CN101279884A - Ethanol dehydration fluidized bed process and reaction - Google Patents
Ethanol dehydration fluidized bed process and reaction Download PDFInfo
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- CN101279884A CN101279884A CNA2008101236181A CN200810123618A CN101279884A CN 101279884 A CN101279884 A CN 101279884A CN A2008101236181 A CNA2008101236181 A CN A2008101236181A CN 200810123618 A CN200810123618 A CN 200810123618A CN 101279884 A CN101279884 A CN 101279884A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000018044 dehydration Effects 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000009834 vaporization Methods 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract 2
- 238000005516 engineering process Methods 0.000 description 14
- 239000008187 granular material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000012546 transfer Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000011143 downstream manufacturing Methods 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- -1 polyethylene, ethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- JLQFVGYYVXALAG-CFEVTAHFSA-N yasmin 28 Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C([C@]12[C@H]3C[C@H]3[C@H]3[C@H]4[C@@H]([C@]5(CCC(=O)C=C5[C@@H]5C[C@@H]54)C)CC[C@@]31C)CC(=O)O2 JLQFVGYYVXALAG-CFEVTAHFSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses an ethanol dehydration fluidized bed process, which takes an ethanol aqueous solution as a material and a molecular sieve as a catalyst, and prepares an ethylene through conducting the dehydration reaction in a fluidized bed reactor. The process comprises the detailed steps that: a molecular sieve catalyst is added to the fluidized bed reactor through a catalyst entrance and the reactor is preheated by heat conducting oil, the ethanol aqueous solution is vaporized, preheated and then supplied to the fluidized bed reactor when reaching the reaction temperature of between 180 and 300 DEG C, the catalyst flows under the action of the airflow of the ethanol water and has the dehydration reaction with the airflow, the reacted gas undergoes the water washing and alkaline washing after the heat exchange, thereby obtaining the ethylene gas. The invention also discloses a high efficient fluidized bed reactor. The process has advantages of improving the heat exchange efficiency, reducing the catalyst consumption and energy consumption, saving costs and improving the ethanol conversion per pass and ethylene yield.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of fluidized-bed process that molecular sieve catalyst carries out ethanol dehydration and fluidized-bed reactor that in this technology, uses of adopting.
Background technology
Ethene is the most important basic material of petrochemical complex industry, also is the chemical of output maximum in the world, and the developmental level of ethylene industry has been represented the overall development level of a national petrochemical industry.The industrial production of ethene all adopts the petroleum route both at home and abroad at present, but petroleum resources are being faced with serious short crisis.Therefore, under the situation of petroleum resources worsening shortages, must seek the road of a sustainable development, solve because oil reduces the negative impact that is brought, this just makes ethene to biological process unprecedented opportunities and challenge is provided.Biological ethane is meant that biomass obtain ethanol by fermentation, ethanol dewaters under the effect of catalyzer and generates ethene, currently mainly in producing ethylene by ethanol dehydration have two gordian techniquies: 1) catalyzer, the catalyzer that industrial ethanol dehydration is adopted mainly is the catalyzer of aluminum oxide and modification thereof.The aluminium oxide catalyst biggest advantage is a good stability, and regenerability is good, the ethene purity height that makes.But aluminium oxide catalyst also exists obvious deficiency: the temperature of reaction height, the charging air speed is low, reacts required energy consumption height.At this problem, what current research was many is molecular sieve catalyst, this catalyst reaction temperatures low (200-300 ℃), and the charging air speed is big, and (liquid hourly space velocity is greater than 1.0h
-1), react required energy consumption and obviously reduce.But the subject matter that this catalyzer exists is less stable, needs often regeneration.2) reaction process flow process, current ethanol dehydration generates the production technique of ethylene process based on U.S. Ha Kang-Scientific Design Company, Inc.'s design, and Kai Fa technology also has the Lummus fixed-bed process on this basis, Holcon/SD technology, Nikki/JGC technology, Petrobras technology etc.
In ethanol dehydration technique,, need carry out pre-treatment in order better ethylene gas to be carried out rectifying, in pre-treatment, soda-wash tower is necessary equipment, and purpose is some sour gas of removing in the gas, and the soda-wash tower of current employing generally is the circulation alkali liquor of the single concentration of one-part form.Because the existence of by product acetaldehyde, polymerization takes place under the alkali lye condition generate polymkeric substance, this material is the indissoluble material, to produce stifled tower to Packed soda-wash tower, for continuity production brings difficulty, domestic certain factory is owing to this reason needs often to stop production to clean, not only influenced the output of ethene, also produced simultaneously a large amount of waste water, filler need be changed when serious, and cost strengthens.
Ethanol dehydration reaction is a strong endothermic reaction, in order to keep the needed temperature of reaction, must adopt external heat source to carry out heat supply.Industrial employing mainly be that fused salt (saltpetre 53%, Sodium Nitrite 40%, SODIUMNITRATE 7%) heats.The advantage of this type of heating is simple to operate, and temperature distribution is more even relatively.But fused salt is serious to equipment corrosion, and thermal lag is big, heats up slowly.
Summary of the invention
The objective of the invention is big at the power consumption of existing ethanol dehydration technique, ethanol conversion is low, yield of ethene is low, the poor catalyst stability inactivation fast, adopt in fused salt heating installation seriously corroded and heat exchange weak effect, the subsequent disposal shortcoming such as the stifled tower of alkali cleaning, provide a kind of employing efficiently fluidized-bed reactor carry out the technology of producing ethylene by ethanol dehydration.
Another object of the present invention provides fluidized-bed reactor efficiently.
Purpose of the present invention can reach by following measure:
A kind of ethanol dehydration fluidized bed process, it is that raw material, molecular sieve are catalyzer with the aqueous ethanolic solution, prepares ethene by carry out dehydration reaction in fluidized-bed reactor.Concrete steps are:
Molecular sieve catalyst is joined in the fluidized-bed reactor by catalyst inlet, and reactor is carried out preheating by thermal oil, after reaching 180-300 ℃ temperature of reaction, to feed fluidized-bed reactor after aqueous ethanolic solution vaporization and the preheating, catalyzer is in the effect current downflow of ethanol water flow, and with air-flow generation dehydration reaction, behind the reacted gas converting heat by the washing and alkali cleaning, obtain ethylene gas.
Wherein the concentration of aqueous ethanolic solution is 10～95%, preferred 20～65%.
Available molecular sieve catalyst is the molecular sieve of ZSM-5, SAPO-31 type, TS-1 type molecular sieve or its modification in above-mentioned technology, as metal ion-modified molecular sieves such as nickel, lanthanum, phosphorus, iron, potassium or ceriums.Catalyzer is in the effect current downflow of air-flow, and with air-flow generation dehydration reaction, bigger granules of catalyst rises with air-flow, speed reduces after reaching expanding reach, come back to reactor bottom, less granules of catalyst is deposited on the gas distribution grid after separating by cyclonic separator.
Reacted gas is at first washed by water wash column, and purpose is to remove some responseless ethanol raw materials and some aldehyde materials; Carry out alkali cleaning by the multi-stage type soda-wash tower again, purpose is to remove some sour gas (CO
2Deng), treated gas enters downstream process then; The multi-stage type soda-wash tower is generally the 2-4 section, and wherein concentration of lye is reduced down certainly successively by last.
A kind of fluidized-bed reactor comprises housing 11 and bottom cone 6, its middle and lower part cone 6 be located at housing 11 lower ends and with its sealing, also comprise be located at housing 11 upper ends and with the internal diameter of its sealing expanding reach 18 greater than housing 11; Be located at expanding reach 18 inside cyclonic separator 17 the upper end be located at expanding reach 18 tops and communicate with pneumatic outlet 19 after the reaction that reactor is interlinked to the outside, the lower end of cyclonic separator 17 communicates 23 with the suitable for reading of centre pipe in the housing 11; Between housing 11 and internal cyclone separators 17, be provided with and refer to jacket tube bank 10; In the bottom of housing 11, refer to below the jacket tube bank 10 and the end opening place of centre pipe 23 is provided with gas distribution grid 8.The built-in cyclonic separator 17 of fluidized-bed reactor can well separate small granules of catalyst entering on the gas distribution grid 8 by centre pipe.
Be provided with and the extraneous catalyst inlet 16 that communicates at the middle part of expanding reach 18, be provided with and the extraneous catalyzer discharge opening 7 that communicates at housing 11 and bottom cone 6 joints.The middle part of bottom cone 6 is provided with and the extraneous fluidized-bed reactor unstripped gas inlet 5 that communicates.
Be provided with and the thermal oil inlet 13 and the thermal oil outlet 14 that refer to that jacket tube bank 10 communicates on housing 11 tops.In order to improve heat exchange efficiency, 13 and two outlets 14 of two thermal oil inlets can be set in cylindrical shell symmetry both sides.
In housing 11, be provided with fixing following parts casing pipe fixed tube 9 and the upper sleeve fixed tube 12 that refers to jacket tube bank 10 and centre pipe 23.
Characteristics of the present invention are to adopt fluidized-bed to substitute traditional fixed-bed reactor, not only improved heat-transfer effect, more significantly adopt thermal oil to come fluid bedreactors to heat, for ethanol dehydration reaction provides energy needed, in addition, in fluidized-bed reactor, cyclonic separator is arranged on the inside of reactor, has improved the utilization ratio of reactor, also make the amount of carrying secretly of catalyzer reduce, reduced cost.The present invention adopts thermal oil as heat transferring medium aspect catalyzer is heated in addition, has improved the heat exchange effect, and the etching problem of equipment also is well solved.In the post-treatment caustic wash process, adopt multi-stage type different concns alkali liquid washing, so not only reduced stifled tower degree, also saved the alkali lye consumption simultaneously, also alleviated pressure for follow-up sewage disposal, below each content is done specified respectively:
Efficient stream fluidized bed reactor of the present invention adopts the built-in cyclonic separator and the thermal oil recycle system, the thermal oil recycle system adopts and refers to molded cannula technology, thermal oil refers in the interior pipe of type pipe from being evenly distributed to each periphery after import enters, flow into the outer tube that another refers to the type pipe from outer tube then, flow into the interior pipe of adjacent finger type pipe again by pipe in it, by that analogy, last upwards being routed up by the interior pipe of a finger type pipe enters into outlet, flow out fluidized-bed reactor, provide reaction needed heat.Adopt this fluidized-bed can to inactivation faster molecular sieve catalyst good application is arranged.
Fluidized-bed is as a kind of reactor in industrial widespread use, the characteristics that himself is arranged: this reactor can use the catalyzer of small grain size, thereby the influence of internal diffusion can be ignored fully, improved the utilization ratio of catalyzer, temperature is even, can realize isothermal operation fully, this requires very narrow catalytic reaction process very suitable for some temperature of reaction, fluidized-bed reactor also very suitable catalyst need the reaction of cyclic regeneration, the adding of catalyzer and draw off all very conveniently, and pressure does not fall with gas speed and changes.
In order better reactive system to be carried out heat supply, the present invention adopts thermal oil to substitute traditional fused salt.Thermal oil is compared with fused salt has following advantage: equipment is not had corrosion, avoided the easy scaling of steam oven pipeline and to the corrodibility of equipment; Be difficult for coking, specific heat and thermal conductivity are big; Heat-conductive characteristic is good; Vapor pressure is lower in the maximum permisible service temperature scope, has reduced total system pressurized grade, thereby has reduced equipment cost, and the pressure build-up rate is little, and vaporization losses is little; Zero pour is low, can be used for cold district, is difficult for blocking pipeline, and equipment viscosity is little, is easy to carry; Thermal oil is that the medium system operating pressure is little.
Adopt fluidized-bed process can well solve the difficult problem of molecular sieve less stable, after adopting fluidization, can regenerate to catalyzer, the loading and unloading of catalyzer are very convenient.Employing refers to difficult problems such as the jacket tube bank can solve fixed bed heat exchange weak effect, and radial temperature difference is big.The good heat transfer and the mass-transfer performance of fluidized-bed can be completely achieved isothermal operation.
At producing the stifled tower problem of soda-wash tower in the Industrial processes, the present invention adopts the multi-stage type soda-wash tower, utilizes the circulation of different concns gradient alkali lye in addition, can effectively slow down the stifled tower time, reduce the consumption of alkali lye, the consumption of washing water also reduces, thereby eases off the pressure for follow-up sewage disposal.
The present invention has the following advantages:
1, adopts fluidized-bed to replace traditional fixed bed, improved heat exchange efficiency, reduced catalyst levels,, adopt fluidized-bed can access higher ethanol per pass conversion and yield of ethene with respect to calandria type fixed bed reactor.
2, adopt fluidized-bed reactor technology, can load and discharging catalyzer easily, this has better application for needs regenerated molecular sieve catalyst.
3, adopt fluidized-bed process, can be applied to this technology by the molecular sieve catalyst that activity is very high, with respect to traditional catalyst, energy consumption can significantly reduce.
4, adopt fluidized-bed process, under same throughput, catalyst levels can reduce, and has reduced production cost.
5, behind employing fluidized-bed process and the molecular sieve catalyst, can adopt thermal oil to heat, because traditional catalyst temperature of reaction height, thermal oil can't satisfy.Adopt thermal oil can reduce equipment corrosion, relatively costly pump for liquid salts adopts the Heat-transfer Oil Pump escapable cost.
6, in subsequent disposal, adopt the soda-wash tower of multi-stage type different concns alkali lye to replace traditional single concentration single hop alkali washing process, saved the alkali lye consumption, improve the anti-stifled ability of soda-wash tower, also alleviated pressure simultaneously for follow-up sewage disposal.
Description of drawings
Fig. 1 adopts the ethanol dehydration technique schema of fluidized-bed for the present invention.
Among the figure 1: head tank; 2: pump; 3: preheater; 4: interchanger; 5 fluidized-bed reactor unstripped gass inlet; 6: the bottom cone; 7: the catalyzer discharge opening; 8: gas distribution grid; 9: following parts casing pipe fixed tube; 10: refer to the jacket tube bank; 11: housing; 12: the upper sleeve fixed tube; 13: the thermal oil inlet; 14: the thermal oil outlet; 15: the cylindrical shell junction; 16: catalyst inlet; 17: cyclonic separator; 18: expanding reach; 19: reaction back pneumatic outlet; 20: water wash column; 21: the multi-stage type soda-wash tower; 22: gas enters downstream processing.
Fig. 2 is for referring to the molded cannula connection diagram.
Fig. 3 is the fluidized-bed reactor vertical view.
Wherein 23 is centre pipe.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described in detail.
Embodiment 1
The lower end of the housing 11 of fluidized-bed reactor and the sealing of the upper end of bottom cone 6, be provided with fluidized-bed reactor unstripped gas inlet 5 at the middle part of bottom cone 6, be provided with catalyzer discharge opening 7 corresponding to housing 11 and the position that bottom cone 6 seals, be provided with gas distribution grid 8 to collect the catalyzer of sinking on the bottom of housing 11, the top of catalyzer discharge opening 7.In housing 11, be provided with two sleeve pipe fixed tube, be respectively down parts casing pipe fixed tube 9 and upper sleeve fixed tube 12, with the centre pipe 23 of cyclonic separator 17 lower ends that fixedly are built in fluidized-bed reactor and be arranged at cyclonic separator 17 and housing 11 between the finger jacket restrain 10.Refer to that the thermal oil entry and exit of jacket tube bank 10 are arranged at the top of housing 11 respectively.The upper end sealing of the lower end of expanding reach 18 and housing 11, the internal diameter of expanding reach 18 main bodys are greater than housing 11, and to slow down air-flow velocity, speed reduced after bigger granules of catalyst reached expanding reach, can come back to reactor bottom.Pneumatic outlet 19 after the top of expanding reach 18 responds, the upper end of cyclonic separator 17 communicates with reaction back pneumatic outlet 19, and the lower end of cyclonic separator 17 communicates with the suitable for reading of centre pipe 23, and the end opening of centre pipe 23 is positioned on the gas distribution grid 8.
Aqueous ethanolic solution in the head tank 1 feeds preheater 3 by pump 2 pressurization backs and vaporizes, and the gas after the vaporization enters in the fluidized-bed reactor from unstripped gas inlet 5 by interchanger 4 backs, is become ethylene gas by catalyst in the air-flow uphill process.Ethylene gas is discharged reactors from pneumatic outlet 19, feeds water wash column 20 by interchanger 4 after with the unstripped gas heat exchange, removes some responseless ethanol raw materials and some aldehyde materials; Carry out alkali cleaning by multi-stage type soda-wash tower 21 again, purpose is to remove some sour gas (CO
2Deng), treated gas is ethylene gas, and purity can reach more than 99%, enters downstream process 22 then.If derived product is ethylene dichloride, oxyethane etc., this purity can reach the production demand, if products such as production polyethylene, ethylene gas also needs can reach production requirement through after the low temperature fractionation.
Embodiment 2
When on this technology, carrying out ethanol dehydration and reacting, be that the ZSM-5 molecular sieve catalyst of 300 μ m lanthanum modifications is loaded in the fluidized-bed reactor with mean particle size at first by catalyst feeds, thermal oil preheating fluidized-bed and catalyzer, when reaching 250 ℃ of temperature of reaction, concentration is that the 50wt% ethanol raw material carries out preheating by preheater, gas after the vaporization enters the fluidized-bed reactor inlet by interchanger, catalyzer begins fluidisation under the effect of air-flow, this reactor pressure is kept constant after stable, bigger granules of catalyst comes back in the fluidized-bed cylindrical shell by expanding reach, and less granules of catalyst is got back on the gas distribution grid via centre pipe by cyclonic separator.Reacted gas enters into water wash column after through the interchanger heat exchange, then by the two-part soda-wash tower, wherein the upper end concentration of lye is 8%, the hypomere concentration of lye is 4%, processing such as ethylene gas drying through alkali cleaning enter the downstream, and ethylene gas purity after treatment can reach more than 99%.Reaction ethanol conversion 98.4%, ethylene selectivity 99.15%.
Embodiment 3
When on this technology, carrying out ethanol dehydration and reacting, be that the cerium modified SAPO-31 molecular sieve catalyst of 300 μ m is loaded in the fluidized-bed reactor with mean particle size at first by catalyst feeds, thermal oil preheating fluidized-bed and catalyzer, when reaching 260 ℃ of temperature of reaction, concentration is that the 65wt% ethanol raw material carries out preheating by preheater, gas after the vaporization enters the fluidized-bed reactor inlet by interchanger, catalyzer begins fluidisation under the effect of air-flow, this reactor pressure is kept constant after stable, bigger granules of catalyst comes back in the fluidized-bed cylindrical shell by expanding reach, and less granules of catalyst is got back on the gas distribution grid via centre pipe by cyclonic separator.Reacted gas enters into water wash column after through the interchanger heat exchange, then by the two-part soda-wash tower, wherein the upper end concentration of lye is 8%, the hypomere concentration of lye is 3%, through the ethylene gas of alkali cleaning then processing such as drying enter the downstream, ethylene gas purity after treatment can reach more than 99%.Reaction ethanol conversion 97.92%, ethylene selectivity 99.54%.
Claims (8)
1, a kind of ethanol dehydration fluidized bed process, it is that raw material, molecular sieve are catalyzer with the aqueous ethanolic solution, prepares ethene by carry out dehydration reaction in fluidized-bed reactor.Concrete steps are:
Molecular sieve catalyst is joined in the fluidized-bed reactor by catalyst inlet, and reactor is carried out preheating by thermal oil, after reaching 180-300 ℃ temperature of reaction, to feed fluidized-bed reactor after aqueous ethanolic solution vaporization and the preheating, catalyzer is in the effect current downflow of ethanol water flow, and with air-flow generation dehydration reaction, behind the reacted gas converting heat by the washing and alkali cleaning, obtain ethylene gas.
2, ethanol dehydration fluidized bed process according to claim 1, the concentration that it is characterized in that described aqueous ethanolic solution is 10～95%.
3, ethanol dehydration fluidized bed process according to claim 1 is characterized in that described molecular sieve is the molecular sieve of ZSM-5, SAPO-31 type, TS-1 type molecular sieve or its modification.
4, ethanol dehydration fluidized bed process according to claim 1 is characterized in that reacted gas carries out alkali cleaning by the multi-stage type soda-wash tower.
5, a kind of fluidized-bed reactor, comprise housing (11) and bottom cone (6), its middle and lower part cone (6) be located at housing (11) lower end and with its sealing, it is characterized in that also comprising be located at housing (11) upper end and with the internal diameter of its sealing expanding reach (18) greater than housing (11); The upper end of being located at the inner cyclonic separator (17) of expanding reach (18) be located at expanding reach (18) top and communicate, suitable for reading the communicating (23) of the centre pipe that the lower end of cyclonic separator (17) and housing (11) are interior with pneumatic outlet (19) after the reaction that reactor is interlinked to the outside; Between housing (11) and internal cyclone separators (17), be provided with and refer to jacket tube bank (10); In the bottom of housing (11), refer to below the jacket tube bank (10) and the end opening place of centre pipe (23) is provided with gas distribution grid (8).
6, fluidized-bed reactor according to claim 5, it is characterized in that being provided with and the extraneous catalyst inlet (16) that communicates, be provided with and the extraneous catalyzer discharge opening (7) that communicates at housing (11) and bottom cone (6) joint at the middle part of described expanding reach (18).
7, fluidized-bed reactor according to claim 5 is characterized in that being provided with and the thermal oil inlet (13) and the thermal oil outlet (14) that refer to that jacket tube bank 10 communicates on described housing (11) top.
8, fluidized-bed reactor according to claim 5 is characterized in that being provided with fixing following parts casing pipe fixed tube (9) and the upper sleeve fixed tube (12) that refers to jacket tube bank (10) and cyclonic separator (17) in described housing (11).
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101236181A CN101279884A (en) | 2008-05-27 | 2008-05-27 | Ethanol dehydration fluidized bed process and reaction |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103108942A (en) * | 2010-05-07 | 2013-05-15 | 道达尔研究技术弗吕公司 | Use of solvent to decrease caustic scrubber fouling |
| CN108940136A (en) * | 2018-08-30 | 2018-12-07 | 中国科学院过程工程研究所 | A kind of gas-solid reaction device and method |
| CN111250006A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Coal-based ethanol-to-ethylene fast fluidized bed reactor and coal-based ethanol-to-ethylene method |
-
2008
- 2008-05-27 CN CNA2008101236181A patent/CN101279884A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103108942A (en) * | 2010-05-07 | 2013-05-15 | 道达尔研究技术弗吕公司 | Use of solvent to decrease caustic scrubber fouling |
| CN108940136A (en) * | 2018-08-30 | 2018-12-07 | 中国科学院过程工程研究所 | A kind of gas-solid reaction device and method |
| CN108940136B (en) * | 2018-08-30 | 2020-10-16 | 中国科学院过程工程研究所 | Gas-solid reaction device and method |
| CN111250006A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Coal-based ethanol-to-ethylene fast fluidized bed reactor and coal-based ethanol-to-ethylene method |
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