CN101633593A - Conversion method of C4 and heavier components - Google Patents
Conversion method of C4 and heavier components Download PDFInfo
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- CN101633593A CN101633593A CN200810140897A CN200810140897A CN101633593A CN 101633593 A CN101633593 A CN 101633593A CN 200810140897 A CN200810140897 A CN 200810140897A CN 200810140897 A CN200810140897 A CN 200810140897A CN 101633593 A CN101633593 A CN 101633593A
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Abstract
The invention discloses a conversion method of C4 and heavier components, thereby improving the yield of ethylene and propylene. The method carries out further cracking on the C4 and the heavier components separated from reaction gas, a catalyst used for cracking is the same with the catalyst of the main reaction, and a cracking device comprises an auxiliary reactor and/or an auxiliary regenerator. The use of the method can improve the total selectivity of ethylene and propylene to 85-90%, and the weight ratio of ethylene to propylene in products can be flexibly regulated between 1.2 and 0.8.
Description
Technical field:
The present invention relates to a kind of (mainly is methyl alcohol, ethanol, dme, C with oxygenatedchemicals
4～C
10Alkylol cpd or its mixture etc.) be raw material, be in the successive reaction and regenerative process of main generation logistics (mainly being ethene and propylene) generating with the low-carbon alkene, by product carbon four reaches more heavy constituent (C
4 +) the further method of producing ethene and propylene of reacting.
Background technology:
Light olefin (ethene, propylene, divinyl) and light aromatics (benzene,toluene,xylene) are the basic raw materials of petrochemical complex.Ethylene production mainly relies on the tube furnace steam cracking technology of light naphthar raw material at present.Because it is not enough that the shortage of crude resources and the raising day by day of price, naphtha resource have more and more seemed, the production cost of low-carbon alkene is more and more higher.The domestic and international positive abundanter ethylene production route of active development raw material sources, the organic oxygen-containing compound raw material is through the katalysis of metal-modified SAPO type aperture phosphorus pure aluminium silicate Zn-Al-P-Si-oxide molecular sieve, can generate reaction product based on ethene, propylene, just be subjected to attention widely both domestic and external, be in industrialization phase.
With methyl alcohol or dme is that the oxygen-containing organic compound of representative is typical oxygen-containing organic compound, mainly by the synthetic gas production of coal-based or Sweet natural gas base.In order to methyl alcohol is that to be raw material production mainly contain the MTO technology of American UOP company at present based on the low-carbon alkene technology of ethene and propylene that (main patent is U.S. Pat P6166282, USP5744680 for the oxygen-containing organic compound of representative; Chinese patent ZL00137259.9), (main patent is USP6673978, USP6717023, USP6613950 to the MTO technology of U.S. ExxonMobil company; Chinese patent ZL00815363.2, ZL00802040.x, ZL03821995.6), the DMTO technology (ZL96115333.4, ZL92109905.3) of MTP technology (EP0448000A, DE233975A1) and the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences.
The reaction characteristics that oxygenatedchemicals (current typical case adopt be methyl alcohol) is produced low-carbon alkene technology (MTO) is that rapid reaction, strong heat release and pure agent are lower frequently, is to react in successive reaction-regenerated dense fluidized bed bioreactor and regenerate.The high-temperature oil gas that is rich in low-carbon alkenes such as ethene and propylene that reaction generates need be carried out chilling and washing, remove wherein catalyzer and cooling after, be sent to the bottom olefin separation system and separate.The purpose product of MTO process unit is ethene and propylene, byproduct liquefied gas, C
5Above component and fuel gas, wherein C
4 +The carbon back yield be about 10%.How this part low value product is converted into the ethene and the propylene of high added value, be the problem of pendulum in face of vast scientific research and project planner always.
In recent years, " methanol-to-olefins technology (MTO) " become the focus and emphasis of insider's research.People have carried out extensive studies and exploration from aspects such as work flow, catalyzer, processing condition and device structures, obtain gratifying achievement, but relevant how with the byproduct C in the MTO process products
4And heavier component (C
4 +) be converted into high added value ethene and propylene bibliographical information few.
The WO200320667 Patent publish a kind of OTO technology, two or more zeolite catalyst has been introduced in this invention, first kind of catalyzer is ZSM-5, second kind of molecular sieve (ZSM-22, ZSM-23, ZSM-35, ZSM-48 etc.) that catalyzer is 10 yuan of rings.ZSM-5 can be considered as modification, the phosphorus modification or the steam modification, micro pore volume is not less than 50% (comparing with the ZSM-5 without the steam modification).Oxygen-containing compound material independently contacts with these two kinds of catalyzer in the reactor at two respectively.Oxygenatedchemicals contacts with first catalyzer and forms olefin product, isolates the minimum 20w% of being of butene content in the logistics that contains butylene, it is contacted with second catalyzer form second olefin product.
US604917, US20040102667 and US5914433 patent all relate to the technology that improves ethene and productivity of propylene in the low-carbon alkene production.With C in the product
4Alkene, C
4 +Alkene or heavier hydrocarbon components transform, and can improve the productive rate of ethene and propylene greatly.
The technology that the US604917 patent relates to can be used for ethylene unit, catalytic cracking unit and MTO process unit.After ethene and propylene Separation and Recovery, the remaining heavy hydrocarbon of part can be got back to reaction zone and further transform, and perhaps carries out the derived product that oligomerisation obtains high value.
The US20040102667 patent relates to the technology that OTO technology improves ethene and productivity of propylene.Adopt silicon aluminium phosphate catalyst.The C that product obtains through separation
4～C
7Middle matter olefin fraction carries out cracking in an independent cracking of olefins reactor.Key step is: (1) will be rich in the charging C of alkene
2～C
8Send into the flash trapping stage device, tell C
2～C
3Light olefin and C
4 +Heavy olefin fraction; (2) will weigh olefin fraction and send into the secondary disengaging zone, tell the second light olefin cut, C
4～C
7Middle matter olefin fraction and C
7 +Heavy olefin fraction; (3) middle matter olefin fraction is sent into the cracking of olefins reactor, making the cracking of at least a portion raw material is C
2～C
3Alkene; (4) C of cracking formation
2～C
3Some gets back to the secondary disengaging zone alkene.Another part is drawn out of; (5) the second light olefin cut told of secondary disengaging zone some turn back to the flash trapping stage district.
The US5914433 patent relates to the technology that OTO produces polymerization-grade alkene.Be characterized in mixed butene in the product and heavy constituent are carried out cracking, thus the output of raising ethene and propylene.Cracking reaction in the riser cracking district or the independent zone of cracking carry out, provide handiness to technology.This technology has overcome the equilibrium-limited of silicon aluminium phosphate catalyst, has also improved life of catalyst, has improved the stability of catalyzer at zone of transformation.
Main processing step is: (1) oxygenatedchemicals (C
1～C
4A kind of alcohol or a kind of ether) raw material dilutes with thinner, adopts silicon aluminium phosphate catalyst (SAPO-34, SAPO-17 or its mixture) and fluidized-bed reactor, obtains the light olefin product stream under reaction conditions; (2) will obtain ethene, propylene and mixed butene heavy constituent after the stream of light olefins separation; (3) taking out at least a portion reclaimable catalyst goes to regenerate; (4) the catalyzer part after the regeneration turns back to fluidized bed reaction zone, and another part mixes with a certain amount of mixed butene and heavy constituent, enters cracking case and obtains second product stream, generates extra ethene and propylene; (5) part second product stream is turned back to fluidized bed reaction zone.
The patent CN1803738A of American UOP company has disclosed and has used mobile technology and independently heavy alkene change step that oxygenate is propylene.These patent main points are to establish two reaction zones, and first moving bed reaction district uses the dual-function catalyst with SAPO and ZSM function, and the oil gas product mainly is a propylene, and small amount of ethylene, butylene and C are arranged simultaneously
4 +Alkene, C
1～C
4Stable hydrocarbon, a small amount of aromatic hydrocarbon and water.The reaction oil gas chilling is divided into steam, the water that comprises unreacted methanol and newly-generated oxygenatedchemicals that is rich in propylene, liquid hydrocarbon three parts that comprise heavier hydro carbons (alkene, stable hydrocarbon, aromatic hydrocarbons) after separating.The recovery part water generation reaction is as the absorption agent of reaction raw materials.Second reaction zone also is a moving-bed, use be the different ZSM of portfolio ratio, SAPO dual-function catalyst, temperature of reaction is higher more than 15 ℃ than first reaction zone, purpose is with C
4 +Conversion of olefines is that propylene is main product, estimates to be similar to the disclosed Atofina OCP C of company
4 +The conversion of olefines process catalyst.First reactor generates contains ethene, butylene and C
4 +Alkene, C
1～C
4The gas-phase product of stable hydrocarbon, a small amount of aromatic hydrocarbon further separates, wherein C
4 +Alkene removes the further conversion of olefines of second reactor.
The patent CN1419527A of U.S. ExxonMobil company has disclosed C in a kind of oxygenate conversion reaction
4 +And more heavies stream is that a kind of heavy conversion of olefines that exists in the product stream that leaves first reaction zone that makes under the situation of not separating heavy alkene from the product that leaves first reaction zone flows becomes the method for carbonaceous sediment on light olefin and the catalyzer to the control method of the conversion of light product.Described method comprises: produce the product stream that leaves first reaction zone, the described product stream that leaves first reaction zone comprises heavy alkene; Under the situation of from the product stream that leaves first reaction zone, not separating described heavy alkene, the product that leaves first reaction zone is drifted to second reaction zone; With the product stream that leaves first reaction zone is contacted with catalyzer under the condition that can form light olefin, described contact causes forming carbonaceous sediment at least a portion of described catalyzer.
The patent US4433188 of BASF AG has disclosed a kind of methyl alcohol/dme system alkene technology, and the borosilicate catalyzer is adopted in this invention, comprises two-stage reaction and two sections separation.Material benzenemethanol/dme contacts the generation catalytic cracking reaction with catalyzer in first section reaction zone, product is told C through first separation system
2～C
4Alkene and C
1～C
4Alkane, remaining C
5 +Component enters second reaction zone and contacts the generation scission reaction with catalyzer, and product removes aromatic component through second separation system, returns first separation system then.The principal feature of this patent is circulation C
5 +Component reacts under different conversion zones and condition with raw material.
The patent CN1962573A of Tsing-Hua University has disclosed the method and the reactor of catalytic cracking for producing propylene using fluid bed, and this invention belongs to alcohol, ether-splitting is separated system propylene technical field, it is characterized in that, the C in low-carbon alkene preparation technology's the product
2And C
2Following component, C
4And C
4Above component is with after purpose product propylene separates, and circulation turns back in the fluid catalytic cracking reaction unit alkene to be changeed reaction zone and carry out conversion of olefines, and by the red-tape operati condition, highly selective is produced propylene.C
2 -, C
4 +Two bursts of logistics had before returning the olefin reaction district speeds to put on a small quantity, to avoid the inert component accumulation.Correspondingly, proposed can be used as the multicompartment fluidized bed structure of reactor in main reaction region or olefin reaction district.This invention has propylene and always receives height, advantage that selectivity is strong.
In sum, though related in some oxygenate conversion reaction carbon four and heavy constituent (C more in the prior art
4 +) the freshening method, but also there are many problems: comprising using different catalyst systems, need build the independently higher C of output investment ratio
4 +Cracking unit, olefin cracking system thermal imbalance, needing specially is C
4 +Cracker provides required heat, and cracking condition is restricted, and transformation efficiency is lower; Only pay close attention to C in unconverted raw material and the product
5 +Component, the common freshening problem that does not relate to butylene; Also having part is that the technology of purpose improves the propylene total recovery by the by product circulation with the propylene, but most simple forms that by product looped back former reactor that adopt, or the like.
Summary of the invention:
Purpose of the present invention just is to provide a kind of carbon four in the oxygen-containing organic compound conversion system alkene resultant is reached more heavy constituent (C
4 +) further be cracked into C
2 =～C
3 =Method, to improve the selectivity of low-carbon alkene, operation conditions optimization is simplified technical process, reduces construction investment.
The invention provides a kind of carbon four and reach the more method for transformation of heavy constituent, it is characterized in that: the reaction gas of main reactor separates through separation system, isolated carbon four and more heavy constituent enter auxiliary reactor and regenerated catalyst contact reacts from auxiliary revivifier, the reaction gas of auxiliary reactor is delivered to separation system with the reaction gas of main reactor and is separated, the reclaimable catalyst of carbon distribution enters auxiliary revivifier in the auxiliary reactor behind stripping, entering auxiliary reactor behind the coke burning regeneration recycles, the regenerated flue gas that comes out from main revivifier top is incorporated into auxiliary revivifier, wherein auxiliary reactor is identical with the main reactor catalyst system therefor, 500～650 ℃ of the temperature of reaction of auxiliary reactor, preferred 550～600 ℃; Reaction pressure 0.1～0.5MPa, preferred 0.1～0.3MPa; Agent/material is than (catalyzer and carbon four reach the more weight ratio of heavy constituent in the auxiliary reactor) 0.5～20, preferred 5～15.550～750 ℃ of the temperature of auxiliary revivifier, preferred 650～700 ℃.
The present invention also provides a kind of carbon four to reach the more method for transformation of heavy constituent, it is characterized in that: the reaction gas of main reactor separates through separation system, isolated carbon four reaches more heavy constituent and enters auxiliary reactor and the regenerated catalyst contact reacts of coming autonomous revivifier, the reaction gas of auxiliary reactor is delivered to separation system with the reaction gas of main reactor and is separated, the reclaimable catalyst of carbon distribution all enters main reactor in the auxiliary reactor behind stripping, or a part enters main reactor, another part enters main revivifier to be mixed with reclaimable catalyst from main reactor and carries out coke burning regeneration, catalyzer after the regeneration enters auxiliary reactor again and recycles, 500～650 ℃ of the temperature of reaction of auxiliary reactor, preferred 550～600 ℃; Reaction pressure 0.1～0.5MPa, preferred 0.1～0.3MPa; Agent/material is than (catalyzer and carbon four reach the more weight ratio of heavy constituent in the auxiliary reactor) 0.5～20, preferred 5～15.550～750 ℃ of the temperature of main revivifier, preferred 650～700 ℃, wherein said auxiliary reactor is a fluidized-bed reactor.
The present invention provides a kind of carbon four to reach the more method for transformation of heavy constituent in addition, it is characterized in that: the reaction gas of main reactor separates through separation system, isolated carbon four reaches more heavy constituent and enters service hoisting pipe reactor and the regenerated catalyst contact reacts of coming autonomous revivifier, the reaction effluent separated into two parts of service hoisting pipe reactor, a part that accounts for service hoisting pipe reactor total reaction effluent 10～50 weight % enters apart from the close phase section of main reactor top 0～6 meter close phase section, the another part that accounts for service hoisting pipe reactor total reaction effluent 50～90 weight % enters the transition section middle part of the close phase pars infrasegmentalis of main reactor, the reaction product of main reactor is separated, reaction gas after the separation is drawn from the main reactor top, the reclaimable catalyst of the carbon distribution after the separation carries out coke burning regeneration and recycles through the laggard revivifier of becoming owner of of stripping, 500～650 ℃ of the temperature of reaction of service hoisting pipe reactor, preferred 550～600 ℃; Reaction pressure 0.1～0.5MPa, preferred 0.1～0.3MPa; Agent/material is than (subsidiary riser catalyst reactor and carbon four reach the more weight ratio of heavy constituent) 0.5～20, preferred 5～15.550～750 ℃ of the temperature of main revivifier, preferred 650～700 ℃.
Oxygenatedchemicals of the present invention can be selected from methyl alcohol, ethanol, dme and C
4～C
10In the oxygen-containing organic compounds such as alkylol cpd one or more.
The method for transformation of carbon four of the present invention and more heavy constituent is fit to all rich C of producing
4 +The full scale plant of alkene, the catalytic cracking unit of especially suitable oil refining process and deriving device thereof, the MTO process unit of methanol-to-olefins, the MTP device of preparing propylene from methanol, the MTA device of methyl alcohol system aromatic hydrocarbons are preferably applied to the MTO process unit.
Method provided by the present invention is compared the superiority with the following aspects with prior art:
(1) the oxygen-containing compound conversion to produce olefine process unit adopts first kind of method for transformation of the present invention, promptly during two cover reaction regeneration devices, in auxiliary revivifier, introduce the regenerated flue gas that is rich in carbon monoxide by main revivifier, utilize the CO burning liberated heat, improve C
4 +The temperature of olefin cracking revivifier can satisfy C
4 +Olefin cracking reacts needed heat, makes C
4 +The olefin cracking reaction can be carried out under the operational condition of optimizing;
(2) adopt method of the present invention, the further cracking unit of heavy constituent is relatively independent because of its carbon four reaches more, carbon four reaches more heavy constituent conversion reaction to carry out in different reactors with the raw material scission reaction, can independently control the temperature and the space velocity conditions of conversion of olefines, the catalyst type of respectively reacting used simultaneously is identical, avoids causing the catalyst contamination problem because of the catalyzer difference.
(3) adopt method of the present invention, reach more heavy constituent further cracking in the method for the invention by by product carbon four with oxygen-containing compound conversion to produce olefine technology, the overall selectivity of ethene and propylene can be brought up to 85～90%, ethene adds propylene the carbon back yield of methanol feedstock is improved 4～6 percentage points, by changing operational condition, ethene and propylene weight ratio can be regulated between 1.2～0.8 in the product.
(4) adopt method of the present invention, the further cracker shared of oxygen-containing compound conversion to produce olefine process unit and its by product carbon four and more heavy constituent overlaps chilling and water wash system, has simplified technical process, reduces construction investment.
(5) the oxygenatedchemicals scission reaction described in the present invention is thermo-negative reaction, and temperature of reaction is lower, and agent/material is smaller.Among the present invention second and the described catalyst recirculation mode of the third method be serial operation, can guarantee that oxygenatedchemicals carries out under the operational condition of optimizing.
The present invention is described further below in conjunction with the drawings and specific embodiments.But do not limit the scope of the invention.
Description of drawings
Fig. 1 is a kind of schematic flow sheet of the present invention.
Fig. 2 is second kind of schematic flow sheet of the present invention.
Fig. 3 is the third schematic flow sheet of the present invention.
Among the figure: 1-main reactor reaction gas; 2-main reactor cyclonic separator;
The 3-oxygenatedchemicals; The 4-main reactor;
5-master's revivifier; The 6-regenerated flue gas;
7-master's revivifier cyclonic separator; The reaction gas of 8-auxiliary reactor 11;
9-auxiliary reactor cyclonic separator; 10-carbon four and more heavy constituent;
The 11-auxiliary reactor; 12-stripping stage to be generated;
13-assists revivifier riser tube to be generated; 14-assists revivifier;
The regenerated flue gas of the auxiliary revivifier 14 of 15-; 16-preheating main air;
17-main reactor stripping stage; 18-service hoisting pipe reactor;
19-auxiliary reactor regeneration riser tube; 20-master's revivifier riser tube to be generated;
21-main reactor regeneration riser tube; The 22-reaction gas;
The close phase section of 23-; 24-master's revivifier stripping stage;
The 25-transition section.
Embodiment
Fig. 1, Fig. 2 and Figure 3 shows that and be used for oxygenatedchemicals system olefin process schematic flow sheet.
Figure 1 shows that two cover reaction regeneration devices, but auxiliary reactor 11 is identical with catalyst system therefor in the main reactor 4.Oxygenatedchemicals 3 is entered by main reactor 4 bottoms, with the catalyzer contact reacts in the main reactor 4, resultant of reaction separates through main reactor cyclonic separator 2, the main reactor reaction gas 1 that is rich in low-carbon alkenes such as ethene and propylene after the separation is drawn by main reactor 4 tops, mix with the reaction gas 8 of the auxiliary reactor 11 that comes out by auxiliary reactor 11, deliver to rear portion chilling water wash system, by the catalyst fines that carries in the further washing reaction gas of chilling, by washing the most of water in the reaction gas is separated, deliver to the alkene separating unit at rear portion then.In the alkene separating unit, reaction gas is separated, the purpose product ethene and the propylene that obtain go out device, isolated carbon four reaches more heavy constituent 10 and enter auxiliary reactor 11 in the gas phase mode after preheating, in auxiliary reactor 11 with from the high-temperature regenerated catalyst of assisting revivifier 14, directly contact, react rapidly at catalyst surface, the reaction gas 8 of auxiliary reactor 11 is drawn after auxiliary reactor cyclonic separator 9 is removed the catalyzer of being carried secretly, after main reactor reaction gas 1 from main reactor 4 tops mixes, deliver to back pre-separation and olefin separation system together and separate, obtain purpose products such as ethene and propylene.
The reclaimable catalyst of reaction back carbon distribution enters stripping stage 12 strippings to be generated in the auxiliary reactor 11, remove the reaction gas that reclaimable catalyst carries, reclaimable catalyst behind the stripping enters auxiliary revivifier riser tube 13 to be generated behind guiding valve to be generated, under the conveying of nitrogen, enter auxiliary revivifier 14, contact coke burning regeneration with preheating main air 16 in auxiliary revivifier 14, the catalyzer after the regeneration enters auxiliary reactor 11 through auxiliary reactor regeneration riser tube 19 and recycles.
Come regenerated flue gas 6 full doses of autonomous revivifier 5 to be incorporated in the auxiliary revivifier 14, be rich in CO (carbon monoxide converter) gas in the regenerated flue gas 6, utilize the CO burning liberated heat to replenish C
4 +Olefin cracking reacts needed heat, controls CO burning with preheating main air 16 simultaneously, and the rate of combustion of carbon monoxide makes regenerated catalyst temperature in desired scope by the strict control of the oxygen level in the regenerated flue gas 15 of auxiliary revivifier 14.The pre-heating mean of main air can be selected from electrical heating method and in revivifier is set up heat collector heating main air method etc., preferred second method.The regenerated flue gas 15 of auxiliary revivifier 14 is by the smoke stack emission atmosphere.
Described auxiliary reactor of Fig. 1 and auxiliary revivifier are the fluidized-bed pattern, can be bubbling bed, turbulent bed or fast bed streaming mode, preferred turbulent flow fluidization operational stage.
Figure 2 shows that the reclaimable catalyst in main reactor 4 and the auxiliary reactor 11 carries out the regenerated form in same main revivifier 5, auxiliary reactor 11 is a fluidized-bed.Oxygenatedchemicals 3 is entered by main reactor 4 bottoms, with the catalyzer contact reacts in the main reactor 4, resultant of reaction separates through main reactor cyclonic separator 2, the main reactor reaction gas 1 that is rich in low-carbon alkenes such as ethene and propylene after the separation is drawn by main reactor 4 tops, mix with the reaction gas 8 of the auxiliary reactor 11 that comes out by auxiliary reactor 11, deliver to rear portion chilling water wash system, by the catalyst fines that carries in the further washing reaction gas of chilling, by washing the most of water in the reaction gas is separated, deliver to the olefin separation system at rear portion then.In the alkene separating unit, reaction gas is separated, obtain purpose product ethene and propylene and go out device, isolated carbon four reaches more heavy constituent 10 and enter auxiliary reactor 11 in the gas phase mode after preheating, in auxiliary reactor 11 with the regenerated catalyst contact reacts of coming autonomous revivifier 5, the reaction gas 8 of auxiliary reactor 11 is drawn after auxiliary reactor cyclonic separator 9 is removed the catalyzer of being carried secretly, after main reactor reaction gas 1 from main reactor 4 tops mixes, delivering to olefin separation system together separates, the reclaimable catalyst of carbon distribution carries out stripping at stripping stage 12 to be generated in the auxiliary reactor 11, remove the reaction gas that reclaimable catalyst carries, reclaimable catalyst part behind the stripping enters main reactor regeneration riser tube 21, under the conveying of 1.0Mpa steam, enter main reactor 4, continue and oxygen-containing compound material 3 reactions.All the other nitrogen or other media (as, process air) conveying enters into main revivifier 5 through main revivifier riser tube 20 to be generated down, the reclaimable catalyst of main reactor 4 is through the laggard main revivifier 5 of main reactor stripping stage 17 strippings, respectively from two strands of reclaimable catalysts coke burning regeneration in main revivifier 5 of main reactor 4 and auxiliary reactor 11.Catalyzer after the regeneration advances main revivifier stripping stage 24 strippings, and the regenerated catalyst behind the stripping turns back to auxiliary reactor 11 through auxiliary reactor regeneration riser tube 19 and recycles.The regenerated flue gas 6 of main revivifier 5 enters atmosphere by main revivifier 5 tops remove the most of catalyzer that carries through main revivifier cyclonic separator 7 after.
The described auxiliary reactor of Fig. 2 is the fluidized-bed pattern, can be bubbling bed, turbulent bed or fast bed streaming mode, preferred turbulent flow fluidization operational stage.
As shown in Figure 3, oxygenatedchemicals 3 is entered by main reactor 4 bottoms, with the catalyzer contact reacts in the main reactor 4, the reaction gas 22 that is rich in low-carbon alkenes such as ethene and propylene is drawn by main reactor 4 tops after main reactor cyclonic separator 2 is removed the catalyzer of being carried secretly, deliver to rear portion chilling water wash system, by the catalyst fines that carries in the further washing reaction gas of chilling, by washing the most of water in the reaction gas is separated, deliver to the olefin separation system at rear portion then.In the alkene separating unit, reaction gas 22 is separated, the purpose product ethene and the propylene that obtain go out device, isolated carbon four reaches more heavy constituent 10 and enter service hoisting pipe reactor 18 in the gas phase mode after preheating, with the catalyzer contact reacts that enters by main revivifier 5, the reaction effluent separated into two parts of service hoisting pipe reactor 18, a part that accounts for service hoisting pipe reactor 18 total reaction effluents 10～50 weight % enters apart from main reactor 4 close phase sections 23 tops 0～6 meter close phase section, the another part that accounts for service hoisting pipe reactor 18 total reaction effluents 50～90 weight % enters transition section 25 middle parts of main reactor 4 close phase pars infrasegmentalises, the reaction product of main reactor 4 is separated through main reactor cyclonic separator 2, reaction gas 22 after the separation is drawn from main reactor 4 tops, delivers to the chilling water wash system then.The reclaimable catalyst of the carbon distribution after the separation enters main reactor stripping stage 17 strippings, removes the reaction gas that reclaimable catalyst carries, and the reclaimable catalyst behind the stripping enters main revivifier 5 under the conveying of nitrogen, coke burning regeneration in main revivifier 5.Catalyzer after the regeneration advances main revivifier stripping stage 24 strippings, and the regenerated catalyst behind the stripping enters service hoisting pipe reactor 18 and recycles.
Carbon four and more the injection phase of heavy constituent 10 be selected from the upper, middle and lower and oxygenate feedstock pipeline of service hoisting pipe reactor 18 top or the bottom of preferred service hoisting pipe reactor 18.
The regenerated flue gas 6 of main revivifier 5 enters atmosphere by main revivifier 5 tops remove the most of catalyzer that carries through main revivifier cyclonic separator 7 after.
Claims (5)
1. a carbon four reaches the more method for transformation of heavy constituent, it is characterized in that: the reaction gas of main reactor separates through separation system, isolated carbon four and more heavy constituent enter auxiliary reactor and regenerated catalyst contact reacts from auxiliary revivifier, the reaction gas of auxiliary reactor is delivered to separation system with the reaction gas of main reactor and is separated, the reclaimable catalyst of carbon distribution enters auxiliary revivifier in the auxiliary reactor behind stripping, entering auxiliary reactor behind the coke burning regeneration recycles, the regenerated flue gas that comes out from main revivifier top is incorporated into auxiliary revivifier, wherein auxiliary reactor is identical with the main reactor catalyst system therefor, 500～650 ℃ of the temperature of reaction of auxiliary reactor, reaction pressure 0.1～0.5MPa, agent/material is than 0.5～20; 550～750 ℃ of the temperature of auxiliary revivifier.
2. a carbon four reaches the more method for transformation of heavy constituent, it is characterized in that: the reaction gas of main reactor separates through separation system, isolated carbon four reaches more heavy constituent and enters auxiliary reactor and the regenerated catalyst contact reacts of coming autonomous revivifier, the reaction gas of auxiliary reactor is delivered to separation system with the reaction gas of main reactor and is separated, the reclaimable catalyst of carbon distribution all enters main reactor in the auxiliary reactor behind stripping, or a part enters main reactor, another part enters main revivifier to be mixed with reclaimable catalyst from main reactor and carries out coke burning regeneration, catalyzer after the regeneration enters auxiliary reactor again and recycles, 500～650 ℃ of the temperature of reaction of auxiliary reactor, reaction pressure 0.1～0.5MPa, agent/material is than 0.5～20; 550～750 ℃ of the temperature of main revivifier, wherein said auxiliary reactor are fluidized-bed reactor.
3. a carbon four reaches the more method for transformation of heavy constituent, it is characterized in that: the reaction gas of main reactor separates through separation system, isolated carbon four reaches more heavy constituent and enters service hoisting pipe reactor and the regenerated catalyst contact reacts of coming autonomous revivifier, the reaction effluent separated into two parts of service hoisting pipe reactor, a part that accounts for service hoisting pipe reactor total reaction effluent 10～50 weight % enters apart from the close phase section of main reactor top 0～6 meter close phase section, the another part that accounts for service hoisting pipe reactor total reaction effluent 50～90 weight % enters the transition section middle part of the close phase pars infrasegmentalis of main reactor, the reaction product of main reactor is separated, reaction gas after the separation is drawn from the main reactor top, the reclaimable catalyst of the carbon distribution after the separation carries out coke burning regeneration through the laggard revivifier of becoming owner of of stripping, catalyzer after the regeneration enters the subsidiary riser reactor cycles again and uses, 500～650 ℃ of the temperature of reaction of service hoisting pipe reactor, reaction pressure 0.1～0.5MPa, agent/material is than 0.5～20; 550～750 ℃ of the temperature of main revivifier.
4. method for transformation according to claim 1 is characterized in that: 550～600 ℃ of the temperature of reaction of auxiliary reactor, and reaction pressure 0.1～0.3MPa, agent/material is than 5～15; 650～700 ℃ of the temperature of auxiliary revivifier.
5. according to claim 2 or 3 described method for transformation, it is characterized in that: 550～600 ℃ of the temperature of reaction of auxiliary reactor, reaction pressure 0.1～0.3MPa, agent/material is than 5～15; 650～700 ℃ of the temperature of main revivifier.
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