CN102924209B - The conversion process of carbon four and more heavy constituent in a kind of preparing low-carbon olefin from oxygen-containing compounds by-product - Google Patents
The conversion process of carbon four and more heavy constituent in a kind of preparing low-carbon olefin from oxygen-containing compounds by-product Download PDFInfo
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Abstract
The invention discloses the conversion process of a kind of carbon four and more heavy constituent, to improve the yield of ethylene and propylene. The method be by the carbon four separated from reaction gas and more heavy constituent crack further, cracking used catalyst identical with primary response catalyst, cracker includes an auxiliary reactor and/or an assisted Regeneration device. Use the inventive method that the overall selectivity of ethylene and propylene can be made to bring up to 85��90%, and in product, ethylene and propylene weight ratio can regulate neatly between 1.2��0.8.
Description
The application is application number: 200810140897.2, and the applying date is: 2008.7.26, and name is called the division of a kind of carbon four and the more method for transformation of heavy constituent.
Technical field:
The present invention relates to a kind of with oxygenatedchemicals (mainly methanol, ethanol, dimethyl ether, C4��C10Alcoholic compound or its mixture etc.) for raw material, generating with low-carbon alkene as mainly generating in successive reaction and the regenerative process of logistics (being mainly ethylene and propylene), by-product carbon four and more heavy constituent (C4 +) the further method reacting preparing ethylene and propylene.
Background technology:
Light olefin (ethylene, propylene, butadiene) and light aromatics (benzene,toluene,xylene) are the base stocks of petrochemical industry. Current ethylene production relies primarily on the tube furnace steam pyrolysis technique of light naphthar raw material. Due to the raising day by day of the shortage of crude resources and price, naphtha resource has increasingly seemed not enough, and the production cost of low-carbon alkene is more and more higher. The ethylene production route that positive active development raw material sources are more rich both at home and abroad, organic oxygen-containing compound raw material is through the catalytic action of metal-modified SAPO type aperture phosphorus aluminium silicate Zn-Al-P-Si-oxide molecular sieve, can generate based on the product of ethylene, propylene, just it is being subject to both domestic and external paying attention to widely, is being in industrialization phase.
It is typical oxygen-containing organic compound with the oxygen-containing organic compound that methanol or dimethyl ether are representative, is mainly produced by coal-based or natural gas base synthesis gas. In order to the oxygen-containing organic compound that methanol is representative, to be raw material production currently mainly have the MTO technology of American UOP company based on the low-carbon alkene technique of ethylene and propylene that (main patent is US Patent No. P6166282, USP5744680; Chinese patent ZL00137259.9), (main patent is USP6673978, USP6717023, USP6613950 for the MTO technology of ExxonMobil company of the U.S.; Chinese patent ZL00815363.2, ZL00802040.x, ZL03821995.6), the DMTO technology (ZL96115333.4, ZL92109905.3) of MTP technique (EP0448000A, DE233975A1) and the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences.
The reaction characteristics of oxygenatedchemicals (current typical case's employing is methanol) preparing low-carbon olefins technique (MTO) is fast reaction, strongly exothermic and alcohol agent ratio is relatively low, is react in the dense fluidized bed bioreactor that continuous print reacts-regenerates and regenerate.Reaction generate the high-temperature oil gas rich in the low-carbon alkene such as ethylene and propylene, it is necessary to carry out chilling and washing, remove wherein catalyst and cooling after, be sent to bottom olefin separation system and be easily separated. The purpose product of MTO process unit is ethylene and propylene, side-product liquefied gas, C5Above component and fuel gas, wherein C4 +Carbon base absorption rate be about 10%. How this part low value product is converted into ethylene and the propylene of high added value, is always up pendulum problem in face of vast scientific research and project planner.
In recent years, " MTO technology (MTO) " has become the focus and emphasis of insider's research. People conduct extensive research from aspects such as work flow, catalyst, process conditions and device structures and explore, and obtain gratifying achievement, but relating to how by the side-product C in MTO process products4And heavier component (C4 +) it is converted into the ethylene of high added value and propylene bibliographical information is few.
WO200320667 patent discloses a kind of OTO technique, this invention describes two or more zeolite catalyst, the first catalyst is ZSM-5, and the second catalyst is the molecular sieve (ZSM-22, ZSM-23, ZSM-35, ZSM-48 etc.) of 10 rings. ZSM-5 can be considered as modifiying, P Modification or steam is modified, micro pore volume is not less than 50% (compared with the ZSM-5 modified without steam). Oxygen-containing compound material contacts with both catalyst respectively in two independent reactors. Oxygenatedchemicals and the contact of the first catalyst form olefin product, isolate butene content in the logistics containing butylene minimum for 20w%, it are contacted with the second catalyst and form the second olefin product.
The technique that US604917, US20040102667 and US5914433 patent all refers to improve ethylene and productivity of propylene during low-carbon alkene produces. By C in product4Alkene, C4 +The hydrocarbon components of alkene or heavier converts, it is possible to be greatly improved the productivity of ethylene and propylene.
The technique that US604917 patent relates to may be used for ethylene unit, catalytic cracking unit and MTO process unit. After ethylene and propylene separation being reclaimed, the heavy hydrocarbon of some residual may return to reaction zone and converts further, or carries out oligomerisation and obtain the downstream product of high value.
US20040102667 patent relates to OTO technique and improves the technology of ethylene and productivity of propylene. Adopt silicon aluminium phosphate catalyst. The C that product is isolated to4��C7Middle matter olefine fraction carries out cracking in an independent cracking of olefins reactor. Have main steps that: (1) will be enriched in the charging C of alkene2��C8Send into flash trapping stage device, separate C2��C3Light olefin and C4 +Heavier olefins fraction; (2) heavier olefins fraction is sent into the second-order separation district, separate the second light olefin fraction, C4��C7Middle matter olefine fraction and C7 +Heavier olefins fraction; (3) middle matter olefine fraction being sent into cracking of olefins reactor, making at least some of crack materials is C2��C3Alkene; (4) C that cracking is formed2��C3Alkene some return to the second-order separation district. Another part is drawn out of; (5) the second light olefin fraction that the second-order separation is distinguished some return to flash trapping stage district.
US5914433 patent relates to the OTO technique producing polymer grade olefin. It is characterized in the mixed butene in product and heavy constituent are carried out cracking, thus improving the yield of ethylene and propylene. Cracking reaction carries out in riser cracking district or the independent zone of cracking, provides motility to technique. This technique overcomes the balance restriction of silicon aluminium phosphate catalyst, also improves the life-span of catalyst, improves the catalyst stability at zone of transformation.
Main processing step is: (1) oxygenatedchemicals (C1��C4A kind of alcohol or a kind of ether) dilution of raw material diluent, adopt silicon aluminium phosphate catalyst (SAPO-34, SAPO-17 or its mixture) and fluidized-bed reactor, obtain Light olefin products logistics at reaction conditions;(2) ethylene, propylene and mixed butene heavy constituent are obtained after stream of light olefins being separated; (3) take out at least some of reclaimable catalyst to go to regenerate; (4) the catalyst part after regeneration returns to fluidized bed reaction zone, and another part mixes with a certain amount of mixed butene and heavy constituent, enters cracker and obtains the second product stream, generates extra ethylene and propylene; (5) part the second product stream is returned to fluidized bed reaction zone.
The patent CN1803738A of American UOP company discloses use mobile technology and independent heavier olefins interconversion procedures converts oxygenate compounds to propylene. This patent is characterized by and sets two reaction zones, and first moving bed reaction district uses the bifunctional catalyst with SAPO and ZSM function, and oil gas product is mainly propylene, has a small amount of ethylene, butylene and C simultaneously4 +Alkene, C1��C4Saturated hydrocarbons, a small amount of aromatic hydrocarbon and water. Reaction oil gas chilling is divided into the steam rich in propylene, the aqueous phase comprising unreacted methanol and newly-generated oxygenatedchemicals, liquid hydrocarbon three part that comprises heavier hydro carbons (alkene, saturated hydrocarbons, aromatic hydrocarbons) after separating. Recovery section water generation reaction is as the absorbent of reaction raw materials. Second reaction zone is also moving bed, uses ZSM, SAPO bifunctional catalyst that portfolio ratio is different, and reaction temperature is higher than the first reaction zone more than 15 DEG C, it is therefore an objective to by C4 +Alkene is converted into the product that propylene is master, estimates to be similar to disclosed Atofina company OCPC4 +Olefin conversion process catalyst. What the first reactor generated contains ethylene, butylene and C4 +Alkene, C1��C4Saturated hydrocarbons, a small amount of aromatic hydrocarbon gas-phase product separate further, wherein C4 +Alkene goes the second further alkene of reactor to convert.
The patent CN1419527A of ExxonMobil company of the U.S. discloses C in a kind of oxygenate conversion reaction4 +And more weight flow to the control method of the conversion of light product, it is that the heavier olefins existed in a kind of product stream making to leave the first reaction zone when not separating heavy alkene from the product stream leaving the first reaction zone changes into the method for carbonaceous sediment on light olefin and catalyst. Described method includes: produce to leave the product stream of the first reaction zone, described in leave the product stream of the first reaction zone and comprise heavier olefins; The product stream leaving the first reaction zone is made to move to second reaction zone when not separating described heavier olefins from the product stream leaving the first reaction zone; With make the product stream leaving the first reaction zone contact with catalyst when light olefin can be formed, described contact cause described catalyst at least some of on form carbonaceous sediment.
The patent US4433188 of BASF AG discloses a kind of methanol/dimethyl ether alkene technology, and this invention adopts borosilicate catalyst, including two-stage reaction and two-phase seperation. Material benzenemethanol/dimethyl ether contacts generation catalytic cracking reaction in first paragraph reaction zone with catalyst, and product separates C through the first piece-rate system2��C4Alkene and C1��C4Alkane, remaining C5 +Component enters second reaction zone and contacts generation cracking reaction with catalyst, and product, through the second piece-rate system Arene removal component, is then back to the first piece-rate system. This patent be mainly characterized by circulation C5 +Component reacts under different conversion zones and condition from raw material.
The patent CN1962573A of Tsing-Hua University discloses method and the reactor of catalytic cracking for producing propylene using fluid bed, and this invention belongs to alcohol, ether cracking propylene technical field, it is characterised in that the C in the product of low-carbon alkene preparation technology2And C2Following components, C4And C4After above component separates with purpose product propylene, looping back to alkene in fluid catalytic cracking reaction unit and turn reaction zone and carry out alkene conversion, by controlling operating condition, high selectivity produces propylene.C2 -��C4 +Two streams had before returning to olefin reaction district speeds to put on a small quantity, to avoid inert component to accumulate. Correspondingly, it is proposed that can be used as the multicompartment fluidized bed structure of reactor in main reaction region or olefin reaction district. This invention has the advantage that height always received by propylene, selectivity is strong.
In sum, although prior art relate in some oxygenate conversion reaction carbon four and more heavy constituent (C4 +) freshening method, but there is also many problems: including using different antigravity systems, it is necessary to build the C that independent output investment ratio is higher4 +Cracking unit, olefin cracking system thermal is uneven, it is necessary to exclusively for C4 +Cracker provides required heat, and cracking condition is restricted, and conversion ratio is relatively low; Only focus on C in unconverted raw material and product5 +Component, is generally not related to the freshening problem of butylene; Also part technology for the purpose of propylene improves propylene total recovery by by-product circulation, but majority adopts the simple form that by-product loops back former reactor, etc.
Summary of the invention:
The purpose of the present invention is that offer is a kind of and transforming oxygenated organic compound alkene generates in by-product carbon four and more heavy constituent (C4 +) it is cracked into C further2 =��C3 =Method, to improve the selectivity of low-carbon alkene, operation conditions optimization, simplification of flowsheet, reduce construction investment.
The present invention provides the conversion process of a kind of carbon four and more heavy constituent, it is characterized in that: the separated system of reaction gas of main reactor separates, isolated carbon four and more heavy constituent enter auxiliary reactor and the regeneration catalyzing agent haptoreaction from assisted Regeneration device, the reaction gas of auxiliary reactor is delivered to piece-rate system together with the reaction gas of main reactor and is easily separated, in auxiliary reactor, the reclaimable catalyst of carbon distribution enters assisted Regeneration device after stripping, enter auxiliary reactor after coke burning regeneration to recycle, it is incorporated into assisted Regeneration device from main regenerator overhead regenerated flue gas out, wherein auxiliary reactor is identical with main reactor used catalyst, the reaction temperature of auxiliary reactor 500��650 DEG C, preferably 550��600 DEG C, reaction pressure 0.1��0.5MPa, it is preferable that 0.1��0.3MPa, agent/material is than (in auxiliary reactor the weight ratio of catalyst and carbon four and more heavy constituent) 0.5��20, it is preferable that 5��15. the temperature of assisted Regeneration device 550��750 DEG C, it is preferable that 650��700 DEG C.
The present invention also provides for the conversion process of a kind of carbon four and more heavy constituent, it is characterized in that: the separated system of reaction gas of main reactor separates, isolated carbon four and more heavy constituent enter auxiliary reactor and carry out the regeneration catalyzing agent haptoreaction of autonomous regenerator, the reaction gas of auxiliary reactor is delivered to piece-rate system together with the reaction gas of main reactor and is easily separated, in auxiliary reactor, the reclaimable catalyst of carbon distribution fully enters main reactor after stripping, or it is partly into main reactor, another part enters main regenerator and mixes with the reclaimable catalyst from main reactor and carry out coke burning regeneration, catalyst after regeneration enters back into auxiliary reactor and recycles, the reaction temperature of auxiliary reactor 500��650 DEG C, preferably 550��600 DEG C, reaction pressure 0.1��0.5MPa, it is preferable that 0.1��0.3MPa, agent/material is than (in auxiliary reactor the weight ratio of catalyst and carbon four and more heavy constituent) 0.5��20, it is preferable that 5��15. the temperature of main regenerator 550��750 DEG C, it is preferable that 650��700 DEG C, wherein said auxiliary reactor is fluidized-bed reactor.
The present invention additionally provides the conversion process of a kind of carbon four and more heavy constituent, it is characterized in that: the separated system of reaction gas of main reactor separates, isolated carbon four and more heavy constituent enter auxiliary riser line reactor and carry out the regeneration catalyzing agent haptoreaction of autonomous regenerator, the reaction effluent of auxiliary riser line reactor is divided into two parts, what account for auxiliary riser line reactor overall reaction effluent 10��50 weight % is partly into the close phase section from 0��6 meter of main reactor close phase section top, the another part accounting for auxiliary riser line reactor overall reaction effluent 50��90 weight % enters in the middle part of the changeover portion of the close phase pars infrasegmentalis of main reactor, the product of main reactor is easily separated, reaction gas after separation is from main reactor Base top contact, the reclaimable catalyst of the carbon distribution after separation carries out coke burning regeneration recycling through stripping laggard regenerator of becoming owner of, the reaction temperature of auxiliary riser line reactor 500��650 DEG C, preferably 550��600 DEG C,Reaction pressure 0.1��0.5MPa, it is preferable that 0.1��0.3MPa; Agent/material is than (in auxiliary riser line reactor the weight ratio of catalyst and carbon four and more heavy constituent) 0.5��20, it is preferable that 5��15. The temperature of main regenerator 550��750 DEG C, it is preferable that 650��700 DEG C.
Oxygenatedchemicals of the present invention can be selected from methanol, ethanol, dimethyl ether and C4��C10In the oxygen-containing organic compounds such as alcoholic compound one or more.
The conversion process of carbon four of the present invention and more heavy constituent is suitable for all rich product C4 +The commercial plant of alkene, is especially suitable for the MTA device of the catalytic cracking unit of oil refining process and deriving device thereof, the MTO process unit of methanol-to-olefins, the MTP device of preparing propylene from methanol, methanol aromatic hydrocarbons, it is preferable that be applied to MTO process unit.
Compared to the prior art technique provided by the present invention have the superiority of the following aspects:
(1) oxygenatedchemicals converts olefin process device processed and adopts the first method for transformation of the present invention, namely during two set reaction regeneration devices, in assisted Regeneration device, introduced the regenerated flue gas rich in carbon monoxide by main regenerator, utilize CO burning liberated heat, improve C4 +The temperature of olefin cracking regenerator, can meet C4 +The heat that olefin cracking reaction is required so that C4 +Olefin cracking reaction can carry out under the operating condition optimized;
(2) method of the present invention is adopted, because the further cracking unit of its carbon four and more heavy constituent is relatively independent, carbon four and more heavy constituent conversion reaction carry out in different reactors from raw material cracking reaction, can independently control temperature and space velocity conditions that alkene converts, the catalyst type that each reaction is used simultaneously is identical, it is to avoid cause catalyst contaminant problems because catalyst is different.
(3) method of the present invention is adopted, by by oxygenatedchemicals convert olefin process processed by-product carbon four and more heavy constituent crack further in the method for the invention, the overall selectivity of ethylene and propylene can be brought up to 85��90%, ethylene adds the propylene carbon base absorption rate to methanol feedstock and improves 4��6 percentage points, by changing operating condition, in product, ethylene and propylene weight ratio can regulate between 1.2��0.8.
(4) adopting method of the present invention, oxygenatedchemicals converts the further cracker of olefin process device processed and its by-product carbon four and more heavy constituent and shares a set of chilling and water wash system, simplifies technological process, minimizing construction investment.
(5) heretofore described oxygenatedchemicals cracking reaction is the endothermic reaction, and reaction temperature is relatively low, and agent/expect is smaller. In the present invention, second is serial operation with the catalyst circulation pattern described in the third method, it can be ensured that oxygenatedchemicals carries out under the operating condition optimized.
Below in conjunction with the drawings and specific embodiments, the present invention is described further. But it does not limit the scope of the invention.
Accompanying drawing explanation
Fig. 1 is one schematic flow sheet of the present invention.
Fig. 2 is the second schematic flow sheet of the present invention.
Fig. 3 is the third schematic flow sheet of the present invention.
In figure: 1-main reactor reaction gas; 2-main reactor cyclone separator;
3-oxygenatedchemicals; 4-main reactor;
The main regenerator of 5-; 6-regenerated flue gas;
The main regenerator cyclone separator of 7-; The reaction gas of 8-auxiliary reactor 11;
9-auxiliary reactor cyclone separator; 10-carbon four and more heavy constituent;
11-auxiliary reactor; 12-stripping section to be generated;
13-assisted Regeneration device riser to be generated;14-assisted Regeneration device;
The regenerated flue gas of 15-assisted Regeneration device 14; 16-preheats main air;
17-main reactor stripping section; 18-auxiliary riser line reactor;
19-auxiliary reactor regeneration riser; The main regenerator of 20-riser to be generated;
21-main reactor regeneration riser; 22-reaction gas;
The close phase section of 23-; The main regenerator stripping section of 24-;
25-changeover portion.
Detailed description of the invention
Fig. 1, Fig. 2 and Fig. 3 show for oxygenatedchemicals olefin process schematic flow sheet.
Fig. 1 show two set reaction regeneration devices, but auxiliary reactor 11 is identical with used catalyst in main reactor 4. oxygenatedchemicals 3 is entered by main reactor 4 bottom, with the catalyst haptoreaction in main reactor 4, reaction product is easily separated through main reactor cyclone separator 2, the main reactor reaction gas 1 rich in the low-carbon alkene such as ethylene and propylene after separation is by main reactor 4 Base top contact, mix with by the reaction gas 8 of auxiliary reactor 11 auxiliary reactor 11 out, deliver to rear portion chilling water wash system, by the catalyst fines carried in the further washing reaction gas of chilling, by washing, the most of water in reaction gas is easily separated, it is then sent to the separation of olefins unit at rear portion. in separation of olefins unit, reaction gas is easily separated, the purpose product ethylene obtained and propylene go out device, auxiliary reactor 11 is entered with vapor mode after isolated carbon four and more heavy constituent 10 are preheated, directly contact with the high-temperature regenerated catalyst from assisted Regeneration device 14 in auxiliary reactor 11, react rapidly at catalyst surface, the reaction gas 8 of auxiliary reactor 11 is drawn after the catalyst that auxiliary reactor cyclone separator 9 removes entrained with, after mixing with the main reactor reaction gas 1 from main reactor 4 top, deliver to rear pre-separation together and olefin separation system is easily separated, obtain the purpose product such as ethylene and propylene.
In auxiliary reactor 11, after reaction, the reclaimable catalyst entrance stripping section 12 to be generated of carbon distribution strips, remove the reaction gas that reclaimable catalyst carries, reclaimable catalyst after stripping enters assisted Regeneration device riser 13 to be generated after guiding valve to be generated, assisted Regeneration device 14 is entered under the conveying of nitrogen, contacting coke burning regeneration with preheating main air 16 in assisted Regeneration device 14, the catalyst after regeneration enters auxiliary reactor 11 through auxiliary reactor regeneration riser 19 and recycles.
Regenerated flue gas 6 full dose carrying out autonomous regenerator 5 is incorporated in assisted Regeneration device 14, rich in CO (carbon monoxide converter) gas in regenerated flue gas 6, utilizes CO burning liberated heat to supplement C4 +The heat that olefin cracking reaction is required, controls CO burning with preheating main air 16 simultaneously, and the burn rate of carbon monoxide strictly controls by the oxygen content in the regenerated flue gas 15 of assisted Regeneration device 14 so that regenerated catalyst temperature is in required scope. The pre-heating mean of main air can be selected from electrical heating method and set up interior heat collector heating main air method etc. at regenerator, it is preferable that second method. The regenerated flue gas 15 of assisted Regeneration device 14 is by smoke stack emission air.
Auxiliary reactor described in Fig. 1 and assisted Regeneration device are fluid bed pattern, it is possible to be bubbling bed, turbulent bed or fast bed streaming mode, it is preferable that Turbulent Fluidization mode of operation.
The reclaimable catalyst that Fig. 2 show in main reactor 4 and auxiliary reactor 11 carries out the form regenerated in same main regenerator 5, and auxiliary reactor 11 is fluid bed.Oxygenatedchemicals 3 is entered by main reactor 4 bottom, with the catalyst haptoreaction in main reactor 4, reaction product is easily separated through main reactor cyclone separator 2, the main reactor reaction gas 1 rich in the low-carbon alkene such as ethylene and propylene after separation is by main reactor 4 Base top contact, mix with by the reaction gas 8 of auxiliary reactor 11 auxiliary reactor 11 out, deliver to rear portion chilling water wash system, by the catalyst fines carried in the further washing reaction gas of chilling, by washing, the most of water in reaction gas is easily separated, it is then sent to the olefin separation system at rear portion. in separation of olefins unit, reaction gas is easily separated, obtain purpose product ethylene and propylene goes out device, auxiliary reactor 11 is entered with vapor mode after isolated carbon four and more heavy constituent 10 are preheated, with the regeneration catalyzing agent haptoreaction carrying out autonomous regenerator 5 in auxiliary reactor 11, the reaction gas 8 of auxiliary reactor 11 is drawn after the catalyst that auxiliary reactor cyclone separator 9 removes entrained with, after mixing with the main reactor reaction gas 1 from main reactor 4 top, deliver to olefin separation system together to be easily separated, in auxiliary reactor 11, the reclaimable catalyst of carbon distribution strips at stripping section 12 to be generated, remove the reaction gas that reclaimable catalyst carries, reclaimable catalyst after stripping is partly into main reactor regeneration riser 21, main reactor 4 is entered under the conveying of 1.0Mpa steam, continue and oxygen-containing compound material 3 reacts. all the other nitrogen or other media (as, plant air) conveying under enter into main regenerator 5 through main regenerator riser to be generated 20, the reclaimable catalyst of main reactor 4 strips laggard main regenerator 5 through main reactor stripping section 17, respectively from two strands of reclaimable catalysts coke burning regeneration in main regenerator 5 of main reactor 4 and auxiliary reactor 11. catalyst after regeneration enters main regenerator stripping section 24 and strips, and the regeneration catalyzing agent after stripping returns to auxiliary reactor 11 through auxiliary reactor regeneration riser 19 and recycles. the regenerated flue gas 6 of main regenerator 5 removes through main regenerator cyclone separator 7 and is entered air by main regenerator 5 top after the most of catalyst carried.
Auxiliary reactor described in Fig. 2 is fluid bed pattern, it is possible to be bubbling bed, turbulent bed or fast bed streaming mode, it is preferable that Turbulent Fluidization mode of operation.
As shown in Figure 3, oxygenatedchemicals 3 is entered by main reactor 4 bottom, with the catalyst haptoreaction in main reactor 4, rich in the reaction gas 22 of the low-carbon alkene such as ethylene and propylene after the catalyst that main reactor cyclone separator 2 removes entrained with by main reactor 4 Base top contact, deliver to rear portion chilling water wash system, by the catalyst fines carried in the further washing reaction gas of chilling, by washing, the most of water in reaction gas is easily separated, is then sent to the olefin separation system at rear portion. in separation of olefins unit, reaction gas 22 is easily separated, the purpose product ethylene obtained and propylene go out device, auxiliary riser line reactor 18 is entered with vapor mode after isolated carbon four and more heavy constituent 10 are preheated, with the catalyst haptoreaction entered by main regenerator 5, the reaction effluent of auxiliary riser line reactor 18 is divided into two parts, what account for auxiliary riser line reactor 18 overall reaction effluent 10��50 weight % is partly into the close phase section from 0��6 meter of main reactor 4 close phase section 23 top, the another part accounting for auxiliary riser line reactor 18 overall reaction effluent 50��90 weight % enters in the middle part of the changeover portion 25 of the close phase pars infrasegmentalis of main reactor 4, the product of main reactor 4 separates through main reactor cyclone separator 2, reaction gas 22 after separation is from main reactor 4 Base top contact, it is then delivered to chilling water wash system.The reclaimable catalyst of the carbon distribution after separation enters main reactor stripping section 17 and strips, and removes the reaction gas that reclaimable catalyst carries, and the reclaimable catalyst after stripping enters main regenerator 5 under the conveying of nitrogen, coke burning regeneration in main regenerator 5. Catalyst after regeneration enters main regenerator stripping section 24 and strips, and the regeneration catalyzing agent after stripping enters auxiliary riser line reactor 18 and recycles.
The injection phase of carbon four and more heavy constituent 10 is on the upper, middle and lower and oxygenate feedstock pipeline of auxiliary riser line reactor 18, it is preferable that the top of auxiliary riser line reactor 18 or bottom.
The regenerated flue gas 6 of main regenerator 5 removes through main regenerator cyclone separator 7 and is entered air by main regenerator 5 top after the most of catalyst carried.
Claims (2)
1. the conversion process of carbon four and more heavy constituent in a preparing low-carbon olefin from oxygen-containing compounds by-product, it is characterized in that: the separated system of reaction gas of main reactor separates, isolated carbon four and more heavy constituent enter auxiliary reactor and carry out the regeneration catalyzing agent haptoreaction of autonomous regenerator, the reaction gas of auxiliary reactor is delivered to piece-rate system together with the reaction gas of main reactor and is easily separated, in auxiliary reactor, the reclaimable catalyst of carbon distribution fully enters main reactor after stripping, or it is partly into main reactor, another part enters main regenerator and mixes with the reclaimable catalyst from main reactor and carry out coke burning regeneration, catalyst after regeneration enters back into auxiliary reactor and recycles, the reaction temperature of auxiliary reactor 500��650 DEG C, reaction pressure 0.1��0.5MPa, agent/material ratio 0.5��20, the temperature of main regenerator 550��750 DEG C, wherein said auxiliary reactor is fluidized-bed reactor, described dose/expect the weight ratio for catalyst in auxiliary reactor and carbon four and more heavy constituent.
2. conversion process according to claim 1, it is characterised in that: the reaction temperature of auxiliary reactor 550��600 DEG C, reaction pressure 0.1��0.3MPa, agent/material ratio 5��15; The temperature of main regenerator 650��700 DEG C, described dose/expect the weight ratio for catalyst in auxiliary reactor and carbon four and more heavy constituent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1453535A (en) * | 1974-06-07 | 1976-10-27 | Bp Chem Int Ltd | Cracking feedstock containing c4 olefins |
| GB1462609A (en) * | 1975-06-11 | 1977-01-26 | Continental Oil Co | Cracking process for producing ethylene |
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| CN1401741A (en) * | 2002-09-16 | 2003-03-12 | 中国石油化工集团公司 | Method and device for reducing olefine in gasoline |
| CN1868983A (en) * | 2006-07-03 | 2006-11-29 | 中国石油化工集团公司 | Method of preparing ethylene and propylene and catalyst used in said method |
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| EP1508555A1 (en) * | 2003-08-19 | 2005-02-23 | Total Petrochemicals Research Feluy | Production of olefins |
| FR2859994B1 (en) * | 2003-09-19 | 2005-10-28 | Inst Francais Du Petrole | PROCESS FOR THE DIRECT CONVERSION OF A CHARGE COMPRISING FOUR AND / OR FIVE ATOMIC CARBON OLEFINS FOR THE PRODUCTION OF PROPYLENE |
| KR101270191B1 (en) * | 2005-08-15 | 2013-05-31 | 상하이 리서치 인스티튜트 오브 페트로케미칼 테크놀로지 시노펙 | Method for preparation of ethylene and propylene by catalytic cracking using a fluid-bed catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1453535A (en) * | 1974-06-07 | 1976-10-27 | Bp Chem Int Ltd | Cracking feedstock containing c4 olefins |
| GB1462609A (en) * | 1975-06-11 | 1977-01-26 | Continental Oil Co | Cracking process for producing ethylene |
| US6049017A (en) * | 1998-04-13 | 2000-04-11 | Uop Llc | Enhanced light olefin production |
| CN1401741A (en) * | 2002-09-16 | 2003-03-12 | 中国石油化工集团公司 | Method and device for reducing olefine in gasoline |
| CN1868983A (en) * | 2006-07-03 | 2006-11-29 | 中国石油化工集团公司 | Method of preparing ethylene and propylene and catalyst used in said method |
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