CN103449948B - Method for preparing olefin through dehydrogenating alkane - Google Patents
Method for preparing olefin through dehydrogenating alkane Download PDFInfo
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- CN103449948B CN103449948B CN201210179765.7A CN201210179765A CN103449948B CN 103449948 B CN103449948 B CN 103449948B CN 201210179765 A CN201210179765 A CN 201210179765A CN 103449948 B CN103449948 B CN 103449948B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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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
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention relates to a method for preparing olefin through dehydrogenating alkane. The method comprises the following steps: preheating a raw material alkane, adding the preheated alkane to the bottom of a dehydrogenation reactor, allowing the preheated alkane to contact with a catalyst for a dehydrogenation reaction, recovering the catalyst from a reaction product in a dilute phase space through a cyclone separator, removing the reaction product from the dehydrogenation reactor, cooling high temperature oil gas, and adding to a separation system; adding the spent catalyst to a spent catalyst stripping segment from the bottom of the dehydrogenation reactor, adding the oil-sprayed spent catalyst to a spent catalyst riser tube, conveying to the bottom of a reactivator through using heated main air, and carrying out scorching and heat supply in the reactivator; allowing the regenerated catalyst to flow to a regenerated catalyst stripping segment, and adding a stripped regenerated catalyst to the bed layer of a dehydrogenation reactor; recovering the catalyst from high-temperature flue gas through a cyclone separator, adding to a three-level cyclone separator for recovering catalyst fine powder, and adding to an exhaust-heat boiler for heat recovery; and adding parts of a dry gas to an auxiliary combustion chamber, and adding parts of the dry gas to a raw material preheating furnace. The method solves a fine powder catalyst fluidization problem and a reaction heat supply problem.
Description
Technical field
The present invention relates to a kind of engineering method of dehydrating alkanes alkene, more specifically to the fluidisation engineering method of alkane catalytic dehydrogenation olefin hydrocarbon apparatus.
Background technology
Alkene and diolefine (ethene, propylene, butylene, iso-butylene, isoprene and divinyl etc.) are widely used in synthetic resins, plastics, stop bracket gasoline blend component (methyl tertiary butyl ether, tert amyl methyl ether(TAME) and alkylate oil) and other high value added product.These alkene are except the steam cracking by hydrocarbon is (as ethane steam cracking, naphtha steam cracking), outside the process such as the catalytic pyrolysis (as Superflex technology) of alkene, the catalytic pyrolysis (as TMP, DCC technology) of heavy oil and heavy-oil catalytic pyrolysis (as CPP technology) produces, alkane catalytic dehydrogenation is also the important technology route that alkene and diolefine are produced.
The dehydrating alkanes industrialization technology abroad developed at present has Oleflex technique, the Catofin technique of Lummus company, the STAR technique of Phillips company, the FBD-4 technique of Snamprogetti company, the Linde technique etc. of Linde company of Uop Inc., but by supplying heat affecting many employings fixed-bed reactor.Alkane dehydrogenating catalyst is fine powder type catalyzer, therefore successfully exploitation can solve dehydrating alkanes simultaneously and will have very strong technical costs advantage to the dehydrating alkanes olefin hydrocarbon apparatus of the fluidized-bed cyclic regeneration of heat problem and fine powder catalyst fluidization problems, and market outlook are boundless.
Summary of the invention
The object of this invention is to provide a kind of method of dehydrating alkanes alkene; The reaction regeneration process of continous-stable is realized by the fluidization technique of system afterburning technology, fine powder catalyst.
The method of dehydrating alkanes alkene of the present invention: starting alkane enters bottom dehydrogenation reactor after alkane-reaction oil gas interchanger and the preheating of raw material preheating stove, by contacting with beds reverse flow uniform after alkane sparger and dehydrogenation reaction occurring, reaction heat is provided by bed catalyst, reaction product leaves dehydrogenation reactor at dilute phase space after cyclonic separator reclaims catalyzer, and high-temperature oil gas enters subsequent separation system after vapour generator, alkane-reaction oil gas interchanger cooling; Reclaimable catalyst enters reclaimable catalyst stripping stage bottom dehydrogenation reactor, in reclaimable catalyst, evenly oil fuel is sprayed in reclaimable catalyst stripping stage, or spray into oil fuel in inclined tube to be generated before riser tube to be generated, reclaimable catalyst after oil spout enters spent riser, be delivered to regenerator bottoms with the main air after auxiliary chamber heating, in revivifier following current complete burn, fuel oil combustion heat release provides sufficient heat for catalyzer; Regenerated catalyst overflow is to regenerated catalyst stripping stage, and the regenerated catalyst after stripping enters dehydrogenation reactor bed top; High-temperature flue gas in revivifier reclaims catalyzer through cyclonic separator, then leaves revivifier and enters the further recovery of catalyst fines of three-stage cyclone separator, and the high-temperature flue gas leaving three-stage cyclone separator enters waste heat boiler and reclaims heat; The self-produced dry gas part of device enters auxiliary chamber combustion heat release for catalyzer provides partial heat, a part of incoming stock preheating oven combustion heating raw material.
Dehydrogenation reactor of the present invention is single hop adverse current constant speed bubble bed reactor; Reactor dense-phase bed is inverted round table shape, top diameter is large, base diameter is little, increased by the step of bed sectional area and realize the linear speeds such as bed, be provided with alkane sparger bottom bed, top is provided with catalyst distributor, be provided with Multilayer grid in the middle of bed, dilute phase space is provided with two stage cyclone separator.
Revivifier of the present invention is single hop following current bubble bed revivifier; Be provided with catalyst distributor bottom regenerator bed, be provided with Multilayer grid in bed, dilute phase space is provided with two stage cyclone separator.
Be provided with Multilayer grid baffle plate in stripping stage of the present invention, grid is symmetrical installation of tilting, and individual layer grid sectional area is less than stripping stage cross-sectional area.
The invention provides a kind of through engineering approaches scheme of fine powder catalyst fluidized-bed successive reaction regeneration of alkane catalytic dehydrogenation alkene, flow process is simple, easy to operate, solve the fluidization problems of fine powder catalyst and the supply problem of reaction heat, thus make this production process continuously and stablize.The present invention is applicable to the full scale plant of the alkane catalytic dehydrogenation alkene adopting fluidized-bed.
Use the full scale plant of this two types formula can realize the successive reaction regenerative process of alkane catalytic dehydrogenation olefine reaction, reduce full scale plant energy consumption, enhance productivity, save manpower and flexible adjustment.Per pass conversion and the equilibrium conversion of the full scale plant starting alkane of use the method are more close, the selectivity of object product (alkene) is higher, Trimethylmethane per pass conversion in embodiment can reach 40-50%, the selectivity of iso-butylene can reach 80-90%(mole), therefore there is good industrial applicibility.
Accompanying drawing explanation
Fig. 1 is dehydrating alkanes olefin hydrocarbon apparatus fine powder catalyst fluidised bed system schematic flow sheet.
Wherein: catalyzer storage tank, 15 critical velocity nozzles are received in 1 alkane-reaction oil gas interchanger, 2 raw material preheating stoves, 3 dehydrogenation reactor 4 oil gas vapour generators, 5 reclaimable catalyst stripping stages, 6 auxiliary chambers, 7 spent risers, 8 regenerated catalyst stripping stages, 9 revivifiers, 10 three-stage cyclone separators, 11 double slide valves, 12 flue gas step-down orifice plates, 13 tetra-cyclones, 14 3 cycles
Embodiment
Below in conjunction with Fig. 1, alkane catalytic dehydrogenation olefin hydrocarbon apparatus is described.
Starting alkane enters bottom dehydrogenation reactor 3 after alkane-reaction oil gas interchanger 1 and raw material preheating stove 2 preheating, by contacting with beds reverse flow uniform after alkane sparger and dehydrogenation reaction occurring, reaction heat is provided by bed catalyst, reaction product leaves dehydrogenation reactor at dilute phase space after cyclonic separator reclaims catalyzer, and high-temperature oil gas enters subsequent separation system through vapour generator 4, alkane-reaction oil gas interchanger 1 after lowering the temperature; Reclaimable catalyst enters reclaimable catalyst stripping stage 5 bottom dehydrogenation reactor, in reclaimable catalyst, evenly oil fuel is sprayed in reclaimable catalyst stripping stage, or spray into oil fuel in inclined tube to be generated before spent riser 7, reclaimable catalyst after oil spout enters spent riser 7, be delivered to bottom revivifier 9 with the main air after auxiliary chamber 6 heats, in revivifier following current complete burn, fuel oil combustion heat release provides sufficient heat for catalyzer; Regenerated catalyst overflow, to regenerated catalyst stripping stage 8, enters dehydrogenation reactor bed top after stripping; High-temperature flue gas in revivifier reclaims catalyzer through two stage cyclone separator, then leave revivifier and enter three-stage cyclone separator 10 recovery of catalyst fines further, the high-temperature flue gas leaving three-stage cyclone separator enters waste heat boiler and reclaims heat after double slide valve 11, the step-down of flue gas step-down orifice plate 12; Catalyst fines bottom three-stage cyclone separator enters tetra-cyclone 13, catalyst fines bottom tetra-cyclone enters three-stage cyclone separator and reclaims catalyzer storage tank 14 and be interrupted outward transport process, and the flue gas at tetra-cyclone top is incorporated to the flue gas pipeline after flue gas step-down orifice plate 12 after critical velocity nozzle 15 step-down.The self-produced dry gas part of device enters auxiliary chamber 6 combustion heat release for catalyzer provides partial heat, a part of incoming stock preheating oven combustion heating raw material.
Isobutane feedstock is heated to 300-550 DEG C, enter bottom reactor bed, regenerated catalyst enters reactor bed top, regenerator temperature controls at 650-750 DEG C, temperature of reaction controls at 500-620 DEG C, reactor head pressure-controlling is in 1-10bar(absolute pressure), the empty time control of quality is built in 2-8h.Use engineering method of the present invention and equipment can obtain the per pass conversion of Trimethylmethane 40-50%, and have iso-butylene 80-90%(mole) selectivity.
Claims (1)
1. the method for a dehydrating alkanes alkene, it is characterized in that: starting alkane enters bottom dehydrogenation reactor after alkane-reaction oil gas interchanger and the preheating of raw material preheating stove, by contacting with beds reverse flow uniform after alkane sparger and dehydrogenation reaction occurring, reaction heat is provided by bed catalyst, reaction product leaves dehydrogenation reactor at dilute phase space after cyclonic separator reclaims catalyzer, and high-temperature oil gas enters subsequent separation system after vapour generator, alkane-reaction oil gas interchanger cooling; Reclaimable catalyst enters reclaimable catalyst stripping stage bottom dehydrogenation reactor, in reclaimable catalyst, evenly oil fuel is sprayed in reclaimable catalyst stripping stage, or spray into oil fuel in inclined tube to be generated before riser tube to be generated, reclaimable catalyst after oil spout enters spent riser, be delivered to regenerator bottoms with the main air after auxiliary chamber heating, in revivifier following current complete burn, fuel oil combustion heat release provides sufficient heat for catalyzer; Regenerated catalyst overflow is to regenerated catalyst stripping stage, and the regenerated catalyst after stripping enters dehydrogenation reactor bed top; High-temperature flue gas in revivifier reclaims catalyzer through cyclonic separator, then leaves revivifier and enters the further recovery of catalyst fines of three-stage cyclone separator, and the high-temperature flue gas leaving three-stage cyclone separator enters waste heat boiler and reclaims heat; The self-produced dry gas part of device enters auxiliary chamber combustion heat release for catalyzer provides partial heat, a part of incoming stock preheating oven combustion heating raw material;
Described dehydrogenation reactor is single hop adverse current constant speed bubble bed reactor; Reactor dense-phase bed is inverted round table shape, top diameter is large, base diameter is little, increased by the step of bed sectional area and realize the linear speeds such as bed, be provided with alkane sparger bottom bed, top is provided with catalyst distributor, be provided with Multilayer grid in the middle of bed, dilute phase space is provided with two stage cyclone separator;
Described revivifier is single hop following current bubble bed revivifier; Be provided with catalyst distributor bottom regenerator bed, be provided with Multilayer grid in bed, dilute phase space is provided with two stage cyclone separator
Be provided with Multilayer grid baffle plate in described stripping stage, grid is symmetrical installation of tilting, and individual layer grid sectional area is less than stripping stage cross-sectional area;
Raw material is heated to 300-550 DEG C, enters bottom reactor bed, and regenerated catalyst enters reactor bed top, regenerator temperature controls at 650-750 DEG C, temperature of reaction controls at 500-620 DEG C, and reactor head pressure-controlling is at 1-10bar, and the empty time control of quality is built in 2-8h.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210179765.7A CN103449948B (en) | 2012-06-01 | 2012-06-01 | Method for preparing olefin through dehydrogenating alkane |
| PCT/CN2012/000836 WO2013177723A1 (en) | 2012-06-01 | 2012-06-15 | Process for producing olefin by dehydrogenation of alkane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210179765.7A CN103449948B (en) | 2012-06-01 | 2012-06-01 | Method for preparing olefin through dehydrogenating alkane |
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| CN103449948A CN103449948A (en) | 2013-12-18 |
| CN103449948B true CN103449948B (en) | 2015-02-25 |
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| CN201210179765.7A Active CN103449948B (en) | 2012-06-01 | 2012-06-01 | Method for preparing olefin through dehydrogenating alkane |
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| WO (1) | WO2013177723A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151122B (en) * | 2014-07-25 | 2016-03-02 | 东华工程科技股份有限公司 | A kind of method being produced iso-butylene by the utilization of C4 feedstock circulation |
| RU2619128C1 (en) * | 2015-12-14 | 2017-05-12 | Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" | Method for obtaining olefin c3-c5 carbohydrates |
| AR109242A1 (en) * | 2016-05-09 | 2018-11-14 | Dow Global Technologies Llc | A PROCESS FOR CATALYTIC DEHYDROGENATION |
| RU2638934C1 (en) * | 2017-04-26 | 2017-12-19 | Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" | Installation of dehydration of paraffin hydrocarbons c3-c5 |
| CN108863703B (en) * | 2017-05-10 | 2021-11-23 | 中石油吉林化工工程有限公司 | Dehydrogenation system and method for removing catalyst in isobutane dehydrogenation product |
| RU2666541C1 (en) * | 2017-12-04 | 2018-09-11 | Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" | Method for obtaining olefin hydrocarbons |
| RU2710017C1 (en) * | 2019-10-28 | 2019-12-24 | Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" | Device for preparation of catalyst in processes of dehydrogenation of paraffin hydrocarbons c3-c5 |
| CN112484064B (en) * | 2020-10-28 | 2022-05-10 | 中石化宁波工程有限公司 | System and method for recovering waste heat boiler flue gas of propane dehydrogenation device |
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| CN1926080A (en) * | 2004-02-09 | 2007-03-07 | 陶氏化学公司 | Process for the preparation of dehydrogenated hydrocarbon compounds |
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| CN101568379A (en) * | 2006-12-28 | 2009-10-28 | 环球油品公司 | Fluidized bed reactor with back-mixing for dehydrogenation of light paraffins |
| CN102040445A (en) * | 2009-10-14 | 2011-05-04 | 青岛石大卓越投资有限公司 | Technology device and method for preparing propylene by dehydrogenating propane or propane-enriched low carbon hydrocarbon |
| CN202122945U (en) * | 2011-05-11 | 2012-01-25 | 上海河图石化工程有限公司 | Circulating fluidized bed type low-carbon alkane dehydrogenizing and olefin generating device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8293670B2 (en) * | 2009-12-09 | 2012-10-23 | Uop Llc | Process for the production of propylene |
| US8624074B2 (en) * | 2010-03-22 | 2014-01-07 | Uop Llc | Reactor flowscheme for dehydrogenation of propane to propylene |
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2012
- 2012-06-01 CN CN201210179765.7A patent/CN103449948B/en active Active
- 2012-06-15 WO PCT/CN2012/000836 patent/WO2013177723A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1926080A (en) * | 2004-02-09 | 2007-03-07 | 陶氏化学公司 | Process for the preparation of dehydrogenated hydrocarbon compounds |
| CN101568379A (en) * | 2006-12-28 | 2009-10-28 | 环球油品公司 | Fluidized bed reactor with back-mixing for dehydrogenation of light paraffins |
| CN101481289A (en) * | 2008-01-11 | 2009-07-15 | 山东科技大学 | Process for preparing propylene by propane riser circulating fluid bed catalysis |
| CN102040445A (en) * | 2009-10-14 | 2011-05-04 | 青岛石大卓越投资有限公司 | Technology device and method for preparing propylene by dehydrogenating propane or propane-enriched low carbon hydrocarbon |
| CN202122945U (en) * | 2011-05-11 | 2012-01-25 | 上海河图石化工程有限公司 | Circulating fluidized bed type low-carbon alkane dehydrogenizing and olefin generating device |
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| Publication number | Publication date |
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| WO2013177723A1 (en) | 2013-12-05 |
| CN103449948A (en) | 2013-12-18 |
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