CN102533321B - Catalytic conversion method and device for reducing sulfur content of gasoline - Google Patents
Catalytic conversion method and device for reducing sulfur content of gasoline Download PDFInfo
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- 239000011593 sulfur Substances 0.000 title claims abstract description 39
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
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- 239000003208 petroleum Substances 0.000 claims description 4
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 14
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- VQYHBXLHGKQYOY-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[Al+3].[Ti+4] VQYHBXLHGKQYOY-UHFFFAOYSA-N 0.000 description 1
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- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a catalytic conversion method and a device for reducing the sulfur content of gasoline, which have stronger desulfurization capability, good product selectivity, high yield of light oil products and easy operation and control. The cyclic catalyst is completely regenerated, the product quality is stable, the operation and the control are easy, and the sulfur of the gasoline is reduced to the maximum extent; the method can avoid instant coking caused by contact between a high-temperature catalyst and oil gas and reduction of the yield of light oil products caused by overhigh temperature of gasoline modification reaction, improve the product distribution and flexibly change the catalyst-oil ratio or the reaction temperature of catalytic cracking reaction; the method can realize 40-80% of FCC gasoline desulfurization. More than 80% of FCC gasoline desulfurization can be achieved if the catalyst is used in combination with a specific catalyst.
Description
Technical field
The present invention relates to a kind of catalysis conversion method and the device thereof that reduce content of sulfur in gasoline, be specifically related to catalysis conversion method and the device thereof of a kind of remarkable reduction content of sulfur in gasoline and olefin(e) centent.
Background technology
Along with the increasingly stringent of environmental regulation, Euro II standard was implemented in 1996 in Europe, and within 2000, implement Eu III standard, within 2005, implement the Europe IV standard, namely gasoline sulfur reaches 10ppm; U.S. Tier2 standard-required gasoline sulfur in 2004 is less than 300ppm, within 2005, reaches 30ppm; Asia Bangkok, THA, India Delhi, Korea S etc. also successively implement Euro II standard in 1999 and 2000 or are equivalent to Euro II standard; Japan is stricter than the standard in Europe, keeps synchronous with the U.S..BeiJing, China performs Euro II standard on July 1st, 2000, and carried out Eu III standard in 2005, ultimate aim is to vehicle emission standards in 2010 and European synchronous.Therefore, the production technology of low-sulphur oil standard is met in the urgent need to exploitation.
Because FCC gasoline is to the contribution (in gasoline product, the sulphur of more than 90% and the alkene of more than 90% come from catalytically cracked gasoline) more than 90% of the sulphur content in gasoline product and olefin(e) centent, therefore FCC gasoline quality receives much concern.At present, the method for reduction FCC gasoline sulphur content is broadly divided into three kinds: one is the sulphur (weighted BMO spaces method) removed in FCC stock oil; Two is direct production low-sulphur oil in FCC process; Three is carry out aftertreatment to FCC gasoline.
FCC raw material weighted BMO spaces is the effective way reducing content of sulfur in gasoline, as CN1351131A discloses a kind of working method of sulphur-bearing crude, the techniques such as atmospheric and vacuum distillation, coking or solvent deasphalting, middle pressure hydrocracking, catalytic cracking are combined, enables refinery process the sour feedstock wet goods of sulphur content 1.8 ~ 2.8%.But this method increase degree of olefin saturation, reduce gasoline octane rating, and this hydroprocessing process investment is large, and process cost is high.
FCC gasoline post-treating method develops kinds of processes at present abroad, as: the ISAL method that INTERVEP and Uop Inc. develop jointly, mainly solve the problem of octane value and sulphur content in FCC gasoline aftertreatment, the octane value of the gasoline obtained by ISAL method, higher than common hydrotreatment gasoline 7.4 units (road method octane value), can meet the requirement of refinery 25ppm sulphur and maintenance gasoline octane rating simultaneously.S-Zorb gasoline desulfur (SRT) method of Philips Petroleum Company's exploitation, can obtain eco-friendly, loss of octane number minimum, gasoline products that hydrogen consumption is very little.CN1485414A discloses a kind of method of catalytically cracked gasoline non-hydrogen aromatization and desulfurization, the method makes distillate or the lighting end after fractionation enter an aromizing desulphurization reactor, carry out alkene aromatization, the hydrogen utilizing aromatization to produce carries out hydrodesulfurization reaction, reduces the alkene in gasoline and sulphur content.Other realize the SCANfining method that industrialized gasoline aftertreatment desulfurization technology also comprises Exxon company and the joint development of Akzo company; The Prime-G of the gasoline ultra-deep desulfurization of IFP's exploitation
+method, the content of sulfur in gasoline obtained is less than 50 μ g/g, and desulfurization degree is 97.5%; The ROK-Finer method of Japan National Oil Corporation's exploitation, within 2004, put into operation, the gasoline sulfur of production is less than 10 μ g/g.Although gasoline aftertreatment desulfurization technology all has higher desulfurization degree, need new device, add facility investment.
In catalytic cracking process, directly reduce content of sulfur in gasoline mainly set about in Catalyst And Method two, wherein, use sulfur-lowing catalyst or auxiliary agent technical elements, the GSR series of Grace Davison company exploitation and the serial sulfur prodegradant of D-Prism (US376608), take aluminum oxide titanium white as matrix, the L-acid constituentss such as load zinc oxide, make FCC gasoline sulphur content reduce about 20%-35%; SATURN FCC catalyzer, commerical test shows to reduce FCC gasoline sulfur-bearing more than 50%.The RESOLVE series auxiliary agent technology of Akzo Nobel company exploitation, when processing the VGO raw material without the sulfur-bearing 0.7% of hydrotreatment, adopt RESOLVE 700 content of sulfur in gasoline can be dropped to 442 μ g/g from 600 μ g/g, after adding the RESOLVE 800 of 10% again, the sulphur content of full range gasoline continues to drop to 340 μ g/g from 442 μ g/g.The NaphthaMax-LSG sulfur-lowing catalyst that Engelhard company develops on NaphthaMax catalyzer basis, adds and falls sulfur functional while having higher transformation efficiency and gasoline yield.In catalytic cracking process directly reduce content of sulfur in gasoline Technology in, US Patent No. 6, 287, LOCC method involved in 522 B1, utilize a kind of Double-lifted pipe catalytic cracking device, by by major part from lighter hydrocarbons riser reactor without steam stripped reclaimable catalyst and the bottom being delivered on a small quantity heavy oil riser reactor from the mixing reclaimable catalyst formed without steam stripped reclaimable catalyst of heavy oil riser reactor by a catalyst transport, mix with the high-temperature regenerated catalyst from revivifier, mixed catalyzer is up in heavy oil riser reactor to react with heavy oil riser reactor feed contacts.This technology utilizes the activity and lower temperature that the reclaimable catalyst of lighter hydrocarbons riser reactor is higher, reduce the temperature with the catalyzer of heavy oil riser reactor feed contacts, the heat cracking reaction of heavy oil riser reactor can be reduced and promote catalytic cracking reaction, improving product slates.But because lighter hydrocarbons riser reactor do not delivered to by the method self-circulation catalyzer, make that the ratio of the catalyzer of lighter hydrocarbons riser reactor and gasoline feeding is less, the reaction times is shorter, thus gasoline desulfur effect is poor.Chinese patent CN1401740A discloses a kind of catalysis conversion method of modifying inferior patrol, comprise a conventional heavy oil catalytic cracking process and an inferior patrol catalyzed conversion upgrading processes, two processes share a catalyst regenerator, use same FCC catalyzer, content of sulfur in gasoline can be made to reduce by 15 ~ 50 percentage points, and gasoline octane rating improves 0.2 ~ 2 unit.Chinese patent CN1176189C discloses a kind of catalysis conversion method and device of modifying inferior patrol, double lifting leg (heavy oil riser reactor and gasoline rising pipe reactor) catalytic cracking process and Conventional catalytic cracking catalyzer is adopted to carry out upgrading to inferior patrol, desulfurization is carried out by the conversion of sulfide in petrol and hydrogen transfer reactions, content of sulfur in gasoline can reduce by 5 ~ 30wt%, and sulphur content reduces limited extent.Chinese patent CN1721055 discloses a kind of Double-lifted pipe catalytic cracking device reducing sulfur content of catalytic cracking gasoline, be mainly used in the general higher problem of sulfur content of catalytic cracking gasoline that the existing Conventional catalytic cracking device of solution is produced, the Double-lifted pipe catalytic cracking device adopted comprises heavy oil riser reactor and gasoline rising pipe reactor, erect riser below gasoline rising pipe reactor lift gas entrance is provided with the round shape bed reactor of expanding structure, erect riser below bed reactor is provided with bed reactor pre-lift medium inlet.Use desulfurization catalyst cracking catalyst in device operating process, the sulphur content of catalytically cracked gasoline can reduce by 50 ~ 70%, and content of olefin in gasoline reduces by 20 ~ 40 volume percentage points, and gasoline octane rating (RON) improves 0.3 ~ 2.0 unit.This patent bed reactor temperature of reaction 630 ~ 720 DEG C, reaction pressure 0.15 ~ 0.45Mpa, catalyst residence times 30 ~ 200s, simultaneously containing gasoline rising pipe reactor.This technology utilizes bed reactor and gasoline rising pipe reactor, although significantly content of sulfur in gasoline can be reduced, but the high temperature catalyst after regeneration directly enters heavy oil riser reactor and bed reactor and hydrocarbons contact without cooling to react, catalyzer moment coking, unstable product quality, not easy operation control; The service temperature of bed reactor is higher in addition, is unfavorable for gasoline upgrading, and yield of gasoline is low.CN1861757 relates to a kind of catalyst cracking method and equipment of high efficient reducing gasoline sulphur content, one or several oxidation-reduction processing unit is increased in the reaction-reclaim equiment of existing riser fluid catalytic cracking, under certain reaction conditions with atmosphere with circulation, the FCC catalyzer of fluidized fully contacts, there is oxidation-reduction reaction, with the valence state of metal component in regulating catalyst, meet desulphurizing activated needs, make the desulphurizing activated of catalyzer maintain higher level all the time; The riser tube that one is accompanied with processing unit is increased further in reaction-reclaim equiment, catalytically cracked gasoline cut is contacted with the catalyst mixture of pyroprocessing again, carry out secondary cracking reaction, reach further desulfurization and reduce olefin(e) centent and increase the object of gasoline octane rating.By this processing method, select specific catalyzer that sulfur content of catalytic cracking gasoline can be made to reduce to reach more than 80%, olefin(e) centent is reduced to 10-25 (v) %, and gasoline Research octane value does not reduce or slightly improves.CN101104815A and CN200610048408.1 proposes and is improved by the gasoline rising pipe in existing Double-lifted pipe catalytic cracking device, change into respectively and fast bed reactor is set in gasoline rising pipe reactor middle and upper part or directly changes gasoline rising pipe into fast bed reactor, although these two kinds of techniques reach the object of gasoline upgrading, but the catalyzer of partial regeneration enters fast bed reactor to react, along with constantly carrying out of reaction, carbon distribution on catalyzer is on the increase, the unstable product quality of gasoline upgrading; The catalyzer entering gasoline upgrading reactor, not through process of effectively lowering the temperature, makes gasoline upgrading temperature of reaction be not easy to be effectively controlled, also can make the unstable product quality of gasoline upgrading.CN1245202A proposes the combined reactor that a kind of Novel hoisting pipe reactor and a kind of riser tube add fluidized-bed, the hydrogen transfer reactions adopting twoth district to react for catalytic cracking provides favourable condition---low temperature, the relatively long residence time, but due to the pressure equilibrium problem of catalyst cracker, no matter be all can not form relatively high level of dense bed in riser tube stage casing or top, the effect of therefore the method actual hydrogen transfer reactions obtained in industrial implementation process is undesirable.For while the reinforcement feedstock conversion degree of depth, suitably control the reaction severity in riser tube, CN1206036 discloses a kind of regenerated catalyst cooling scheme, namely partial regeneration catalyzer is cooled, cooled regenerator mixes at the pre lift zone of riser tube with uncooled high temperature regeneration agent, and upwards flow under the effect of pre-lift medium, above-mentioned catalyzer contacts with stock oil at conversion zone, reacts.Breach the thermally equilibrated restriction of catalyzer by catalyzer cooling, can regulate the agent-oil ratio in reaction process easily, strengthen heavy oil conversion performance, improve product slates, but the high problem of content of olefin in gasoline is not resolved, the effect of falling sulphur does not embody.CN1200083C relate to a kind of catalytic cracking combination process, the method makes the regenerator of 10 ~ 80 heavy % enter in the reaction zone of circular fluidized-bed reactor after cooling, contact with gasoline, react, the reaction oil gas generated sends into follow-up gasoline conversion product separation equipment; And stripping is carried out in the stripping zone that reacted catalyzer enters circular fluidized-bed reactor; Catalyzer 40 ~ 90 % by weight after stripping returns to reaction zone and recycles, and rest part is delivered in riser reactor, mixes with without the regenerator cooled, and upwards flows along riser tube under the effect of pre-lift medium; Hydrocarbon raw material injecting lift pipe, with the catalyst exposure in it, reaction, reactant flow enters settling vessel through leg outlet; Separating reaction oil gas and catalyzer, oil gas sends into subsequent product separating device, and after reaction, the catalyzer of carbon deposit uses through stripping, regeneration Posterior circle.By this technique, the conversion capability of heavy oil improves and quality product improves, but constantly carrying out with reaction, carbon deposit on catalyzer in circulation fluidized-bed raises gradually, have impact on the product performance of gasoline upgrading, unstable product quality, can not realize falling sulphur to greatest extent; Catalyst temperature after regeneration is higher, enters riser reactor and contacts with stock oil, easy coking, and operation is not steady, and the quality of product can not ensure.CN02149314.6 proposes a kind of method and apparatus of catalytic gasoline upgrading Olefin decrease, by the high reactivity after catalytic gasoline upgrading, the reclaimable catalyst of low temperature is introduced in a catalyst mix tank newly added, high-temperature regenerated catalyst is introduced from former revivifier simultaneously, the catalyzer having neither part nor lot in reaction of former catalytic cracking unit normal need displacement is introduced simultaneously, three bursts of catalyst stream mix under the rheomorphism of the fluidization air introduced from catalyst mix pot bottom, carry out burning reaction simultaneously, gasoline upgrading reactor is selected from riser reactor, turbulent bed reactor or fast bed reactor.Although this technique reaches reduce olefin(e) centent and the object increasing octane value, but catalyzer burns to be needed to carry out at higher than the temperature of 600 DEG C, catalyzer after so burning effectively can not reduce temperature in mixing tank, what guarantee entered gasoline upgrading reactor is all low temperature catalysts, and the catalyzer of comparatively high temps enters gasoline upgrading reactor, carry out upgrading to gasoline and easily caused cracking, product selectivity is unstable; The catalyzer that same temperature is higher enters heavy oil riser reactor and reacts easy coking; Three bursts of catalyst mix use in addition, operate more wayward, unstable product quality.CN101591562A relates to a kind of fluidized catalytic cracking method and device thereof, catalyzer from revivifier is mixed into the riser tube of reactor I, fast bed reactor and settling vessel at mixing section through heat-obtaining and heavy raw oil, HYDROCARBON-BEARING REGION separation column, catalyzer enters revivifier regeneration; Reactor II is mixed into from another part catalyzer of revivifier and lightweight material oil, reaction oil gas and catalyst compound enter settling vessel, oil gas enters separation column, catalyzer enters revivifier and regenerates, reactor I produces qualified gasoline, reactor II produces alkene, utilizes set of device to meet the needs producing gasoline and industrial chemicals.Although the method meets the demand of producing gasoline and industrial chemicals, the catalyzer of coking enters fast bed reactor when continuing to contact with oil gas, well can not reduce sulphur content in gasoline and improve product slates.CN1081222C discloses a kind of catalysis conversion method reducing olefin(e) centent in liquefied gas and gasoline, the method is the bottom and the catalyst exposure that the traditional cracking stock oil after preheating are entered riser tube in riser tube or the compound reactor that is made up of riser tube and fluidized-bed, the oil gas generated after reaction goes upward to the middle part of riser tube or the top of riser tube and the catalyst exposure after lowering the temperature and proceeds to react, and after reaction, effluent enters settling vessel; Reaction product isolated, reclaimable catalyst is divided into two portions after stripping, regeneration, and wherein a part enters the bottom of riser tube, and another part enters the middle part of riser tube or the top of riser tube after cooling.Alkene during this technique makes gasoline form is reduced to 12.32 heavy %, isoparaffin can be increased to 41.83 heavy %, but the serious carbon distribution of the reacted catalyst surface of riser tube, activity reduces greatly, the touch opportunity of oil gas and catalyzer is reduced, well can not reduce the sulphur content in gasoline.CN00100823.4 discloses a kind of gas-solid and flow folding type fast fluidization bed reaction device, this invention comprises riser reactor, downer reactor, gas-solid separator and stripper, the lifting inner concentric tube that riser tube sends out heroic spirit is provided with downer reactor, gas-solid quick disconnector is connected with there being outer communicating pipe between stripper, obviously improve although device of the present invention makes gas-particle two-phase contact homogeneity, avoided the appearance of the phenomenons such as cracking, improve selectivity, but two reactors installed with one heart can influence each other, temperature of reaction is wayward, products distribution is unstable, and adopt multiple gas-solid separator and cyclonic separator, add the investment of equipment, cost is large.CN200410060323.6 proposes a kind of catalysis conversion method and device of producing clean fuel oil by petroleum hydrocarbon stock, this device is made up of the stock oil riser reactor be set up in parallel and gasoline rising pipe reactor, petrol vapour solid separator in stock oil reactor, the upper and lower outlet of gas-solid separator connects gasoline riser and catalyzer depressant prescription pipe respectively, gasoline rising pipe reactor outlet is connected with the petrol vapour solid separator in stock oil riser reactor, and gasoline riser stretches out stock oil riser reactor.This technique makes gasoline and heavy oil react mutually to coordinate, has complementary advantages, in product, olefin(e) centent is low, but hydrocarbon raw material behind the first reaction zone without separation, continue to react with the cooling catalyst exposure from gasoline rising pipe, hot mixture and low temperature catalyst instantaneous touch, easy coking, product slates is unstable, operates wayward.
Reactor involved by above-mentioned patent adopts double lifting leg or combined reactor, wherein a part not only increases extra reactor unit and carries out the reduction treatment of catalyst activity component or carry out gasoline high temperature (600 ~ 700 DEG C) pre-reaction, also can increase facility investment and technical process, decrease yield of gasoline; A part adopts partial regeneration in addition, and after regeneration, high temperature catalyst is without cooling, causes product selectivity poor, fluctuation of service; Also have the compound reactor adopted in addition, do not regenerate after one section of catalyzer and gas-oil separation, direct and hydrocarbons contact carries out second-stage reaction, and agent oil touch opportunity is greatly reduced.
Summary of the invention
The object of this invention is to provide a kind ofly have that stronger sweetening power, simultaneously light oil yield are high, the FCC desulphurization technological process of flexible operation and equipment, realize FCC gasoline desulfurization 40 ~ 80%.If in conjunction with the use of special catalyst, then can realize FCC gasoline desulfurization more than 80%.It is active that this specific catalyzer has higher cracking reaction, and its B acid is relatively high with L acid content, enhances the Preferential adsorption to sulfide and cracking function.
The present invention improves existing heavy oil fluid catalytic cracking riser arrangement, a kind of device reducing the catalyzed conversion of content of sulfur in gasoline is provided, include reactor, settling vessel, revivifier, riser tube catalyst transport pipeline and fluid catalyst transport pipe, it is characterized in that reactor is compound reactor, by coaxial, riser reactor 5 from bottom to top, gas-solid separator 6, fluidized-bed reactor 7 is formed, the top exit of fluidized-bed reactor 7 is connected with settling vessel, the bottom of fluidized-bed reactor 7 downward vertical standpipe is provided with gasoline feeding entrance 18 and fluid catalyst transport pipe 20, erect riser below riser reactor 5 is provided with riser reactor lift gas entrance 1 and heavy oil feed mouth 4, gas-solid separator 6 side exit is provided with riser tube catalyst transport pipeline 19.
Fluidized-bed reactor diameter is preferably 3 ~ 10 times of heavy oil riser reactor diameter, and its blade diameter length ratio is preferably 0.1 ~ 0.4.The blade diameter length ratio of fluidized-bed is excessive or too small, and excessive or too small all easily the causing in fluidized-bed of diameter forms jet or channel, and gas-solid contact efficiency and operational stability are reduced.Include gas-solid separator 6 in device of the present invention, the top exit of gas-solid separator is connected with bottom fluidized-bed reactor 7, and the position of gas-solid separator is located at the position of riser tube+fluidized bed height 40 ~ 60%.
Gas-solid separator of the present invention can be cyclonic separator, catalytic cracking quick disconnector (VQS) and strainer.It can need according to test the separation degree changing catalyzer and oil gas flexibly.Gas-solid separator is provided with release button to control the degree be separated, and separating effect can be 40 ~ 100%, and preferably 80 ~ 100%.
The gas-solid separator increased makes the catalyzer of the first reaction zone partly or entirely be separated with oil gas, increases the activity of catalyzer of second reaction zone and the touch opportunity with oil gas, reduces the sulphur content in gasoline further; Increase the fluidized-bed reactor that catalytically cracked gasoline carries out the reaction of catalysis secondary cracking, reduce the content of sulphur and alkene in catalytically cracked gasoline further, guarantee that the octane value of gasoline does not reduce simultaneously; Reacted coked catalyst all regenerates, constant product quality, and selectivity is good, easy operation control, can reach and reduce gasoline sulfur to greatest extent; Increase cooling apparatus, high temperature catalyst and hydrocarbons contact moment coking and the too high light oil yield caused of gasoline upgrading temperature of reaction is avoided to reduce, improve product slates, for the agent-oil ratio or temperature of reaction changing catalytic cracking reaction neatly creates favourable conditions.
The present invention more specifically provides a kind of catalytic convention design using the reduction content of sulfur in gasoline of this device, it is characterized in that the top exit of riser reactor communicates with gas-solid separator 6, bottom is connected with revivifier 10 by the first regenerator sloped tube 13, standpipe 12, the top exit of fluidized-bed reactor is connected with settling vessel 8, and the erect riser that fluidized-bed reactor 7 is provided with below gasoline feeding entrance 18, fluidized-bed reactor is connected with the outlet of gas-solid separator 6; The bottom of fluidized-bed reactor downward vertical standpipe is connected with revivifier 10 by fluid catalyst transport pipe 20, second regenerator sloped tube 14, standpipe 12; Riser tube water cooler 22 and fluidized bed cooler 23 is respectively equipped with at the middle part of the first regenerator sloped tube 13 and the second regenerator sloped tube 14.
Contriver is surprised to find, adopt beneficial effect of the present invention to comprise: in operating process, be fluidized bed bioreactor pre-lift medium (catalytic cracked dry gas, hydrogen, water vapor, carbon monoxide) after catalyzer of the present invention cooling and promote to enter in fluidized-bed reactor to mix with the hydrocarbons contact that heavy oil riser reactor produces and react.The diameter of fluidized-bed reactor is relatively large, for 3 ~ 10 times of common riser reactor diameter, length relatively short (being generally 0.2 ~ 0.8 times of conventional lift length of tube), therefore with Conventional riser reacting phase ratio, the reaction characteristics of this fluidized-bed reactor is that finish is long for duration of contact, there is oil gas and catalyzer back-mixing simultaneously.Gasoline and catalyzer have at relatively low temperature and contact more fully, sulfide in gasoline is decomposed to greatest extent, promote the fully saturated of gasoline olefin, thus more effectively the sulfide in gasoline removed and reduce olefin(e) centent, keep higher light oil yield simultaneously.
What adopt in the present invention is the form of heavy oil riser reactor+gas-solid separator+fluidized-bed reactor, the sulphur content reduced in gasoline mainly utilizes the long duration of contact of fluidized-bed, if adopt riser catalytic cracking to fall sulphur insufficient amplitude, and the high temperature catalyst after regeneration enters heavy oil riser reactor and hydrocarbons contact, the easy coking of catalyzer.
A kind of catalysis conversion method using the reduction content of sulfur in gasoline of this device that the present invention also provides, is included in aforesaid device and carries out following steps:
A () heavy oil feed 3 enters riser reactor 5 by heavy oil feed mouth 4, riser reactor lift gas 2 (being generally water vapour) enters riser reactor 5 by riser reactor lift gas entrance 1.The regenerated catalyst coming from revivifier enters riser reactor 5 through standpipe 12, first regenerator sloped tube 13, mixes with heavy oil feed 3 in the bottom of riser reactor 5.Heavy oil feed 3 is up along heavy oil riser reactor 5 with regenerated catalyst afterwards, contacts and react in riser reactor 5 under Conventional catalytic cracking condition.Obtain the first reactant flow after reaction terminates, reactant flow enters gas-solid separator 6 by the top exit of riser reactor 5.In gas-solid separator 6, reactant flow carries out reclaimable catalyst and gas-oil separation, and isolated mixed oil and gas enters fluidized-bed reactor; Isolated reclaimable catalyst enters settling vessel stripping stage 11 through riser tube catalyst transport pipeline 19, enters revivifier 10 after settling vessel stripping stage 11 is with water vapour stripping.
B () reclaimable catalyst carries out coke burning regeneration in revivifier 10, the regenerated catalyst portion after regeneration returns riser reactor 5 through standpipe 12, first regenerator sloped tube 13, riser tube water cooler 15, enters the second regenerator sloped tube 14;
C () comes from the regenerated catalyst of the revivifier 10 of process (a), enter fluidized-bed reactor 7 through standpipe 12, second regenerator sloped tube 14, fluidized bed cooler 16, fluid catalyst transport pipe 20; Promote medium inlet 22 by fluidized-bed reactor and pass into fluidized-bed reactor pre-lift medium 21, fluidized-bed reactor pre-lift medium 21 mixes backward upper flowing with the regenerated catalyst from the second regenerator sloped tube 14, enters fluidized-bed reactor 7 by the bottom inlet of fluidized-bed reactor 7.In fluidized-bed reactor 7, gasoline feeding 17 (comprising the mixed oil and gas of riser reactor) enters fluidized-bed reactor 7 by gasoline feeding mouth 18, be 300 ~ 550 DEG C in temperature of reaction, the charge ratio of regenerated catalyst and gasoline feeding 17 is 1 ~ 15, and reaction velocity is 4.0 ~ 60.0h
-1contact with the regenerated catalyst risen through pre-lift air lift under condition and react, the second reactant flow obtained after reaction leaves fluidized-bed reactor 7 by the top exit of fluidized-bed reactor 7;
D () enters settling vessel 8 from the second reactant flow of fluidized-bed reactor 7.In settling vessel 8, carry out reclaimable catalyst and gas-oil separation to reactant flow, isolated oil gas 9 enters fractionation apparatus and carries out fractionation, and isolated reclaimable catalyst enters revivifier 10 after settling vessel stripping stage 11 is with water vapor stripping.Reclaimable catalyst carries out coke burning regeneration in revivifier, then carries out step (b), realizes recycling of catalyzer.
The reaction conditions of heavy oil feed in riser reactor is Conventional catalytic cracking condition, principal reaction condition is usually as follows: temperature of reaction (riser reactor top exit temperature) is generally 300 ~ 700 DEG C, reaction times is generally 0.5 ~ 5s, agent-oil ratio (weight ratio) is generally 3 ~ 10, and reaction pressure (absolute pressure) is generally 0.15 ~ 0.4MPa; The reaction conditions of fluidized-bed reactor is: temperature of reaction is generally 300 ~ 550 DEG C, is preferably 350 ~ 500 DEG C; The agent-oil ratio of fluidized-bed reactor is generally 1 ~ 15, is preferably 2 ~ 10; The reaction velocity (volume space velocity) of fluidized-bed reactor is generally 4.0 ~ 60.0h
-1, be preferably 6.0 ~ 30.0h
-1.Gas-solid separator separation degree is 40 ~ 100%, preferably 80 ~ 100%.From the reclaimable catalyst of riser reactor and fluidized-bed reactor under catalytic cracking catalyst regeneration condition in revivifier coke burning regeneration, regeneration temperature general control is at 650 ~ 750 DEG C; Catalyzer after regeneration uses through cooling Posterior circle.Settling vessel stripping stage adopts conventional operational condition.In the present invention, in order to avoid too high temperature of reaction causes crossing cracking and reducing yield of gasoline of gasoline, catalyzer after regeneration enters fluidized-bed reactor through overcooling, and the temperature of reaction of fluidized-bed reactor relatively low (best 350 ~ 500 DEG C), recycling catalyst all regenerates; Simultaneously in order to improve the touch opportunity of catalyzer and oil gas, at the position of riser tube+fluidized bed height 40 ~ 60%, setting up a gas-solid separator, effectively can be separated catalyzer and the oil gas of riser reactor.
Heavy oil feed described in the present invention comprises long residuum, vacuum residuum, straight-run gas oil, wax tailings, shale oil, synthetic oil, crude oil, coal tar, recycle stock, slurry oil, deasphalted oil, also can be the blending oil of above various oil product.Fluidized-bed reactor both can carry out desulfurization to the gasoline that the riser reactor of catalytic cracking process of the present invention itself is produced, and also can process the sour gasoline, particularly high sulfur oil produced by other devices as known in the art; Said sour gasoline charging comprises the gasoline of the higher gasoline of light FCC gasoline, catalytic cracking heavy petrol, thermo-cracking and thermally splitting petroleum naphtha, thermo-cracking and thermally splitting heavy petrol, light coker naphtha and the sulphur content such as coking heavy petrol, cracking ethylene preparation gasoline and different boiling range scope, also can be the blending oil of above various oil product.
In process (c), the charging of fluidized-bed reactor is the mixed oil and gas that sour gasoline and/or riser reactor itself are produced.
In the present invention, fluidized-bed reactor pre-lift medium used comprises one or more in following gas: catalytic cracked dry gas, hydrogen, water vapor and carbon monoxide.The rear gaseous media (mainly gasoline, liquefied gas tank, dry gas, hydrogen etc.) generated of reaction and the fluidized-bed pre-lift medium (mainly catalytic cracked dry gas, hydrogen, water vapor, carbon monoxide) not participating in reaction upwards flow in company with catalyzer, catalyzer is separated in settling vessel with oil gas, and after settling vessel stripping stage water vapor stripping, enters revivifier carry out coke burning regeneration.In regenerative process, attachment sulfide generation oxidizing reaction on a catalyst generates sulfur oxide, enters rear portion equipment together with flue gas, and the catalyst recirculation after regeneration uses.
After Conventional catalytic cracking technique, cracking technology transform present invention process as, aforesaid method all can be adopted to carry out gasoline desulfur.
Riser tube of the present invention-fluid bed reactor catalysis process method is adopted to carry out catalytic cracking and desulfurizing, compared with adopting the riser catalytic cracking technique of routine, the present invention can make content of sulfur in gasoline reduce by 40 ~ 80% under the constant condition of total liquid yield (referring to the liquefied gas of catalytic cracking reaction, gasoline and diesel oil three sum), gasoline olefin reduces by 20 ~ 40 volume percentage points, gasoline octane rating (RON) improves 1 ~ 5 unit, and full device product distribution is good.
Accompanying drawing explanation
Fig. 1 illustrates application a kind of flow process reducing the embodiment of content of sulfur in gasoline catalysis conversion method of the present invention, and the shape and size of equipment and pipeline not by the restriction of accompanying drawing, but are determined as the case may be.
In accompanying drawing, 1-riser reactor lift gas entrance, 2-riser reactor lift gas, 3-heavy oil feed, 4-heavy oil feed mouth, 5-riser reactor, 6-gas-solid separator, 7-fluidized-bed reactor, 8-settling vessel, 9-mixed oil and gas, 10-revivifier, 11-settling vessel stripping stage, 12-standpipe, 13-first regenerator sloped tube, 14-second regenerator sloped tube, 15-riser tube water cooler, 16-fluidized bed cooler, 17-gasoline feeding, 18-gasoline feeding mouth, 19-riser tube catalyst transport pipeline, 20-fluid catalyst transport pipe, 21-fluidized-bed reactor pre-lift medium, 22-fluidized-bed reactor promotes medium inlet.
Embodiment
See Fig. 1, riser tube-fluid catalytic cracking process of the present invention, comprise riser reactor, gas-solid separator, fluidized-bed reactor, settling vessel, revivifier, the top exit of riser reactor communicates with bottom gas-solid separator, and bottom is connected with revivifier by the first regenerator sloped tube, standpipe.Fluidized-bed reactor is provided with gasoline feeding entrance, fluidized-bed reactor lift gas entrance, the top exit of fluidized-bed reactor is connected with settling vessel, and the bottom of fluidized-bed reactor lift gas entrance downward vertical standpipe is connected with revivifier by the second regenerator sloped tube, standpipe; Riser tube water cooler and fluidized bed cooler is respectively equipped with at the middle part of the first regenerator sloped tube and the second regenerator sloped tube.
Method provided by the invention is implemented by following proposal:
The compound reactor that riser tube-gas-solid separator-fluidized-bed is formed, reacted catalyzer and oil gas enter gas-solid separator to carry out part (or all) and is separated, catalyzer after separation enters settling vessel, oil gas after separation continues to contact to react with the catalyzer after cooling in fluidized-bed, and after reaction, effluent enters settling vessel; Reaction product isolated, reclaimable catalyst is divided into two portions after stripping, regeneration, and wherein a part enters the bottom of riser tube through cooling, another part cooling laggard enter the bottom of fluidized-bed.
The reaction conditions of riser reactor is: temperature of reaction (riser reactor top exit temperature) is generally 300 ~ 700 DEG C, reaction times is generally 0.5 ~ 5s, agent-oil ratio (weight ratio) is generally 3 ~ 10, and reaction pressure (absolute pressure) is generally 0.15 ~ 0.4MPa.
The reaction conditions of fluidized-bed reactor is: temperature of reaction is generally 300 ~ 550 DEG C, is preferably 350 ~ 500 DEG C; The agent-oil ratio of fluidized-bed reactor is generally 1 ~ 15, is preferably 2 ~ 10; The reaction velocity (volume space velocity) of fluidized-bed reactor is generally 4.0 ~ 60.0h
-1, be preferably 6.0 ~ 30.0h
-1.
The present invention illustrates method provided by the invention with embodiment above, but method provided by the invention is not limited to above-mentioned embodiment.
Embodiment: for the catalytic cracking unit of riser tube-fluidized-bed reactor, heavy oil feed after preheating enters and catalyst exposure from the bottom of riser reactor, the oil gas generated after reaction enters gas-solid separator and is separated, oil gas after separation contacts with the catalyzer after cooling and proceeds to react in fluidized-bed, and after reaction, effluent enters settling vessel; Catalyzer after gas-solid separator is separated enters settling vessel.Reaction product isolated, reclaimable catalyst is divided into two portions after stripping, regeneration, and wherein a part enters the bottom of riser tube after cooling, another part cooling laggard enter fluidized-bed.
Below in conjunction with accompanying drawing, method provided by the present invention is further described.
As shown in Figure 1, the flow process of embodiment is as follows:
This embodiment reactor used is riser tube-gas-solid separator-fluidized-bed compound reactor.
A () heavy oil feed 3 enters riser reactor 5 by heavy oil feed mouth 4, riser reactor lift gas 2 (being generally water vapour) enters riser reactor 5 by riser reactor lift gas entrance 1.The regenerated catalyst coming from revivifier enters riser reactor 5 through standpipe 12, first regenerator sloped tube 13, mixes with heavy oil feed 3 in the bottom of riser reactor 5.Heavy oil feed 3 is up along heavy oil riser reactor 5 with regenerated catalyst afterwards, contacts and react in riser reactor 5 under Conventional catalytic cracking condition.Obtain the first reactant flow after reaction terminates, reactant flow enters gas-solid separator 6 by the top exit of riser reactor 5.In gas-solid separator 6, reactant flow carries out reclaimable catalyst and gas-oil separation, and isolated mixed oil and gas enters fluidized-bed reactor; Isolated reclaimable catalyst enters settling vessel stripping stage 11 through riser tube catalyst transport pipeline 19, enters revivifier 10 after settling vessel stripping stage 11 is with water vapour stripping.
B () reclaimable catalyst carries out coke burning regeneration in revivifier 10, the regenerated catalyst portion after regeneration returns riser reactor 5 through standpipe 12, first regenerator sloped tube 13, riser tube water cooler 15, enters the second regenerator sloped tube 14;
C () comes from the regenerated catalyst of the revivifier 10 of process (a), enter fluidized-bed reactor 7 through standpipe 12, second regenerator sloped tube 14, fluidized bed cooler 16, fluid catalyst transport pipe 20; Promote medium inlet 22 by fluidized-bed reactor and pass into fluidized-bed reactor pre-lift medium 21, fluidized-bed reactor pre-lift medium 21 mixes backward upper flowing with the regenerated catalyst from the second regenerator sloped tube 14, enters fluidized-bed reactor 7 by the bottom inlet of fluidized-bed reactor 7.In fluidized-bed reactor 7, gasoline feeding 17 (comprising the mixed oil and gas from riser reactor) enters fluidized-bed reactor 7 by gasoline feeding mouth 18, it is 300 ~ 550 DEG C in temperature of reaction, the ratio of regenerated catalyst and gasoline feeding 17 charging is 1 ~ 15, and reaction velocity is 4.0 ~ 60.0h
-1contact with the regenerated catalyst risen through pre-lift air lift under condition and react, the second reactant flow obtained after reaction leaves fluidized-bed reactor 7 by the top exit of fluidized-bed reactor 7;
D () enters settling vessel 8 from the second reactant flow of fluidized-bed reactor 7.In settling vessel 8, carry out reclaimable catalyst and gas-oil separation to reactant flow, isolated oil gas 9 enters fractionation apparatus and carries out fractionation, and isolated reclaimable catalyst enters revivifier 10 after settling vessel stripping stage 11 is with water vapor stripping.Reclaimable catalyst carries out coke burning regeneration in revivifier, then carries out step (b), realizes recycling of catalyzer.
Embodiment 1
Riser tube shown in Fig. 1-fluid bed reactor catalysis cracking testing installation carries out the present invention.Riser reactor stock oil adopts 3,000,000 tons/year heavily to urge raw material (sulphur content is 0.61wt%), and its character is in table 1; The mixed oil and gas (content of sulfur in gasoline is 679 μ g/ml) that the gasoline feeding of fluidized-bed reactor produces for riser reactor.The blade diameter length ratio of fluidized-bed reactor is 0.17, and its diameter is attached most importance to 7.1 times of oil riser reactor diameter.Gas-solid separator separating effect is 100%.The main character of operational condition and gasoline lists in table 2.
Adopt the LBO-16 catalyzer that Petrochina Lanzhou Petrochemical Company's catalyst plant is produced.This catalyzer, through 100% water vapor, 800 DEG C, uses after 10 hours aging process on above-mentioned testing installation.
Comparative example 1
Adopt Conventional catalytic cracking method, stock oil is identical with embodiment 1.The method only comprises a riser reactor.The LBO-16 commercial catalysts that catalyzer uses Catalyst Factory of Lanzhou Petrochemical Company to produce.(not comprising fluidized-bed reactor and gas-solid separator)
The operational condition of embodiment 1 and comparative example 1 and the main character of gasoline list in table 2.
Embodiment 2
Carry out the present invention by embodiment 1, difference is the temperature of reaction of riser reactor is 400 DEG C, and agent-oil ratio is 8.7, and the reaction times is 4.03s, and the temperature of reaction of fluidized-bed reactor is 450 DEG C, and agent-oil ratio is 5, and gas-solid separator separating effect is 80%.The main character of operational condition and gasoline lists in table 2.
Embodiment 3
Carry out the present invention by embodiment 1, difference is the temperature of reaction of riser reactor is 600 DEG C, and agent-oil ratio is 4.0, and the reaction times is 1.03s, and the agent-oil ratio of fluidized-bed reactor is 5, and gas-solid separator separating effect is 60%.The main character of operational condition and gasoline lists in table 2.
Embodiment 4
The equipment identical with embodiment 1 is used to carry out the present invention.The present embodiment, heavy oil riser tube stock oil adopts decompressed wax oil blending 30% Xinjiang, Xinjiang vacuum residuum (sulphur content is 0.38wt%), and its character is in table 1; The gasoline feeding of fluidized-bed reactor is attached most importance to the mixed oil and gas (content of sulfur in gasoline is 450 μ g/ml) that oil riser reactor produces.The temperature of reaction of riser reactor is 500 DEG C, and agent-oil ratio is 7.4, and the reaction times is 3.58s, and gas-solid separator separating effect is 100%.The LHO-1 catalyzer that catalyzer uses Catalyst Factory of Lanzhou Petrochemical Company to produce.
Comparative example 2
Adopt Conventional catalytic cracking method, stock oil is identical with embodiment 4 with catalyzer.This equipment only comprises a riser reactor.(not comprising fluidized-bed reactor and gas-solid separator)
The operational condition of embodiment 4 and comparative example 2 and the main character of gasoline list in table 3.
Embodiment 5
Carry out the present invention by embodiment 4, difference is the agent-oil ratio of riser reactor is 5.6, and the reaction times is 2.02s, and the temperature of reaction of fluidized-bed reactor is 450 DEG C, and agent-oil ratio is 2, and air speed is 24.0h
-1.The main character of operational condition and gasoline lists in table 3.
Embodiment 6
Test method therefor is with embodiment 1.The present embodiment, heavy oil riser reactor stock oil is 3,000,000 tons/year and heavily urges raw material (sulphur content is 0.61wt%), and its character is in table 1; The mixing oil that the gasoline feeding of fluidized-bed reactor produces for riser reactor.Gas-solid separator separating effect is 100%.Catalyzer is the composite 25%LB-2 commercial catalysts of 75%LBO-16 commercial catalysts.
Comparative example 3
Adopt Conventional catalytic cracking method, the mixing raw material oil identical with embodiment 6.This equipment only comprises a riser reactor.The mixing oil produced obtains gasoline (content of sulfur in gasoline is 1003 μ g/ml) through fractionation.The LBO-16 commercial catalysts that catalyzer uses Catalyst Factory of Lanzhou Petrochemical Company to produce.
Embodiment 7
Carry out the present invention by embodiment 6, difference is the agent-oil ratio of heavy oil riser reactor is 7.4, and fluidized-bed reactor agent-oil ratio is 10.The main character of operational condition and gasoline lists in table 4.
Embodiment 8
Carry out the present invention by embodiment 6, difference is the reaction times of riser reactor is 3.47s, and the agent-oil ratio in fluidized-bed reactor is 2.Fluidized-bed reactor blade diameter length ratio is 0.33, and its diameter is 8.8 times of riser reactor diameter.The main character of operational condition and gasoline lists in table 4.
Embodiment 9
Carry out the present invention by embodiment 6, difference is riser reactor temperature of reaction is 470 DEG C, and the reaction times is 3.67s.The main character of operational condition and gasoline lists in table 4.
Embodiment 10
Carry out the present invention by embodiment 6, difference is riser reactor temperature of reaction is 470 DEG C, and agent-oil ratio is 6.0, and the reaction times is 2.8s, and the agent-oil ratio of fluidized-bed reactor is 10.The main character of operational condition and gasoline lists in table 4.
Embodiment 11
Test method therefor is with embodiment 1.The present embodiment, the decompressed wax oil (sulphur content is 0.73wt%) that riser reactor stock oil Shandong Shenghua refinery provides; The gasoline feeding of fluidized-bed reactor is attached most importance to the mixed oil and gas that oil riser reactor produces.Gas-solid separator separating effect is 100%.Catalyzer is the composite 25%LB-2 commercial catalysts of 75%LBO-12 commercial catalysts.The main character of operational condition and gasoline lists in table 5.
Comparative example 4
Adopt Conventional catalytic cracking method, stock oil is identical with embodiment 11.This equipment only comprises a riser reactor.Catalyzer is the LRC-99 commercial catalysts that Catalyst Factory of Lanzhou Petrochemical Company is produced, and the main character of operational condition and gasoline lists in table 5.
Embodiment 12
Test method therefor is with embodiment 1, and heavy oil riser reactor stock oil is with embodiment 6; The gasoline feeding of fluidized-bed reactor is attached most importance to the mixing oil that oil riser reactor produces.The LB-2 commercial catalysts that catalyzer uses Catalyst Factory of Lanzhou Petrochemical Company to produce.The operational condition of heavy oil riser reactor and fluidized-bed reactor is with embodiment 3.Gas-solid separator separating effect is 100%.The product slates of two-stage reaction and the main character of gasoline list in table 6.
Comparative example 5
Test method therefor is with embodiment 1, and difference does not have gas-solid separator, is only riser tube+fluidized-bed.The product slates of two-stage reaction and the main character of gasoline list in table 6.
Table 1 stock oil character
Table 2 mixes operational condition and the gasoline main character of heavy oil
Note: table 2 [1]: relative to comparative example 1, reduces percentage ratio.
Table 2 [2]: relative to comparative example 1, absolute increased value.
Table 2 [3]: relative to comparative example 1, absolute decreasing value.
Table 3 mixes operational condition and the gasoline main character of heavy oil
Note: table 3 [1]: relative to comparative example 2, reduces percentage ratio.
Table 3 [2]: relative to comparative example 2, absolute increased value.
Table 3 [3]: relative to comparative example 2, absolute decreasing value.
Table 4 mixes operational condition and the gasoline main character of heavy oil
Note: table 4 [1]: relative to comparative example 4, reduces percentage ratio.
Table 4 [2]: relative to comparative example 4, absolute increased value.
Table 4 [3]: relative to comparative example 4, absolute decreasing value.
Table 5 decompressed wax oil and gasoline main character
Note: table 5 [1]: relative to comparative example 5, reduces percentage ratio.
Table 5 [2]: relative to comparative example 5, absolute increased value.
Table 5 [3]: relative to comparative example 5, absolute decreasing value.
The product slates of table 6 two-stage reaction and the main character of gasoline
| Project | Comparative example 5 | Embodiment 12 |
| Dry gas | 1.43 | 1.03 |
| Liquefied gas | 15.67 | 16.37 |
| C 5 +Gasoline | 41.25 | 42.85 |
| Diesel oil | 21.12 | 21.22 |
| Heavy oil | 9.43 | 8.23 |
| Coke | 10.93 | 10.13 |
| Light receipts/m% | 62.37 | 64.07 |
| Total liquid yield/m% | 78.04 | 80.44 |
| Sulphur content/μ g/ml | 343 | 287 |
| Octane value (RON) | 91.4 | 92.6 |
| Olefin(e) centent/v% | 12.55 | 8.55 |
Claims (11)
1. one kind is reduced the device of the catalyzed conversion of content of sulfur in gasoline, include reactor, settling vessel, revivifier, riser tube catalyst transport pipeline and fluid catalyst transport pipe, it is characterized in that reactor is compound reactor, by coaxial, riser reactor (5) from bottom to top, gas-solid separator (6), fluidized-bed reactor (7) is formed, the top exit of fluidized-bed reactor (7) is connected with settling vessel, the bottom of fluidized-bed reactor (7) downward vertical standpipe is provided with gasoline feeding entrance (18) and fluid catalyst transport pipe (20), the erect riser of riser reactor (5) below is provided with riser reactor lift gas entrance (1) and heavy oil feed mouth (4), gas-solid separator (6) side exit is provided with riser tube catalyst transport pipeline (19).
2. device according to claim 1, it is characterized in that the top exit of riser reactor communicates with gas-solid separator (6), bottom is connected with revivifier (10) by the first regenerator sloped tube (13), standpipe (12), the top exit of fluidized-bed reactor is connected with settling vessel (8), and the erect riser that fluidized-bed reactor (7) is provided with below gasoline feeding entrance (18), fluidized-bed reactor is connected with the outlet of gas-solid separator (6); The bottom of fluidized-bed reactor downward vertical standpipe is connected with revivifier (10) by fluid catalyst transport pipe (20), the second regenerator sloped tube (14), standpipe (12); Riser tube water cooler (15) and fluidized bed cooler (16) is respectively equipped with at the middle part of the first regenerator sloped tube (13) and the second regenerator sloped tube (14).
3. device according to claim 1, it is characterized in that fluidized-bed reactor diameter is 3 ~ 10 times of riser reactor diameter, the blade diameter length ratio of fluidized-bed reactor is 0.1 ~ 0.4.
4. device according to claim 1, is characterized in that gas-solid separator is cyclonic separator, catalytic cracking quick disconnector or strainer.
5. use a catalysis conversion method for the reduction content of sulfur in gasoline of device described in claim 1, it is characterized in that comprising the steps:
(a): heavy oil feed (3) enters riser reactor (5) by heavy oil feed mouth (4), riser reactor lift gas (2) enters riser reactor (5) by riser reactor lift gas entrance (1); The regenerated catalyst coming from revivifier enters riser reactor (5) through standpipe (12), the first regenerator sloped tube (13), mixes with heavy oil feed (3) in the bottom of riser reactor (5); Heavy oil feed (3) is up along riser reactor (5) with regenerated catalyst afterwards, reacts in riser reactor (5); Obtain the first reactant flow after reaction terminates, reactant flow enters gas-solid separator (6) by the top exit of riser reactor (5); In gas-solid separator (6), reactant flow carries out reclaimable catalyst and gas-oil separation, and isolated mixed oil and gas enters fluidized-bed reactor; Isolated reclaimable catalyst enters settling vessel stripping stage (11) through riser tube catalyst transport pipeline (19), enters revivifier (10) after settling vessel stripping stage (11) is with water vapour stripping;
(b): reclaimable catalyst carries out coke burning regeneration in revivifier (10), regenerated catalyst portion after regeneration returns riser reactor (5) through standpipe (12), the first regenerator sloped tube (13), riser tube water cooler (15), enters the second regenerator sloped tube (14);
C (): the regenerated catalyst coming from the revivifier (10) of process (b), enters fluidized-bed reactor (7) through standpipe (12), the second regenerator sloped tube (14), fluidized bed cooler (16), fluid catalyst transport pipe (20); Promote medium inlet (22) by fluidized-bed reactor and pass into fluidized-bed reactor pre-lift medium (21), fluidized-bed reactor pre-lift medium (21) mixes backward upper flowing with the regenerated catalyst from the second regenerator sloped tube (14), enters fluidized-bed reactor (7) by the bottom inlet of fluidized-bed reactor (7); In fluidized-bed reactor (7), gasoline feeding (17) enters fluidized-bed reactor (7) by gasoline feeding mouth (18), it is 300 ~ 550 DEG C in temperature of reaction, the charge ratio of regenerated catalyst and gasoline feeding (17) is 1 ~ 15, and reaction velocity is 4.0 ~ 60.0h
-1contact with the regenerated catalyst risen through pre-lift air lift under condition and react, the second reactant flow obtained after reaction leaves fluidized-bed reactor (7) by the top exit of fluidized-bed reactor (7);
(d): the second reactant flow from fluidized-bed reactor (7) enters settling vessel (8); In settling vessel (8), reclaimable catalyst and gas-oil separation are carried out to reactant flow, isolated oil gas (9) enters fractionation apparatus and carries out fractionation, and isolated reclaimable catalyst enters revivifier (10) after settling vessel stripping stage (11) is with water vapor stripping; Reclaimable catalyst carries out coke burning regeneration in revivifier, then carries out step (b), realizes recycling of catalyzer.
6. catalysis conversion method according to claim 5, it is characterized in that in process (a) that the reaction conditions of riser reactor is riser tube top exit temperature is 300 ~ 700 DEG C, reaction times is 0.5 ~ 5s, the ratio of regenerated catalyst and heavy oil feed is 3 ~ 10, and reaction pressure is 0.15 ~ 0.4MPa.
7. catalysis conversion method according to claim 5, it is characterized in that from the reclaimable catalyst of riser reactor and fluidized-bed reactor under catalytic cracking catalyst regeneration condition in revivifier coke burning regeneration, regeneration temperature controls at 650 ~ 750 DEG C.
8. catalyst cracking method according to claim 5, is characterized in that mink cell focus is heavy oil, long residuum, vacuum residuum, straight-run gas oil, wax tailings, shale oil, synthetic oil, crude oil, coal tar, recycle stock, slurry oil and/or deasphalted oil.
9. the catalyst cracking method of reduction content of sulfur in gasoline according to claim 5, is characterized in that the gasoline of fluidized-bed reactor in process (c) is the gasoline that sour gasoline and/or riser reactor itself are produced.
10. the catalyst cracking method of reduction content of sulfur in gasoline according to claim 9, is characterized in that sour gasoline refers to light FCC gasoline, catalytic cracking heavy petrol, thermo-cracking petroleum naphtha, thermally splitting petroleum naphtha, thermo-cracking heavy petrol, thermally splitting heavy petrol, light coker naphtha, coking heavy petrol and/or cracking ethylene preparation gasoline.
The catalyst cracking method of 11. reduction content of sulfur in gasoline according to claim 3, is characterized in that the pre-lift medium of fluidized-bed reactor is one or more in catalytic cracked dry gas, hydrogen, water vapor and carbon monoxide.
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| CN103788996B (en) * | 2012-10-29 | 2015-05-20 | 中国石油化工股份有限公司 | Adsorption desulfurization reaction device and adsorption desulfurization method |
| CN103789003A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Method for determining reactivity of desulphurization adsorbent |
| CN104593042B (en) * | 2013-10-31 | 2016-07-06 | 中国石油化工股份有限公司 | An adsorption desulfurization reaction device and an adsorption desulfurization method |
| CN105441114B (en) * | 2014-09-12 | 2017-05-24 | 中石化洛阳工程有限公司 | Catalytic cracking apparatus |
| CN105623733B (en) * | 2014-10-27 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of desulfurizing method by adsorption of petroleum hydrocarbon |
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| CN1664074A (en) * | 2005-03-23 | 2005-09-07 | 李莉 | Method and device for catalytic conversion of heavy oil |
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| CN1664074A (en) * | 2005-03-23 | 2005-09-07 | 李莉 | Method and device for catalytic conversion of heavy oil |
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