
8. the response system that methanol converts, this system includes: methanol conversion, stripper (9) and regenerator (12); The catalyst inlet of methanol conversion is communicated to regenerator (12) by catalyst transport pipeline (5); The spent agent outlet of methanol conversion is to stripper (9); The bottom of stripper (9) is communicated to the bottom of regenerator (12) by spent agent feed-line (17); Described methanol conversion is the reactor in claim 1-7 described in any one.
9. system according to claim 8, wherein, this system also includes: stripping gas outlet (8) offered on the top of stripper (9), the regeneration gas offered on the top of regenerator (12) outlet (11).
10. system according to claim 8, wherein, this system also includes: fresh dose of entrance (18), regenerative agent transfer valve (6) and the loosening gas entrance (7) offered on catalyst transport pipeline (5); And, stripping gas entrance (10), conveying gas entrance (15), spent agent transfer valve (14) and the regeneration gas inlet (13) offered on spent agent feed-line (17).
11. methanol convert a method, the method includes: when methanol converts, methanol is introduced methanol conversion response system from bottom to top with catalyst counter current contacting, carry out the reaction of methanol conversion; The response system that described methanol converts is the system in claim 8-10 described in any one.
12. method according to claim 11, wherein, described the reaction of methanol conversion is preparing gasoline by methanol, and the temperature of reaction is 350-500 DEG C, and the pressure of reaction is 0.1-4MPa, and the weight (hourly) space velocity (WHSV) of methanol feeding is 0.5-8h-1, the one way time of staying of described catalyst is 14-240h.
13. method according to claim 11, wherein, described the reaction of methanol conversion is preparing propylene from methanol, and the temperature of reaction is 380-420 DEG C, and the pressure of reaction is 1-3MPa, and the weight (hourly) space velocity (WHSV) of methanol feeding is 0.5-8h-1, the one way time of staying of described catalyst is 14-240h.
14. the method according to any one in claim 11-13, wherein, described catalyst is at least one in ZSM-5 molecular sieve, phosphorous modified ZSM-5 molecular sieve or rare-earth metal modified ZSM-5 molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410592192.XA CN105617948B (en) | 2014-10-29 | 2014-10-29 | A kind of methanol conversion and the method for reaction system and methanol conversion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410592192.XA CN105617948B (en) | 2014-10-29 | 2014-10-29 | A kind of methanol conversion and the method for reaction system and methanol conversion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105617948A true CN105617948A (en) | 2016-06-01 |
| CN105617948B CN105617948B (en) | 2019-07-23 |
Family
ID=56033525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410592192.XA Active CN105617948B (en) | 2014-10-29 | 2014-10-29 | A kind of methanol conversion and the method for reaction system and methanol conversion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105617948B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110678252A (en) * | 2017-06-02 | 2020-01-10 | 卡萨乐有限公司 | Catalytic bed reactor |
| CN111701541A (en) * | 2020-06-19 | 2020-09-25 | 宁波巨化化工科技有限公司 | Catalytic auxiliary device for gas-phase aldehyde hydrogenation reactor |
| CN115678595A (en) * | 2021-07-30 | 2023-02-03 | 中国石油化工股份有限公司 | Deep desulfurization method and system for gasoline |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2350119Y (en) * | 1998-10-30 | 1999-11-24 | 中国科学院化工冶金研究所 | Multilayer moving fluid-bed reactor |
| CN202270515U (en) * | 2011-10-25 | 2012-06-13 | 奎屯西龙无纺土工制品有限公司 | Multi-row-tube sectional heat-exchange type fluidized bed reaction device |
| JP2012143717A (en) * | 2011-01-13 | 2012-08-02 | Japan Oil Gas & Metals National Corp | Catalyst recovery system, hydrocarbon synthesis reaction apparatus, hydrocarbon synthesis reaction system, and catalyst recovery method |
| CN102659498A (en) * | 2012-05-14 | 2012-09-12 | 神华集团有限责任公司 | Device and method for converting methanol into low-carbon olefins |
-
2014
- 2014-10-29 CN CN201410592192.XA patent/CN105617948B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2350119Y (en) * | 1998-10-30 | 1999-11-24 | 中国科学院化工冶金研究所 | Multilayer moving fluid-bed reactor |
| JP2012143717A (en) * | 2011-01-13 | 2012-08-02 | Japan Oil Gas & Metals National Corp | Catalyst recovery system, hydrocarbon synthesis reaction apparatus, hydrocarbon synthesis reaction system, and catalyst recovery method |
| CN202270515U (en) * | 2011-10-25 | 2012-06-13 | 奎屯西龙无纺土工制品有限公司 | Multi-row-tube sectional heat-exchange type fluidized bed reaction device |
| CN102659498A (en) * | 2012-05-14 | 2012-09-12 | 神华集团有限责任公司 | Device and method for converting methanol into low-carbon olefins |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110678252A (en) * | 2017-06-02 | 2020-01-10 | 卡萨乐有限公司 | Catalytic bed reactor |
| CN111701541A (en) * | 2020-06-19 | 2020-09-25 | 宁波巨化化工科技有限公司 | Catalytic auxiliary device for gas-phase aldehyde hydrogenation reactor |
| CN111701541B (en) * | 2020-06-19 | 2021-03-09 | 宁波巨化化工科技有限公司 | Catalytic auxiliary device for gas-phase aldehyde hydrogenation reactor |
| WO2021254192A1 (en) * | 2020-06-19 | 2021-12-23 | 宁波巨化化工科技有限公司 | Catalytic auxiliary device for gas-phase aldehyde hydrogenation reactor |
| CN115678595A (en) * | 2021-07-30 | 2023-02-03 | 中国石油化工股份有限公司 | Deep desulfurization method and system for gasoline |
| CN115678595B (en) * | 2021-07-30 | 2024-03-12 | 中国石油化工股份有限公司 | Deep desulfurization method and system for gasoline |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105617948B (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9827544B2 (en) | Reaction device for preparing light olefins from methanol and/or dimethyl ether | |
| CN106854128B (en) | A kind of method that toluene produces paraxylene with methanol | |
| CN101402541B (en) | Fluidized bed process and apparatus for producing ethylene with acetylene hydrogenation | |
| JP6817427B2 (en) | High-speed fluidized bed reactors, equipment and methods for producing propylene and C4 hydrocarbons from oxygen-containing compounds. | |
| WO2015149646A1 (en) | Fluidized bed apparatus and method for preparing polymethoxy dimethylether from methylal and paraformaldehyde | |
| KR20190138870A (en) | Apparatus and method for producing paraxylene with methanol and / or dimethyl ether and toluene and simultaneous production of low carbon olefins | |
| CN111054271A (en) | Low-agent-consumption reaction device and reaction method for preparing aniline by nitrobenzene hydrogenation | |
| CN111484387B (en) | Method for converting raw material containing naphtha into low-carbon olefin and/or aromatic hydrocarbon | |
| KR20190140467A (en) | Fluidized bed apparatus and method for the preparation of paraxylene with methanol and / or dimethylether and toluene and the simultaneous production of low carbon olefins | |
| CN105617948A (en) | Methanol conversion reactor and reaction system and methanol conversion method | |
| EP3868474A1 (en) | Gas replacement method and device, and hydrogenation method for nitro compound | |
| KR102309236B1 (en) | Fluidized bed apparatus and method for the simultaneous production of low-carbon olefins and the production of para-xylene with methanol and/or dimethyl ether and benzene | |
| US6143915A (en) | Reaction process in hybrid reactor for propylene ammoxidation | |
| CN105617954A (en) | Methanol conversion reactor and reaction system and methanol conversion method | |
| CN111054280B (en) | Reaction device and reaction method for preparing aniline by hydrogenation of multi-zone nitrobenzene | |
| US20230002682A1 (en) | Fluidized bed reactor, device and method for preparing low-carbon olefins from oxygen-containing compound | |
| WO2020083279A1 (en) | Liquid-solid axial moving bed reaction and regeneration device, and solid acid alkylation method | |
| US20220119719A1 (en) | System for catalytic cracking of naphtha with mixed spent and regenerated catalyst | |
| CN115106028B (en) | Vertical multistage fluidized bed reactor and preparation method for preparing olefin from methanol | |
| CN105001036A (en) | Methanol to propylene reactor | |
| TW202027854A (en) | Liquid-solid radial moving bed reaction device and solid acid alkylation method | |
| CN104801352A (en) | Method for burning off deposition carbon on catalyst in radial moving bed regeneration unit | |
| CN114286720B (en) | Baffled turbulent/fast fluidized bed reactor for maximizing low carbon olefin yield | |
| CN105268381B (en) | Down-flow fluidized bed using ECT reaction regeneration device and its reaction method for methanol-to-olefins | |
| CN220026958U (en) | Fluidized bed reactor for producing low-carbon olefin from methanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |