CN103464061B - A kind of by alkane fluidized bed plant preparing aromatic hydrocarbons and preparation method thereof - Google Patents
A kind of by alkane fluidized bed plant preparing aromatic hydrocarbons and preparation method thereof Download PDFInfo
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- CN103464061B CN103464061B CN201310392479.3A CN201310392479A CN103464061B CN 103464061 B CN103464061 B CN 103464061B CN 201310392479 A CN201310392479 A CN 201310392479A CN 103464061 B CN103464061 B CN 103464061B
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 51
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 298
- 238000009826 distribution Methods 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 34
- 238000011084 recovery Methods 0.000 claims abstract description 34
- 230000008929 regeneration Effects 0.000 claims abstract description 23
- 238000011069 regeneration method Methods 0.000 claims abstract description 23
- 230000008676 import Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 205
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 92
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 239000001294 propane Substances 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 235000013844 butane Nutrition 0.000 claims description 29
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 29
- 241001120493 Arene Species 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 239000011229 interlayer Substances 0.000 claims description 27
- 239000001273 butane Substances 0.000 claims description 24
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 27
- 238000005516 engineering process Methods 0.000 description 17
- 239000012530 fluid Substances 0.000 description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 16
- 229910052725 zinc Inorganic materials 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 230000007246 mechanism Effects 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000004047 hole gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- 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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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of by alkane fluidized bed plant preparing aromatic hydrocarbons and preparation method thereof.Described device comprises gas access, gas vent, gas distributor and catalyst recovery system, also comprise distribution grid, heating tube, outer overflow pipe, catalyst inlet and decaying catalyst outlet, wherein: distribution grid is placed horizontally in described device, heating tube is arranged on below distribution grid and top, and heating tube import and export are connected with described device inwall, outer overflow pipe lower openings passes in bottom beds, outer overflow pipe top and described device parallel longitudinal, catalyst inlet bottom is connected with described device left side wall, top tilts upward from described device left side wall stretches out, decaying catalyst top is connected with described device right side wall, bottom is tilted to from described device right side wall stretches out.Described preparation method comprises: pass into gas while adding catalyst; Be energized or pass into medium to heating tube; Pass into unstrpped gas; Divided gas flow product and catalyst; Reclaim catalyst; Obtain gas products; Catalyst regeneration; Circulation said process.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of fluidized bed plant and the method thereof of being prepared aromatic hydrocarbons by alkane.
Background technology
Aromatic hydrocarbons is one of important basic chemical, and in the preparation of traditional chemical industry, aromatic hydrocarbons obtains mainly through petroleum refining and dry distillation of coal process.The aromatic hydrocarbons purity obtained by oil is high, is suitable for preparing various high-quality chemicals.The aromatic hydrocarbons obtained by the dry distillation of coal is due to containing thiophene-based impurity, and quality is relatively low, and application is limited to.Along with petroleum resources worsening shortages, the supply of aromatic hydrocarbons is nervous trend, and price can be in any more, greatly improves the production cost of production subsequent chemicals, makes it sell and is affected.Be the technology of aromatic hydrocarbons by feedstock conversion such as methane, liquefied gas or methyl alcohol, can reform to aromatic hydrocarbons and the oil aromatic hydrocarbons mode such as cracking of ethylene form beneficial complement.
Especially, liquefied gas component both can derive from petroleum cracking and prepare aromatic hydrocarbons process, also can derive from Methanol for alkene, gasoline or aromatic hydrocarbons process.Meanwhile, because the temperature of conversion process is higher, catalyst easy in inactivation, catalyst can shift out by moving bed and fluidized-bed reactor easily, carries out reaction regeneration, becomes the mainstream reactor that liquefied gas transforms gradually.But except a small amount of technology, it is olefin component in conversion liquefied gas that the essence of most of technology transforms, and cannot reforming alkanes, particularly propane and/or butane, or and C
5-C
7the mixture of non-aromatics.
Patent reports recently can simultaneously by alcohol ether or C
3-C
4hydrocarbon is converted to catalyst and the fluidized-bed reactor of aromatic hydrocarbons.But, wherein C
3-C
4hydrocarbon is still the mixture of alkane and alkene, its be converted into micro-heat absorption or micro-enter thermal response.And propane and/or butane, or propane and/or butane and C
5-C
7the process that the mixture of non-aromatics is converted into aromatic hydrocarbons is strong endothermic reaction, and the engineering that temperature is high becomes very serious for heat problem.Meanwhile, in single hop fluidized-bed reactor, gas-solid back-mixing is serious.The propane that difficulty is transformed and/or butane, or propane and/or butane and C
5-C
7the mixture of non-aromatics, process driving force is not high, and conversion ratio and aromatics yield not easily improve, and need the material quantity of circulation to increase, process energy consumption is high.And, although heating tube has been applied under the high temperature conditions to different system heat supply at present, owing to there is a large amount of moving particle in fluidized-bed reactor, will impact the intensity of heating tube under hot conditions.Therefore, the heating tube of fluidized-bed reactor can not be long, again can not be too much, causes heating efficiency to be restricted.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention proposes a kind of fluidized bed plant and the method thereof of being prepared aromatic hydrocarbons by alkane, can either improve the heat capacity of fluidized-bed reactor, can realize again large scale industry and produce.For achieving the above object, the present invention adopts following technical scheme:
The fluidized bed plant being prepared aromatic hydrocarbons by alkane comprises: gas access, gas vent, gas distributor and a catalyst recovery system, wherein: top, described gas access is connected with described bottom of device, and bottom is stretched out from described bottom of device; Described gas distributor, above gas access, is connected with described device inside; Described gas vent top is stretched out from described device top, and bottom is connected with catalyst recovery system top; Described catalyst recovery system top is connected with gas vent, and bottom does not contact described device inwall.Said apparatus also comprises distribution grid, heating tube, outer overflow pipe, catalyst inlet, decaying catalyst outlet, wherein: described distribution grid is connected with described device inwall, is placed horizontally in said apparatus; Described heating tube is arranged on below distribution grid and top, and heating tube import and export be connected with described device inwall, described outer overflow pipe lower openings passes in bottom beds, outer overflow pipe top and described device parallel longitudinal; Described catalyst inlet its underpart is connected with described device left side wall, and top tilts upward from described device left side wall stretches out; Described decaying catalyst outlet top is connected with described device right side wall, and bottom is tilted to from described device right side wall stretches out.
Described device is divided into 2-4 beds by the distribution grid of said apparatus, for stacking catalyst, beds is the first catalyst layer from bottom to up, second catalyst layer, 3rd catalyst layer, 4th beds, each beds has 1 catalyst inlet, and most top layer catalyst inlet position is 0.4-1.5m above outer overflow pipe upper outlet position outside its neighboring devices, the regenerated catalyst quality that each catalyst inlet enters described device all accounts for the 10-50% of catalyst gross mass respectively.
The distribution grid of said apparatus is horizontal multihole distributor, quantity is 1-3, wherein distribution grid percent opening described in first and second catalyst bed interlayer is 1-1.4 times of the second and the 3rd distribution grid percent opening described in catalyst bed interlayer, is 1-2 times of distribution grid percent opening described in the 3rd and the 4th catalyst bed interlayer.
The tube bank of the heating tube of said apparatus is parallel with described device lateral, heating tube outer surface is fin structure, and the distribution of one meter, each fin interval, the conduit on adjacent both ends fin is not exclusively corresponding, heating tube cross-sectional area account for device radial cross-section long-pending 20-35%.
The outer overflow pipe upper outlet position of said apparatus and below it adjacent distributions plate distance be 0.1-2 times of described assembly dia, all outer overflow pipe lower inlet positions are all in bottom beds, in three sections of bed apparatus and four sections of bed apparatus, outer overflow pipe top cross-sectional area is 1.2-1.5 times of its underpart cross-sectional area, and from the catalyst that outer overflow pipe upper outlet enters, contained gas causes near described device inner catalyst recovery system through pipeline.
The present invention also provides a kind of and uses above-mentioned fluidized bed plant to prepare the method for aromatic hydrocarbons by alkane, comprises the steps:
(1) add catalyst and pass into gas simultaneously;
(2) be energized or pass into medium to heating tube;
(3) unstrpped gas is passed into;
(4) divided gas flow product and catalyst;
(5) catalyst is reclaimed;
(6) gas products is obtained;
(7) catalyst regeneration;
(8) circulation said process.
Said method step (1) passes into 300-600 DEG C of nitrogen or air by gas access through gas distributor while loading catalyst.
The medium of said method step (2) is lightweight carbon nanomaterial and inert gas.
The medium temperature of said method step (2) is 700-900 DEG C, is directly heated to reaction bed temperature and is 530-650 DEG C.
Before said method step (3) passes into unstrpped gas, pass into nitrogen by gas access through gas distributor and replace.
Alkane described in said method step is propane and/or butane, or propane and/or butane and C
5-C
7the mixture of non-aromatics.
Said method step (4) is front, and unstrpped gas is after beds, and 530-650 DEG C time, conversion of propane is 45%-80%, and arenes selectivity alkyl is 46%-55%; Butanes conversion is 58%-80%, and arenes selectivity alkyl is greater than 55%.
The present invention compared with prior art, has the following advantages and beneficial effect:
1. heating tube is set, the heat of apparatus of the present invention is supplied and does not rely on heat that regenerated catalyst is with, add independence and the operating flexibility of course of reaction.
2. adopt the heating tube of fin, specific area is large, can effectively conduct heat in fluid bed, again can bubble crushing, increase gas-solid contact and changing effect.Therefore, the heating tube in the alternative conventional fluidization bed bioreactor of finned heating tube, both saved manufacturing cost, made again the mechanical deformation of heating tube under hot conditions little, operated safer, was easy to realize large scale industry and produced.
3. use lightweight carbon nanomaterial and high temperature inert gas heating medium in fin heats pipe, effectively can utilize thermal conductive resin and the mobility of lightweight carbon nanomaterial, thus increase the heat transfer coefficient of high temperature inert gas heating medium side to fluid bed side, high temperature inert gas heating medium consumption is reduced, and the cost that economizes in raw materials is about 10-20%.Meanwhile, reduce heating tube area, equipment cost can be reduced and be about 5-10%, and increase the security of course of reaction.
4., compared with single hop fluidized bed plant, in the present invention, multiple stage fluidized-bed device can improve alkane or alkane and non-aromatics and is catalytically converted into the conversion ratio of aromatic hydrocarbons and the yield of aromatic hydrocarbons, especially for raising propane and/or butane, or propane and/or butane and C
5-C
7the conversion ratio of non-aromatics and the yield of aromatic hydrocarbons, make the material of conversion and cycle tail off, and separating energy consumption reduces 10-20%.
5. multiple catalyst inlet is set, conveniently can adjusts the catalyst activity in different catalysts bed, the alkane remained is contacted with high activated catalyst, improve alkane conversion and do not increase catalyst abrasion amount again.
6. because the percent opening of catalyst bed interlayer distribution grid from bottom to up reduces successively, when fluidized bed gas volume is increased, distribution grid overhead gas is speeded by the via hole gas speed of distribution grid, therefore, increase contact effect and the changing effect of distribution grid overhead gas and catalyst, be specially adapted to propane and/or butane, or propane and/or butane and C
5-C
7the characteristic that non-aromatics difficulty transforms.Simultaneously in three sections, four sections fluidized bed plants, because outer overflow pipe top is larger than its underpart cross-sectional area, therefore catalyst circulation can be made to circulate, all the time a large amount of catalyst is had to exist in bottom beds, thus ensure large industry equipment decentralization, improve the security of equipment operating.
7. bottom beds is all stretched in outer overflow pipe bottom intersegmental for difference, make different section pressure balance be more prone to control, be conducive to the quiet run of maximization reactor bed.
Accompanying drawing explanation
Fig. 1 a is two-section flowing bed device schematic diagram of the present invention, comprises an outer overflow pipe.
Fig. 1 b is fin heats pipe schematic diagram of the present invention.
Fig. 2 is the stage fluidized bed device schematic diagram of the present invention, comprises two outer overflow pipes.
Fig. 3 is the present invention's four sections of fluidized bed plant schematic diagrames, comprises three outer overflow pipes.
In figure: 1. gas access; 2. gas distributor; 3. distribution grid; 4. heating tube; 5. outer overflow pipe; 6. catalyst recovery system; 7. gas vent; 8. catalyst inlet; 9. decaying catalyst outlet.
Detailed description of the invention
Below by detailed description of the invention, the present invention is described.
Embodiment 1:
Two-section flowing bed device as shown in Figure 1, outer overflow pipe upper outlet position is adjacent 0.1 times that below distribution grid spacing is assembly dia.Outer overflow pipe lower inlet position is in ground floor beds.Two catalyst inlets pass in two beds respectively, and second layer beds catalyst inlet position is than overflow pipe upper outlet height 0.4m outer outside device.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system through pipeline.Set fin heats pipe cross-sectional area account for device radial cross-section long-pending 20%.
By gas access 1 while gas distributor 2 passes into 600 DEG C of air, by fluidizer type catalyst from catalyst inlet 8 charging apparatus, wherein catalyst main active is zinc and ZSM-5 molecular sieve, the mass ratio of zinc and ZSM-5 molecular sieve is 1:10, its particle diameter 20-500 μm, bulk density is 650kg/m
3.After catalyst being heated to 300 DEG C, pass into 700 DEG C of high-temperature flue gas to heating tube 4, control first, second reaction bed temperature and be respectively 650 DEG C, 530 DEG C.Pass into nitrogen from gas access 1 through gas distributor 2 to replace, when oxygen purity is less than 0.5% in gas vent 7 gas, pass into unstrpped gas 100% propane, the weight space velocity controlling to enter gas access propane is 0.1h
-1, reaction pressure is 0.1MPa, and gas speed is 0.5m/s.Unstrpped gas is after two beds, and its conversion ratio is greater than 62%, and one way arenes selectivity alkyl is greater than 50%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Be continuously removed by decaying catalyst outlet 9 by decaying catalyst and regenerate, the catalyst after regeneration returns fluidized bed plant continuously through catalyst inlet 8.The catalyst quality regenerated from catalyst inlet 8 access to plant of first, second beds respectively accounts for 50% of catalyst gross mass.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 100% conversion of propane is greater than 60%, the catalyst life time lengthening 50% that arenes selectivity alkyl is greater than 50%.
Embodiment 2
Two-section flowing bed device as shown in Figure 1, outer overflow pipe 5 upper outlet position is adjacent 1 times that below distribution grid spacing is assembly dia.Outer overflow pipe lower inlet position is in the first beds.Two catalyst inlets pass in two beds respectively, and second layer beds catalyst inlet 8 position is than overflow pipe 5 upper outlet height 1.5m outer outside device.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system 6 through pipeline.Set fin heats pipe cross-sectional area account for device radial cross-section long-pending 35%.
By device gas access while gas distributor passes into 300 DEG C of air, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is copper and ZSM-5 molecular sieve, the mass ratio of copper and ZSM-5 molecular sieve is 1:100, its particle diameter 40-300 μm, bulk density is 1300kg/m
3.After catalyst being heated to 250 DEG C, pass into 750 DEG C of high temperature nitrogen containing 50% carbon nanopowder body to heating tube, the temperature controlling first, second beds is respectively 530 DEG C, 530 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 100% propane, the weight space velocity controlling gas access propane is 3h
-1, reaction pressure is 0.3MPa, gas speed 0.5m/s.Unstrpped gas is after two beds, and its conversion ratio is greater than 45%, and one way arenes selectivity alkyl is greater than 55%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration returns fluidized bed plant continuously through catalyst inlet.The catalyst quality entering the regeneration of fluid bed from the catalyst inlet of first, second beds accounts for 60% and 40% of catalyst gross mass respectively.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 100% conversion of propane is greater than 45%, the catalyst life time lengthening 60% that arenes selectivity alkyl is greater than 55%.
Embodiment 3
Two-section flowing bed device as shown in Figure 1, outer overflow pipe upper outlet position is adjacent 2 times that below distribution grid spacing is assembly dia.Outer overflow pipe lower inlet position is in the first beds.Two catalyst inlets pass in two beds respectively, and the position of second layer beds catalyst inlet is than the upper outlet height 1m of overflow pipe outer outside device.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system through pipeline.Set fin heats pipe cross-sectional area account for device radial cross-section long-pending 25%.
By gas access while gas distributor passes into 600 DEG C of nitrogen, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is zinc, platinum and ZSM-5 molecular sieve, the mass ratio of zinc, platinum and ZSM-5 molecular sieve is respectively 1:15 and 1:1000, its particle diameter 20-500 μm, bulk density is 450kg/m
3.After catalyst being heated to 300 DEG C, pass into 900 DEG C of high-temperature flue gas to heating tube, the temperature controlling first, second beds is respectively 530 DEG C and 600 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 100% butane, the weight space velocity controlling gas access butane is 1h
-1, reaction pressure is 1MPa, gas speed 0.8m/s.Unstrpped gas is after two beds, and its conversion ratio is greater than 70%, and one way arenes selectivity alkyl is greater than 60%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration returns fluidized bed plant continuously through catalyst inlet.The catalyst quality entering the regeneration of fluid bed from the catalyst inlet of first, second beds accounts for 10% and 90% of catalyst gross mass respectively.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 100% butanes conversion is greater than 70%, the catalyst life time lengthening 40% that arenes selectivity alkyl is greater than 60%.
Embodiment 4:
Two-section flowing bed device as shown in Figure 1, outer overflow pipe upper outlet position is adjacent 1.2 times that below distribution grid spacing is assembly dia.Outer overflow pipe lower inlet position is in the first beds.Two catalyst inlets pass in two beds respectively, and second layer beds catalyst inlet position is than the upper outlet height 0.8m of overflow pipe outer outside device.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system through pipeline.Set fin heats pipe cross-sectional area account for fluid bed radial cross-section long-pending 30%.
By gas access while gas distributor passes into 300 DEG C of nitrogen, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is zinc and ZSM-5 molecular sieve, the mass ratio of zinc and ZSM-5 molecular sieve is 1:10, its particle diameter 20-200 μm, bulk density is 650kg/m
3.After catalyst being heated to 250 DEG C, to heating tube electrified regulation, the temperature controlling first, second beds is respectively 650 DEG C and 600 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 50% propane and 50% butane (mass fraction), the weight space velocity controlling gas access propane is 0.5h
-1, reaction pressure is 1MPa, gas speed 0.2m/s.Unstrpped gas 50% propane is after two beds, and its conversion ratio is greater than 68%, and one way aromatics yield carbon back is greater than 50%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration is through the continuous return mechanism of catalyst inlet.The catalyst quality entering the regeneration of fluid bed from the catalyst inlet of first, second beds accounts for 90% and 10% of catalyst gross mass respectively.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 50% conversion of propane is greater than 68%, the catalyst life time lengthening 50% that arenes selectivity alkyl is greater than 50%.
Embodiment 5
Stage fluidized bed device as shown in Figure 2, first and second catalyst bed interlayer distribution grid percent opening is second and the 3rd 1.2 times of catalyst bed interlayer distribution grid percent opening.Outer overflow pipe upper outlet position is adjacent 0.1 times that below distribution grid spacing is assembly dia.The position of outer overflow pipe lower inlet is in the first beds.Three catalyst inlets pass in three beds respectively, and third layer beds catalyst inlet position is than the upper outlet height 0.6m of overflow pipe outer outside its neighboring devices.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system through pipeline.Outer overflow pipe top cross-sectional area is 1.3 times of its underpart cross-sectional area.Set fin heats pipe cross-sectional area account for fluid bed radial cross-section long-pending 20%.
By gas access while gas distributor passes into 600 DEG C of nitrogen, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is copper, silver and ZSM-5 molecular sieve, the mass ratio of copper, silver and ZSM-5 molecular sieve is respectively 1:12 and 1:100, its particle diameter 20-250 μm, bulk density is 650kg/m
3.After catalyst being heated to 300 DEG C, pass into 900 DEG C of high-temperature flue gas to heating tube, the temperature controlling first, second, third beds is respectively 650 DEG C, 600 DEG C, 530 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 100% propane, the weight space velocity controlling gas access propane is 3h
-1, reaction pressure is 1MPa, gas speed 0.2m/s.Unstrpped gas is after three beds, and its conversion ratio is greater than 66%, and one way arenes selectivity alkyl is greater than 50%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration is through the continuous return mechanism of catalyst inlet.The catalyst quality entering the regeneration of fluid bed from the catalyst inlet of first, second, third beds accounts for 50%, 40%, 10% of catalyst gross mass respectively.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 100% conversion of propane is greater than 66%, the catalyst life time lengthening 50% that arenes selectivity alkyl is greater than 50%.
Embodiment 6
Stage fluidized bed device as shown in Figure 2, first and second catalyst bed interlayer distribution grid percent opening is second and the 3rd 1 times of catalyst bed interlayer distribution grid percent opening.The position of outer overflow pipe upper outlet is adjacent 0.8 times that below distribution grid spacing is assembly dia.The position of outer overflow pipe lower inlet is in the first beds.Three catalyst inlets pass in three beds respectively, and third layer catalyst inlet position is than the upper outlet height 1.5m of overflow pipe outer outside its neighboring devices.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system through pipeline.Outer overflow pipe top cross-sectional area is 1.2 times of its underpart cross-sectional area.Set fin heats pipe cross-sectional area account for device radial cross-section long-pending 35%.
By gas access while gas distributor passes into 600 DEG C of air, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is gallium, platinum and ZSM-5 and ZSM-11 molecular sieve, the mass ratio of gallium, platinum and ZSM-5 molecular sieve is respectively 1:20 and 1:500, the mass ratio of gallium and ZSM-11 molecular sieve is 1:80, its particle diameter 30-300 μm, bulk density is 850kg/m
3.After catalyst being heated to 300 DEG C, passing into 700 DEG C of high-temperature flue gas, control first, second to heating tube, the temperature of the 3rd beds is respectively 600 DEG C, 650 DEG C, 530 DEG C.Pass into nitrogen from gas access through gas distributor to replace, after oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 40% propane, 30% butane and 30%C
5-C
7hydrocarbon, the weight space velocity controlling gas access propane is 0.3h
-1, reaction pressure is 0.5MPa, gas speed 0.4m/s.Unstrpped gas 40% propane is after three beds, and its conversion ratio is greater than 69%, and one way arenes selectivity alkyl is greater than 50%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration is through the continuous return mechanism of catalyst inlet.The catalyst quality entering the regeneration of fluid bed from the catalyst inlet of first, second, third beds accounts for 50%, 30%, 20% of catalyst gross mass respectively.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 40% conversion of propane is greater than 69%, the catalyst life time lengthening 45% that arenes selectivity alkyl is greater than 50%.
Embodiment 7
Stage fluidized bed device as shown in Figure 2, the percent opening of first and second catalyst bed interlayer distribution grid is second and the 3rd 1.1 times of percent opening of catalyst bed interlayer distribution grid.The position of outer overflow pipe upper outlet and below it distribution grid spacing be 1.3 times of assembly dia.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system through pipeline.Outer overflow pipe top cross-sectional area is 1.5 times of its underpart cross-sectional area.The position of outer overflow pipe lower inlet is in the first beds.Three catalyst inlets pass in three beds respectively, and the position of third layer beds catalyst inlet is than the upper outlet height 1.5m of overflow pipe outer outside its neighboring devices.Set fin heats pipe cross-sectional area account for device radial cross-section long-pending 28%.
By gas access while gas distributor passes into 500 DEG C of air, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is zinc, silver, ZSM-5, ZSM-11 molecular sieve, the mass ratio of zinc, silver and ZSM-5 molecular sieve is 1:30 and 1:20, the mass ratio of zinc and ZSM-11 is 1:50, its particle diameter 20-400 μm, bulk density is 1050kg/m
3.Catalyst is heated to 280 DEG C, passes into 700 DEG C of argon gas containing 80% carbon nanopowder body to heating tube, the temperature controlling first, second, third beds is respectively 530 DEG C, 570 DEG C and 650 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 70% butane and 30%C
5-C
7hydrocarbon, the weight space velocity controlling gas access butane is 2h
-1, reaction pressure is 0.8MPa, gas speed 0.6m/s.Unstrpped gas 70% butane is after two beds, and its conversion ratio is greater than 80%, and one way arenes selectivity alkyl is greater than 60%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration is through the continuous return mechanism of catalyst inlet.The catalyst quality entering the regeneration of fluid bed from the catalyst inlet of first, second, third beds accounts for 10%, 40%, 50% of catalyst gross mass respectively.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 70% butanes conversion is greater than 80%, the catalyst life time lengthening 50% that arenes selectivity alkyl is greater than 60%.
Embodiment 8
Stage fluidized bed device as shown in Figure 2, the percent opening of first and second catalyst bed interlayer distribution grid is second and the 3rd 1.4 times of catalyst bed interlayer distribution grid percent opening.The position of outer overflow pipe upper outlet is adjacent 2 times that below distribution grid spacing is assembly dia.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system through pipeline.Outer overflow pipe top cross-sectional area is 1.4 times of its underpart cross-sectional area.The position of outer overflow pipe lower inlet is in the first beds.Three catalyst inlets pass in three beds respectively, and the position of third layer beds catalyst inlet is than overflow pipe upper outlet height 0.4m outer outside its neighboring devices.The cross-sectional area of set fin heats pipe account for device radial cross-section long-pending 20%.
By gas access while gas distributor passes into 500 DEG C of nitrogen, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is zinc, silver, ZSM-5, ZSM-11 molecular sieve, the mass ratio of zinc, silver and ZSM-5 molecular sieve is 1:30 and 1:20, the mass ratio of zinc and ZSM-11 is 1:50, its particle diameter 20-400 μm, bulk density is 750kg/m
3.Catalyst is heated to 250 DEG C, passes into 700 DEG C of high-temperature flue gas to heating tube, the temperature controlling first, second, third beds is respectively 620 DEG C, 600 DEG C, 530 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 100% propane, the weight space velocity controlling gas access propane is 3h
-1, reaction pressure is 1MPa, gas speed 0.2m/s.Unstrpped gas is after three beds, and its conversion ratio is greater than 60%, and one way arenes selectivity alkyl is greater than 54%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration is through the continuous return mechanism of catalyst inlet.The catalyst quality entering the regeneration of fluid bed from the catalyst inlet of first, second, third beds accounts for 10%, 50%, 40% of catalyst gross mass respectively.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 100% conversion of propane is greater than 60%, the catalyst life time lengthening 50% that arenes selectivity alkyl is greater than 54%.
Embodiment 9
Four sections of fluidized bed plants as shown in Figure 3, the percent opening of first and second catalyst bed interlayer distribution grid is second and the 3rd 1 times of percent opening of catalyst bed interlayer distribution grid, is 2 times of the 3rd and the 4th catalyst bed interlayer distribution grid percent opening.The position of outer overflow pipe upper outlet is adjacent 0.1 times that below distribution grid spacing is assembly dia.From the catalyst that outer overflow pipe upper end outlet enters, contained gas causes near fluid bed top catalyst recovery system through pipeline, enters fluid bed inside.The cross-sectional area of the outer overflow pipe of epimere is 1.5 times of the outer overflow pipe cross-sectional area of adjacent hypomere.The position of outer overflow pipe lower end import is in the first beds.Three catalyst inlets pass in three beds respectively, and the position of the 4th layer of beds catalyst inlet is than the upper end outlet height 0.4m of overflow pipe outer outside its neighboring devices.Set fin heats pipe cross-sectional area account for device radial cross-section long-pending 20%.
By gas access while gas distributor passes into 450 DEG C of air, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is silver, ZSM-5, ZSM-11 molecular sieve, silver is 1:20 with the mass ratio of ZSM-5 molecular sieve, silver is 1:60 with the mass ratio of ZSM-11 molecular sieve, its particle diameter 30-240 μm, bulk density is 1070kg/m
3.Catalyst is heated to 300 DEG C, pass into 800 DEG C of argon gas containing 50% carbon nanopowder body to heating tube, the temperature controlling first, second, third, fourth beds is respectively 600 DEG C, 600 DEG C, 580 DEG C, 530 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 100% butane, the weight space velocity controlling gas access butane is 1h
-1, reaction pressure is 0.5MPa, gas speed 0.4m/s.Unstrpped gas is after four beds, and its conversion ratio is greater than 82%, and one way arenes selectivity alkyl is greater than 55%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration is through the continuous return mechanism of catalyst inlet.30%, 10%, 50% of catalyst gross mass is accounted for respectively, 10% from the regenerated catalyst quality of the catalyst inlet access to plant of first, second, third, fourth beds.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 100% butanes conversion is greater than 82%, the catalyst life time lengthening 50% that arenes selectivity alkyl is greater than 55%.
Embodiment 10
Four sections of fluidized bed plants as shown in Figure 3, the percent opening of first and second catalyst bed interlayer distribution grid is second and the 3rd 1.4 times of percent opening of catalyst bed interlayer distribution grid, is 1 times of the percent opening of the 3rd and the 4th catalyst bed interlayer distribution grid.Outer overflow pipe upper outlet position is adjacent 0.5 times that below distribution grid spacing is assembly dia.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system through pipeline.Outer overflow pipe top cross-sectional area is 1.5 times of its underpart cross-sectional area.The position of outer overflow pipe lower inlet is in the first beds.Three catalyst inlets pass in three beds respectively, and the 4th layer of beds catalytic amount entry position is than overflow pipe upper outlet height 0.5m outer outside its neighboring devices.Set fin heats pipe cross-sectional area account for device radial cross-section long-pending 35%.
By gas access while gas distributor passes into 550 DEG C of air, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is gallium, ZSM-5, ZSM-11 molecular sieve, the mass ratio of gallium and ZSM-5 molecular sieve is respectively 1:20, the mass ratio of gallium and ZSM-11 molecular sieve is 1:20, its particle diameter 30-180 μm, bulk density is 1300kg/m
3.After catalyst being heated to 280 DEG C, to heating tube energising, control first, second, the 3rd, the temperature of the 4th beds is 600 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 100% propane, the weight space velocity controlling gas access propane is 2h
-1, reaction pressure is 0.8MPa, gas speed 0.2m/s.Unstrpped gas is after four beds, and its conversion ratio is greater than 60%, and one way arenes selectivity alkyl is greater than 50%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration is through the continuous return mechanism of catalyst inlet.30%, 50%, 10% of catalyst gross mass is accounted for respectively, 10% from the regenerated catalyst quality of the catalyst inlet access to plant of first, second, third, fourth beds.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 100% conversion of propane is greater than 60%, the catalyst life time lengthening 50% that arenes selectivity alkyl is greater than 50%.
Embodiment 11
Four sections of fluidized bed plants as shown in Figure 3, the percent opening of first and second catalyst bed interlayer distribution grid is second and the 3rd 1.2 times of percent opening of catalyst bed interlayer distribution grid, is 1.5 times of the percent opening of the 3rd and the 4th catalyst bed interlayer distribution grid.The position of outer overflow pipe upper outlet is adjacent 0.8 times that below distribution grid spacing is assembly dia.From the catalyst that outer overflow pipe upper outlet enters, contained gas causes near device inner catalyst recovery system through pipeline.Outer overflow pipe top cross-sectional area is 1.2 times of its underpart cross-sectional area.Outer overflow pipe lower inlet position is in the first beds.Three catalyst inlets pass in three beds respectively, and the 4th layer of beds catalyst inlet position is than the upper outlet height 1.5m of overflow pipe outer outside its neighboring devices.Set fin heats pipe cross-sectional area account for device radial cross-section long-pending 23%.
By gas access while gas distributor passes into 500 DEG C of nitrogen, by fluidizer type catalyst from catalyst inlet charging apparatus, wherein catalyst main active is zinc, platinum, silver and ZSM-5 molecular sieve, zinc, platinum, mass ratio that is silver-colored and ZSM-5 molecular sieve are respectively 1:30 and 1:600 and 1:80, its particle diameter 30-500 μm, and bulk density is 1050kg/m
3.After catalyst being heated to 300 DEG C, passing into 900 DEG C of high-temperature flue gas, control first, second, the 3rd to heating tube (4), the temperature of the 4th beds is respectively 600 DEG C, 600 DEG C, 580 DEG C and 550 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 50% propane, 45% butane and 5%C
5-C
7hydrocarbon, the weight space velocity controlling propane in fluid bed is 0.5h
-1, reaction pressure is 0.15MPa, gas speed 0.8m/s.Unstrpped gas 50% propane is after four beds, and conversion ratio is greater than 58%, and one way arenes selectivity alkyl is greater than 53%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration is through the continuous return mechanism of catalyst inlet.20%, 20%, 10% of catalyst gross mass is accounted for respectively, 50% from the regenerated catalyst quality of the catalyst inlet access to plant of first, second, third, fourth beds.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 50% conversion of propane is greater than 58%, the catalyst life time lengthening 50% that arenes selectivity alkyl is greater than 53%.
Embodiment 12
Four sections of fluidized bed plants as shown in Figure 3, the percent opening of first and second catalyst bed interlayer distribution grid is second and the 3rd 1.4 times of percent opening of catalyst bed interlayer distribution grid, is 1.4 times of the percent opening of the 3rd and the 4th catalyst bed interlayer distribution grid.The position of outer overflow pipe upper outlet is adjacent 2 times that below distribution grid spacing is reactor diameter.From the catalyst that outer overflow pipe upper end outlet enters, contained gas causes near fluid bed top catalyst recovery system through pipeline, enters fluid bed inside.The cross-sectional area of the outer overflow pipe of epimere is 1.3 times of the outer overflow pipe cross-sectional area of adjacent hypomere.The position of outer overflow pipe lower end import is in the first beds.Three catalyst inlets pass in three beds respectively, and the 4th layer of beds catalyst inlet position is than the upper outlet height 1.2m of overflow pipe outer outside its neighboring devices.Set fin heats pipe cross-sectional area account for device radial cross-section long-pending 30%.
By gas access while gas distributor passes into 400 DEG C of nitrogen, fluidizer type catalyst is loaded four sections of fluid beds from catalyst inlet, wherein catalyst main active is zinc, copper, platinum, ZSM-5 molecular sieve, zinc, copper, mass ratio that is silver-colored and ZSM-5 molecular sieve are respectively 1:20 and 1:80 and 1:300, its particle diameter 20-350 μm, bulk density is 680kg/m
3.Catalyst is heated to 300 DEG C, passes into 800 DEG C of high-temperature flue gas, control first, second, the 3rd to heating tube, the temperature of the 4th beds is respectively 600 DEG C, 580 DEG C, 550 DEG C and 530 DEG C.Pass into nitrogen from gas access through gas distributor to replace, when oxygen purity is less than 0.5% in the gas of gas vent, pass into unstrpped gas 30% propane, 60% butane, 10%C
5-C
7hydrocarbon, the weight space velocity controlling gas access propane is 0.3h
-1, reaction pressure is 0.5MPa, gas speed 0.4m/s.Unstrpped gas 30% propane is after four beds, and conversion ratio is greater than 60%, and one way arenes selectivity alkyl is greater than 60%, then after catalyst recovery system is separated, flows out obtain gas products from device.
Exported to be continuously removed by decaying catalyst by decaying catalyst and regenerate, the catalyst after regeneration is through the continuous return mechanism of catalyst inlet.10%, 50%, 10% of catalyst gross mass is accounted for respectively, 30% from the regenerated catalyst quality of the catalyst inlet access to plant of first, second, third, fourth beds.Repeat said process, process is carried out continuously.
The present invention is compared with single hop fluidized-bed conversion technology, and unstrpped gas 30% conversion of propane is greater than 60%, the catalyst life time lengthening 60% that arenes selectivity alkyl is greater than 60%.
Claims (8)
1. prepared a fluidized bed plant for aromatic hydrocarbons by alkane, comprising: gas access (1), gas vent (7), gas distributor (2) and catalyst recovery system (6), wherein:
Described gas access (1) top is connected with described bottom of device, and bottom is stretched out from described bottom of device,
Described gas distributor (2), above gas access, is connected with described device inside,
Described gas vent (7) top is stretched out from described device top, and bottom is connected with catalyst recovery system (6) top,
Described catalyst recovery system (6) top is connected with gas vent, and bottom does not contact described device inwall,
It is characterized in that, described device also comprises distribution grid (3), heating tube (4), outer overflow pipe (5), catalyst inlet (8), decaying catalyst outlet (9), wherein:
Described distribution grid (3) is connected with described device inwall, is placed horizontally in described device,
Described heating tube (4) is arranged on below distribution grid and top, and heating tube import and export are connected with described device inwall,
Described outer overflow pipe (5) lower openings passes in bottom beds, outer overflow pipe top and described device parallel longitudinal,
Catalyst inlet (8) bottom is connected with described device left side wall, and top tilts upward from described device left side wall stretches out,
Described decaying catalyst outlet (9) top is connected with described device right side wall, and bottom is tilted to from described device right side wall stretches out;
Described device is divided into 4 beds by described distribution grid, for stacking catalyst; Beds is the first beds from bottom to up, the second beds, the 3rd beds, the 4th beds; Each beds has 1 catalyst inlet, and most top layer catalyst inlet position 0.4-1.5m above overflow pipe upper outlet position outside, and the regenerated catalyst quality that each catalyst inlet enters described device accounts for the 10-50% of this layer of catalyst gross mass;
Described distribution grid is horizontal multihole distributor, quantity is 1-3, wherein distribution grid percent opening described in first and second catalyst bed interlayer be the 1-1.4 of the second and the 3rd distribution grid percent opening described in catalyst bed interlayer doubly, be 1-2 times of distribution grid percent opening described in the 3rd and the 4th catalyst bed interlayer;
The tube bank of described heating tube is parallel with described device lateral, and heating tube outer surface is fin structure, and the distribution of one meter, each fin interval, the conduit on adjacent both ends fin is not exclusively corresponding, and heating tube cross-sectional area is the 20-35% that described device radial cross-section amasss;
Described outer overflow pipe upper outlet position and below it adjacent distributions plate distance be the 0.1-2 of described assembly dia doubly, all outer overflow pipe lower inlet positions are all in bottom beds, in three sections of bed apparatus and four sections of bed apparatus, outer overflow pipe top cross-sectional area is 1.2-1.5 times of its underpart cross-sectional area, and from the catalyst that outer overflow pipe upper outlet enters, contained gas causes near described device inner catalyst recovery system through pipeline.
2. use fluidized bed plant described in claim 1 to prepare a method for aromatic hydrocarbons by alkane, it is characterized in that, comprise the steps:
(1) gas is passed into while adding catalyst;
(2) be energized or pass into medium to heating tube;
(3) unstrpped gas is passed into;
(4) divided gas flow product and catalyst;
(5) catalyst is reclaimed;
(6) gas products is obtained;
(7) catalyst regeneration;
(8) circulation said process.
3. method according to claim 2, is characterized in that, described step (1) passes into 300-600 DEG C of nitrogen or air by gas access through gas distributor while loading catalyst.
4. method according to claim 2, it is characterized in that, the medium of described step (2) is lightweight carbon nanomaterial and inert gas.
5. method according to claim 2, it is characterized in that, the medium temperature of described step (2) is 700-900 DEG C, and direct heatable catalyst bed temperature is 530-650 DEG C.
6. method according to claim 2, is characterized in that, before described step (3) passes into unstrpped gas, pass into nitrogen replace by gas access through gas distributor.
7. method according to claim 2, it is characterized in that, described alkane is propane and/or butane, or propane and/or butane and C
5-C
7the mixture of non-aromatics.
8. method according to claim 7, it is characterized in that, described step (4) is front, and unstrpped gas is after beds, and when 530-650 DEG C, conversion of propane is 45%-80%, and arenes selectivity alkyl is 46%-55%; Butanes conversion is 58%-80%, and arenes selectivity alkyl is greater than 55%.
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| CN1958146A (en) * | 2006-10-13 | 2007-05-09 | 宜宾天原股份有限公司 | Multiple stage fluidized-bed reactor and method for synthesizing chloroethylene |
| CN101121635A (en) * | 2007-07-19 | 2008-02-13 | 新疆天业（集团）有限公司 | Method for preparing vinyl chloride by circulating fluidized bed reactor and device thereof |
| CN102482179A (en) * | 2009-03-12 | 2012-05-30 | 国际壳牌研究有限公司 | Process for conversion of lower alkanes to aromatic hydrocarbons |
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| CN1958146A (en) * | 2006-10-13 | 2007-05-09 | 宜宾天原股份有限公司 | Multiple stage fluidized-bed reactor and method for synthesizing chloroethylene |
| CN101121635A (en) * | 2007-07-19 | 2008-02-13 | 新疆天业（集团）有限公司 | Method for preparing vinyl chloride by circulating fluidized bed reactor and device thereof |
| CN102482179A (en) * | 2009-03-12 | 2012-05-30 | 国际壳牌研究有限公司 | Process for conversion of lower alkanes to aromatic hydrocarbons |
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