CN1664074A - Method for catalytic conversion of heavy oil and device thereof - Google Patents
Method for catalytic conversion of heavy oil and device thereof Download PDFInfo
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- CN1664074A CN1664074A CN 200510055695 CN200510055695A CN1664074A CN 1664074 A CN1664074 A CN 1664074A CN 200510055695 CN200510055695 CN 200510055695 CN 200510055695 A CN200510055695 A CN 200510055695A CN 1664074 A CN1664074 A CN 1664074A
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Abstract
The invention provides a method of heavy raw material catalytic conversion and the device, comprising: the heavy hydrocarbon raw material passing through the first and second reaction area of the raiser reactor and contacting with catalyst for first reaction and second reaction, the reactants entering into the settler for the separation of catalyst and oil gas, steam stripping the separated catalyst through stripping section and introducing it to the reactivator for carbon burning reactivation, the reactivated catalyst returning to the raiser reactor after cooled or directly to the raiser reactor for reuse. After the heavy oil passing through the device said above, the volume content of olefin decreases by 10~40%, octane value increases 0.5~1 units, sulfur content in petrol decreases 10~30% by weight. After the poor petrol passing through the device said above, the volume content of olefin decreases by 10~60%, octane value increases 0.5~40 units, sulfur content in petrol decreases 10~50% by weight.
Description
Technical field
The invention belongs to the catalytic cracking field, particularly utilize catalytic cracking to carry out method for catalytic conversion of heavy oil and device thereof.The charging that The present invention be more particularly directed to contain high boiling fraction is as surpassing the catalyzed conversion upgrading of 560 ℃ and inferior patrol.
Background technology
Along with the poor qualityization of crude quality and increasingly sharpening of heaviness trend, the improving constantly of the residual oil mixed refining ratio of catalytic cracking, explained hereafter qualities of gasoline such as catalytic cracking, coking, thermally splitting become poorer.Alkene in the gasoline is the high-octane rating active principle on the one hand, produces more contaminants environment on the other hand in combustion processes.Though it is very low to utilize traditional hydrofining the alkene in the gasoline can be dropped to, and has lost octane value significantly.In order to address the above problem, improve the quality of gasoline products, refine oil the boundary abroad also to have done number of research projects.
The MGD technology that the having of Beijing Research Institute of Petro-Chemical Engineering exploitation reduced gasoline olefin volume content function (" refining of petroleum and chemical industry " 2002 2 phase the 19th～22 page) is divided into two sections hypomeres to conventional FCC master's riser reactor as the gasoline upgrading reaction zone, epimere is as FCC master's riser reaction zone, utilize high agent-oil ratio and high activated catalyst reformulated gasoline, this technology will be taken into account the reaction conditions of main riser tube heavy oil fluid catalytic cracking, the effect of gasoline upgrading is limited, it is also not ideal to fall the alkene amplitude, can make the FCC gasoline olefin reduce by 10～12 volume percentage points.
China Petroleum Univ. (East-China) adopts two sections series connection riser tube Technologies (CN1302843A), the reaction oil gas series connection, catalyzer relay operation, realize improving yield of light oil, improve the purpose alkene volume content of catalytic gasoline quality, but this technology adopts the series connection of two-stage riser reaction oil gas, the technology of catalyzer relay, must make technical process very complicated, the handiness of device operation is restricted, simultaneously because two-stage riser reaction oil gas serial operation, the gasoline upgrading reaction influences each other with other component reaction, the purpose product selectivity is affected, the gasoline olefin volume content range of decrease is limited, can reduce about 15 volume percentage points.
USP5,154,818 disclose a kind of method of catalyzed cracking processing gasoline, and its main contents are as follows: riser reactor is divided into first reaction zone and second reaction zone from bottom to top; At first reaction zone, light petroleum hydrocarbons such as oil liquefied gas, light gasoline fraction, heavy naphtha and the reclaimable catalyst reaction that contains shape-selective molecular sieve or mesoporous molecular sieve, reaction product and catalyzer are along being advanced into second reaction zone on the riser tube; At second reaction zone, atmospheric gas oil, vacuum gas oil, diasphaltene wet goods heavy petroleum hydrocarbon and contain the Y type or the regenerated catalyst of USY type molecular sieve reaction; The separation of reaction product and the regeneration of catalyzer are all carried out according to a conventional method.
Heavy oil fluid catalytic cracking is heavy because of raw material, and the carbon residue height rises coke yield, and heat causes the heat surplus more than institute of system heat requirement.Therefore, heavy oil catalytically cracking equipment must be installed the heat-obtaining facility, takes out superfluous heat from system, can keep two device heat balances.The catalyst cooler kind of extraction system superfluous heat is a lot of in the existing heavy oil catalytic cracking process.
US5451313 discloses a kind of FCC method, wherein circulates with regenerator by spent agent and reduces the severity of method, improves the atomizing of charging, and promotion contacts with catalyzer.But the regenerator cooling that catalyst cooler is used for regenerator bed cooling and riser cracking charging is not simultaneously proposed.
" x design " technology (" world oil science " of Uop Inc.'s exploitation, 1996,3 (9)), characteristics are that part spent agent (treating regenerated catalyst) directly returns riser reactor without charcoal regeneration with regenerator after the mixing tank blending, because of the regenerator cooling, agent-oil ratio is improved.The shortcoming of this technology is that regenerator and spent agent directly mix, and the catalyst activity that enters riser reactor is reduced, and is unfavorable for catalytic cracking reaction.
Existing heat-obtaining technology is because of only causing disadvantageous effect at the close phase section of revivifier heat-obtaining to the optimization of reactive system, and the technology of existing optimization reactive system operation all has its weak point.
On the basis of above-mentioned prior art, the purpose of this invention is to provide a kind of FCC method that is mainly used in cracking heavy feedstocks, reduce the economy of content of olefin in gasoline and sulphur, nitrogen content simultaneously and effective FCC method, with the residual oil mixed refining that solves current catalytic cracking than improve and the gasoline upgrade and replacement process in the problem that run into.
The present invention utilizes catalytic cracking process catalyzer cooling technology commonly used and multi-reaction-area technology, mixing temperature control techniques, annotate technology such as terminator, guaranteeing under the prerequisite that sufficiently high regenerator temperature and good revival are sold, reduce the temperature of the regenerator that enters reactor, improve the fuel oil preheating temperature, improve the stock oil atomizing effect, the rising agent oil ratio is improved product and is distributed, and improves liquid yield.
Summary of the invention
Technical problem to be solved by this invention provides a kind of heavy feed stock catalysis conversion method, utilizes catalytic cracking process catalyzer cooling technology and multi-reaction-area technology commonly used, when improving residual oil mixed refining ratio, reduces the alkene and the foreign matter content of gasoline.Concrete technical scheme is specified in down:
The invention provides a kind of heavy feed stock catalysis conversion method and device thereof:
Comprise a fluid catalytic cracking process: hydrocarbon raw material riser reactor and catalyzer contact reacts, reactant flow enter settling vessel carry out the separating of catalyzer and oil gas, isolated reclaimable catalyst through the catalyzer behind the stripping stage stripping, after entering revivifier coke burning regeneration, regeneration through cooling or directly return riser reactor and recycle.Its specific embodiment is as follows:
(1) the heavy oil riser reactor is divided into pre-lifting zone and two or more reaction zone.At first reaction zone, heavy crude hydro carbons raw material is to contact under 0.11～0.4MPa condition with mix the back from the cyclic regeneration catalyzer (temperature is less than or equal to the temperature of revivifier) of pre-lifting zone temperature of reaction 400-650 ℃ of (preferred 520-600 ℃), absolute pressure, 0.05～5 second duration of contact (preferred 0.1-3 second), catalyzer is generally 3～10 with the raw material weight ratio, preferred 5～8, mainly carry out primary first-order equations such as cracking, reaction product and the mixture of catalysts of leaving first reaction zone enter second reaction zone behind riser tube and cold shock agent hybrid cooling.
Heavy crude hydro carbons raw material can be the mixture of several petroleum fractionss, also can be a certain cut of petroleum hydrocarbon, and the different raw material of cracking performance can enter first reaction zone simultaneously, also can enter the different positions of first reaction zone respectively.
(2) at second reaction zone, mixing the new blend that obtains from the reaction product of first reaction zone with mixture of catalysts and cold shock agent is to contact under 0.11～0.4MPa condition temperature of reaction 350-620 ℃ of (preferred 450-530 ℃), absolute pressure, 0.5～30 second duration of contact (preferred 1-5 second), mainly carry out secondary reactions such as hydrogen transference, isomerization, aromizing.
(3) leave the reaction product of second reaction zone and mixture of catalysts along riser tube, enter settling vessel carry out the separating of catalyzer and oil gas, isolated reclaimable catalyst behind the stripping stage stripping, enter the revivifier coke burning regeneration, regeneration temperature is controlled at catalyzer after 650～800 ℃ (preferred 680-760 ℃), the regeneration through cooling or directly return riser reactor without cooling and recycle.
Revivifier is provided with one or more interior or outside heat removing equipment, i.e. catalyst coolers.Catalyst cooler-A is mainly used in the temperature of reaction of regulating first reaction zone, makes it remain on optimum value.Catalyst cooler-B is mainly used in the temperature of reaction of regulating second reaction zone, makes it remain on optimum value.Catalyst cooler-C is mainly used in the adjusting regenerator temperature, makes it remain on optimum value.
According to processing requirement, catalyst cooler-the C that regulates regenerator temperature can not establish yet, and regenerator temperature comprises the flow of air, steam etc. by the fluidizing medium of regulating catalyst cooler-B or catalyst cooler-A and returns the catalytic amount of revivifier or control by the thermal equilibrium of reaction-regeneration system.Catalyst cooler-the A that regulates the temperature of reaction of first reaction zone can not establish yet, and hot regenerated catalyst directly enters first reaction zone.
(4) part is directly entered the pre-lifting zone of heavy oil riser reactor from the regenerated catalyst of revivifier without catalyst cooler, perhaps be cooled to 200-720 ℃ (preferred 300-500 ℃) and another part and mix without the refrigerative hot regenerated catalyst and obtain entering after the mixed regeneration catalyst mix that temperature is lower than regenerator temperature, perhaps do not mix directly entering the pre-lifting zone of heavy oil riser reactor with hot regenerated catalyst through catalyst cooler-A.The temperature of above-mentioned mixed regeneration catalyzer can obtain independent control by the ratio of regulating above-mentioned cold and hot regenerated catalyst.When cold regenerated catalyst directly entered first reaction zone, temperature obtained independent control by the catalytic amount of regulating fluidizing medium and comprise air, steam equivalent and return revivifier.Therefore, agent-oil ratio of first reaction zone (ratio of regenerated catalyst and raw material) and temperature of reaction all can obtain independent control.
(5) part is cooled to 200-720 ℃ (preferred 300-600 ℃) and another part from the regenerated catalyst of revivifier through catalyst cooler-B and mixes without the refrigerative regenerated catalyst and obtain entering after the mixed regeneration catalyst mix of temperature that temperature is lower than revivifier, perhaps do not mix directly entering subsidiary riser or gasoline rising pipe with hot regenerated catalyst.By subsidiary riser or gasoline rising pipe and the reaction product of leaving first reaction zone with enter second reaction zone after mixture of catalysts is mixed.The temperature of above-mentioned mixed regeneration catalyzer can obtain independent control by the ratio of regulating above-mentioned cold and hot regenerated catalyst.When cold regenerated catalyst directly entered subsidiary riser or gasoline rising pipe, temperature obtained independent control by the catalytic amount of regulating fluidizing medium and comprise air, steam equivalent and return revivifier.Therefore, agent-oil ratio of second reaction zone (ratio of regenerated catalyst and raw material) and temperature of reaction all can obtain independent control.
Catalyst cooler of the present invention has one or more catalyst outlets, one is used to carry cold regenerated catalyst to return revivifier, the temperature of revivifier can comprise the flow of air, steam etc. and the flow that catalyzer return tube delivery medium comprises air, steam etc. by regulating fluidizing medium, makes it remain on optimum value.Another or two are respectively applied for and carry cold regenerated catalyst to be circulated to one or two riser tube (reactor), the temperature of riser reaction zone also can comprise the flow of air, steam etc. and the flow that catalyzer return tube delivery medium comprises air, steam etc. by regulating fluidizing medium, makes it remain on optimum value.
Described cold shock agent can be gaseous state or liquid water, various oil product (comprising inferior patrol, recycle stock, clarification wet goods), also can be that cold catalyzer comprises cold regenerated catalyst, treats coldly living catalyzer, cold half regenerated catalyst etc. (preferred cold regenerated catalyst or from the reclaimable catalyst of gasoline upgrading system), or the mixture of the arbitrary proportion of above-mentioned cold shock agent.
The decanting point of described gas or liquid cold shock agent can perhaps in the ingress of subsidiary riser, with the temperature of convenient each reaction zone of control, or form another reaction zone in upstream, the downstream of cold catalyzer decanting point.
The present invention can implement separately, promptly independently finishes processes such as reaction, regeneration, separation; Also can with the catalytic convention design Joint Implementation of another set of riser tube or fluidized-bed, when finishing the conversion reaction of heavy oil hydrocarbon material catalytic, realize catalyzed conversion upgrading reaction to gasoline fraction.
Below independent enforcement and Joint Implementation are specifically described.
1) the present invention implements separately
When the present invention implements separately, meet the catalyzer of requirement of the present invention with the heavy oil feedstock after the preheating enters riser reactor on riser tube or fluidized bed catalytic cracker, be in or be not under the water vapor existence and react through the revivifier regenerated; Reaction oil gas, water vapor and reacted reclaimable catalyst carry out gas solid separation; Reaction product isolated obtains gasoline products and a spot of dry gas, liquefied gas, diesel oil.Reclaimable catalyst is imported revivifier behind the water vapor stripping, carry out coke burning regeneration in the presence of oxygen-containing gas, and the catalyzer after the regeneration divides two-way to recycle after cooling off or without the direct Returning reactor of cooling.
The present invention implements separately two riser tubes are set, a heavy oil riser tube, and a subsidiary riser, subsidiary riser is connected with the middle part of heavy oil riser tube.Be divided into a plurality of reaction zones by processing requirement, the heavy oil riser tube is at least two reaction zones, subsidiary riser is a transfer lime, be connected with heavy oil riser reactor middle part (joint portion of first reaction zone, second reaction zone), water, water vapour or dry gas are done to promote gas, only are used to carry cold catalyzer to do the cold shock agent.
A part is directly entered the pre-lifting zone of heavy oil riser reactor from the regenerated catalyst of revivifier without catalyst cooler, perhaps be cooled to 200-720 ℃ (preferred 300-500 ℃) and another part and mix without the refrigerative hot regenerated catalyst and obtain entering after the mixed regeneration catalyst mix that temperature is lower than regenerator temperature, perhaps do not mix directly entering the pre-lifting zone of heavy oil riser reactor with hot regenerated catalyst through catalyst cooler-A.The temperature of above-mentioned mixed regeneration catalyzer can obtain independent control by the ratio of regulating above-mentioned cold and hot regenerated catalyst.When cold regenerated catalyst directly entered first reaction zone, temperature obtained independent control by the catalytic amount of regulating fluidizing medium and comprise air, steam equivalent and return revivifier.Therefore, agent-oil ratio of first reaction zone (ratio of regenerated catalyst and raw material) and temperature of reaction all can obtain independent control.
A part is cooled to 200-720 ℃ (preferred 300-600 ℃) and another part from the regenerated catalyst of revivifier through catalyst cooler-B mixes without the refrigerative regenerated catalyst and obtain entering after the mixed regeneration catalyst mix of temperature that temperature is lower than revivifier, perhaps do not mix directly entering subsidiary riser with hot regenerated catalyst.By subsidiary riser and the reaction product of leaving first reaction zone with enter second reaction zone after mixture of catalysts is mixed.The temperature of above-mentioned mixed regeneration catalyzer can obtain independent control by the ratio of regulating above-mentioned cold and hot regenerated catalyst.When cold regenerated catalyst directly entered subsidiary riser or gasoline rising pipe, temperature obtained independent control by the catalytic amount of regulating fluidizing medium and comprise air, steam equivalent and return revivifier.Therefore, agent-oil ratio of second reaction zone (ratio of regenerated catalyst and raw material) and temperature of reaction all can obtain independent control.
The catalyzer and the raw material after the preheating that meet requirement of the present invention enter heavy oil riser reactor first reaction zone, are in or be not under the water vapor existence to carry out cracking reaction; Leaving the reaction product of first reaction zone and mixture of catalysts enters second reaction zone behind riser tube and the cold shock agent hybrid cooling from subsidiary riser and mainly carries out secondary reactions such as hydrogen transference, isomerization, aromizing.The reaction product of leaving second reaction zone and mixture of catalysts enter settling vessel along riser tube and carry out separating of catalyzer and oil gas, obtain gasoline, liquefied gas, diesel oil and a spot of dry gas, reclaimable catalyst is imported revivifier behind the water vapor stripping, in the presence of oxygen-containing gas, carry out coke burning regeneration, catalyzer separated into two parts after the regeneration directly returns riser reactor and recycles through cooling back respectively or without cooling off.
Revivifier is provided with one or more interior or outside heat removing equipment, i.e. catalyst coolers.Catalyst cooler-A is mainly used in the temperature of reaction of regulating first reaction zone, makes it remain on optimum value.Catalyst cooler-B is mainly used in the temperature of reaction of regulating second reaction zone, makes it remain on optimum value.Catalyst cooler-C is mainly used in the adjusting regenerator temperature, makes it remain on optimum value.
According to processing requirement, catalyst cooler-the C that regulates regenerator temperature can not establish yet, and regenerator temperature is by regulating catalyst cooler-A or catalyst cooler-B fluidizing medium and comprise the flow of air, steam etc. and returning the catalytic amount of revivifier or control by the thermal equilibrium of reaction-regeneration system.Catalyst cooler-the A that regulates the temperature of reaction of first reaction zone can not establish yet, and hot regenerated catalyst directly enters first reaction zone without cooling.
Above-mentioned catalyst cooler can be connected as a single entity with revivifier, also can link to each other with revivifier by pipeline.
2) Joint Implementation of the present invention
During Joint Implementation of the present invention, two riser tubes are set, a heavy oil riser tube, a gasoline rising pipe reactor (having or do not have fluidized-bed reactor) is divided into a plurality of reaction zones (being generally three reaction zones) by processing requirement.At least 2 reaction zones of heavy oil riser tube, catalyzer that cold shock is used or mixture of catalysts are entered by heavy oil riser reactor middle part (joint portion of first reaction zone, second reaction zone).
A part is directly entered the pre-lifting zone of heavy oil riser reactor from the regenerated catalyst of revivifier without catalyst cooler, perhaps be cooled to 200-720 ℃ (preferred 300-500 ℃) and another part and mix without the refrigerative hot regenerated catalyst and obtain entering after the mixed regeneration catalyst mix that temperature is lower than regenerator temperature, perhaps do not mix directly entering the pre-lifting zone of heavy oil riser reactor with hot regenerated catalyst through catalyst cooler-A.The temperature of above-mentioned mixed regeneration catalyzer can obtain independent control by the ratio of regulating above-mentioned cold and hot regenerated catalyst.When cold regenerated catalyst directly entered first reaction zone, temperature obtained independent control by the catalytic amount of regulating fluidizing medium and comprise air, steam equivalent and return revivifier.Therefore, agent-oil ratio of first reaction zone (ratio of regenerated catalyst and raw material) and temperature of reaction all can obtain independent control.
A part is cooled to 200-720 ℃ (preferred 300-600 ℃) and another part from the regenerated catalyst of revivifier through catalyst cooler-B mixes without the refrigerative regenerated catalyst and obtain entering after the mixed regeneration catalyst mix of temperature that temperature is lower than revivifier, perhaps do not mix directly entering gasoline rising pipe (having or do not have fluidized-bed reactor, have or do not have pre-lifting zone) with hot regenerated catalyst.Pass through gasoline rising pipe; Perhaps fluidized-bed reactor or petrol sediment bulb through stripping behind the stripping or not and the reaction product of leaving first reaction zone with enter second reaction zone after mixture of catalysts is mixed.The temperature of above-mentioned mixed regeneration catalyzer can obtain independent control by the ratio of regulating above-mentioned cold and hot regenerated catalyst.When cold regenerated catalyst directly entered gasoline rising pipe, temperature obtained independent control by the catalytic amount of regulating fluidizing medium and comprise air, steam equivalent and return revivifier.Therefore, agent-oil ratio of second reaction zone (ratio of regenerated catalyst and raw material) and temperature of reaction all can obtain independent control.
Meet the cold catalyzer of a part of requirement of the present invention and the heavy oil feedstock after the preheating and enter riser reactor first reaction zone, be in or be not under the water vapor existence and carry out cracking reaction; Leaving the reaction product of first reaction zone and mixture of catalysts enters second reaction zone behind riser tube and reclaimable catalyst (cold shock agent) hybrid cooling from inferior patrol riser tube or fluidized-bed reactor and mainly carries out secondary reactions such as hydrogen transference, isomerization, aromizing, the reaction product of leaving second reaction zone and mixture of catalysts enter settling vessel along riser tube and carry out separating of catalyzer and oil gas, obtain gasoline products, liquefied gas, diesel oil and a spot of dry gas.
Another part cold regenerated catalyst enters and is used to transform in the riser tube or fluidized-bed reactor of gasoline fraction; Contact with the gasoline fraction after not preheating or the preheating, being in or be not in water vapor exists down, temperature of reaction 300-650 ℃ of (preferred 400-560 ℃), absolute pressure is to contact under 0.11～0.4MPa condition, 0.5～30 second duration of contact (preferred 1-15 second), catalyzer is generally 1～50 with the raw material weight ratio, and is preferred 2～20, mainly carries out gasoline upgradings reactions such as isomerization, aromizing, reach and reduce alkene and sulphur content, the purpose of boosting of octane rating.
The reaction product of gasoline fraction and mixture of catalysts and finish the heavy oil hydrocarbon material catalytic and transform after the reaction product and the subsequent reactions and the separation system of mixture of catalysts can be shared, also can be provided with separately:
(1) shared subsequent reactions and separation system
The reaction product of gasoline fraction enters second reaction zone with mixture of catalysts without separating directly with behind the reaction product of leaving first reaction zone and the mixture of catalysts hybrid cooling.The reaction product of leaving second reaction zone and mixture of catalysts enter settling vessel and carry out separating of catalyzer and oil gas, obtain gasoline products, liquefied gas, diesel oil and a spot of dry gas.
Perhaps (2) shared subsequent separation system
The reaction product that the reaction product of gasoline fraction and mixture of catalysts and heavy oil hydrocarbon material catalytic transform and mixture of catalysts enter same settling vessel (reaction product of gasoline fraction and catalyzer separate and the stripping facility can set up, also can be shared) carry out separating of catalyzer and oil gas, shared gas-oil separation and recovery system obtain gasoline products, liquefied gas, diesel oil and a spot of dry gas.Separating and stripping facility when being provided with separately of the reaction product of gasoline fraction and catalyzer, reclaimable catalyst after finishing gasoline fraction and transforming without stripping or separately behind the stripping all or part of middle part that enters the heavy oil riser tube do the cold shock agent, perhaps without stripping or stripping rear section or all enter settling vessel separately through overflow.
Perhaps (3) set up subsequent separation system separately
The reaction product that the reaction product of gasoline fraction and mixture of catalysts and heavy oil hydrocarbon material catalytic transform and mixture of catalysts can enter two settling vessels respectively and carry out separating of catalyzer and oil gas, oil gas separates separately and reclaims, and obtains gasoline products, liquefied gas, diesel oil and a spot of dry gas respectively.The reaction product of gasoline fraction and the settling vessel of catalyzer has or do not have fluidized-bed reactor.
The reclaimable catalyst of finishing the reclaimable catalyst after gasoline fraction transforms and finishing after the heavy oil hydrocarbon material catalytic transforms can be distinguished stripping, also can mix the common stripping in back.Reclaimable catalyst behind the stripping shared cover regeneration system rapidly in the presence of oxygen-containing gas carries out coke burning regeneration.
When adopting two cover subsequent separation system, the reclaimable catalyst (1) that comes from inferior patrol riser tube or fluidized-bed reactor is through water vapor stripping rear section or all import shared regeneration system rapidly and carry out coke burning regeneration, perhaps (2) stripping or stripping rear section or the middle part of all importing the heavy oil riser tube do not do the cold shock agent, perhaps (3) not stripping or stripping after upflow tube is partly or entirely imported the heavy oil settling vessel.
Catalyzer separated into two parts after the regeneration directly returns each reactor cycles use after cooling off respectively or without cooling.
Revivifier is provided with one or more interior or outside heat removing equipment, i.e. catalyst coolers.Catalyst cooler-A is mainly used in the temperature of reaction of regulating first reaction zone, makes it remain on optimum value.Catalyst cooler-B is mainly used in the temperature of reaction of regulating second reaction zone, makes it remain on optimum value.Catalyst cooler-C is mainly used in the adjusting regenerator temperature, makes it remain on optimum value.
According to processing requirement, catalyst cooler-the C that regulates regenerator temperature can not establish yet, and regenerator temperature is by regulating catalyst cooler-A or catalyst cooler-B fluidizing medium and comprise air, steam equivalent and returning the catalytic amount of revivifier or control by the thermal equilibrium of reaction-regeneration system.Catalyst cooler-the A that regulates the temperature of reaction of first reaction zone can not establish yet, and hot regenerated catalyst directly enters first reaction zone
Above-mentioned catalyst cooler can be connected as a single entity with revivifier, also can link to each other with revivifier by pipeline.
The inferior patrol hydrocarbon raw material that the present invention is suitable for is a gasoline fraction, comprises straight-run spirit, condensate oil, catalytically cracked gasoline, catalytic cracking petroleum naphtha, pyrolysis gasoline, coker gasoline, cracking ethylene preparation gasoline and their two or more blend gasoline.
This gasoline fraction can be full cut, for example, the cut about initial boiling point to 220 ℃: also can be part narrow fraction wherein, for example, 70～145 ℃ of cuts.This gasoline fraction can be the mixture of time processing gasoline fraction such as straight-run spirit, condensation wet goods, secondary processing of gasoline cut such as coker gasoline, FCC gasoline, visbreaking gasoline, pressure gasoline etc. or more than one gasoline fraction.The olefin(e) centent of this gasoline fraction can be 0～80 heavy %, and contains impurity such as a spot of sulphur, nitrogen, and for example, sulphur content is greater than 200ppm, and nitrogen content is greater than 30ppm.
Heavy oil riser reactor raw material of the present invention is that various heavy oil comprise: long residuum, vacuum residuum, straight-run gas oil, wax tailings, shale oil, synthetic oil, crude oil, coal tar, recycle stock, slurry oil, deasphalted oil, heavy gas oil with and two kinds and two or more mixtures, the charging that particularly contains high boiling fraction in the heavy oil feedstock is as above 560 ℃, and greater than 500 ℃ components (as vacuum residuum) content is 10-100%, is preferably 30-100%.According to the characteristic of different material oil, charging simultaneously also can be in many places different positions charging.
The present invention adopts industrial sophisticated any conventional catalytic cracking catalyst, comprising: synthetic zeolite catalysts cracking catalyzer and amorphous silicon aluminium catalytic cracking catalyst etc.
The catalyzer that the regenerated catalyst that enters gasoline rising pipe, subsidiary riser or heavy oil riser tube of the present invention is the various carbon contents behind the coke burning regeneration comprises regenerated catalyst, half regenerated catalyst or their mixture.
Described regenerated catalyst is meant regenerated catalyst after the holomorphosis or two sections regenerated catalysts behind the two-stage regeneration; Half regenerated catalyst is meant the regenerated catalyst of incomplete regen-eration or one section regenerated catalyst of two-stage regeneration.
The pre-lifting medium that enters gasoline rising pipe, subsidiary riser or heavy oil riser tube of the present invention can be one or more in water (comprising water vapour), various oil refinery dry gas, the various oil product (comprising inferior patrol etc.); The reaction medium that enters gasoline rising pipe also can be other various oil products (comprising recycle stock, clarification wet goods).
The separation of reaction product and the regeneration of catalyzer are all carried out according to a conventional method, and the various reaction regeneration patterns that can adopt riser catalytic cracking technology and device to use comprise various riser tube patterns, regeneration pattern and various combination form thereof.Reclaimable catalyst carries out coke burning regeneration at revivifier under conventional catalytic cracking catalyst regeneration condition, general regeneration temperature is controlled at 650～800 ℃ (preferred 680-760 ℃).Riser catalytic cracking technology and device are for the mature industry process, and those of ordinary skills are perfectly clear to its operation and control process, the present invention to its catalyzer select for use with processing condition without any restriction.
The present invention has following advantage compared to existing technology:
1, the present invention by reducing regenerated catalyst temperature, makes agent-oil ratio become independent regulated variable under the condition that does not reduce regeneration temperature.Under identical riser tube mixing temperature, but the rising agent oil ratio improves raw material preheating temperature, improves the atomizing of raw material, and promotion contacts with catalyzer.
But the temperature of reaction of 2 each reaction zone of flexible and the regeneration temperature of revivifier, and remain on optimum value.Therefore first reaction zone can adopt shorter reaction times and the temperature of reaction of Geng Gao; Can process heavier hydrocarbon feed, mixing of vacuum residuum refined than reaching 100%, promptly process 100% vacuum residuum, reduce the productive rate of undesirable product such as coke and gas, improve the productive rate that gasoline and light gold-plating divide simultaneously, improve gasoline octane rating, reduce oil product alkene and foreign matter content, thereby improved the economy of this method.
3, regeneration temperature is not subjected to the restriction of agent-oil ratio and raw material preheating temperature, and regeneration temperature can improve, and helps highly efficient regeneration, and plays heavy metal-passivated effect.High regeneration temperature makes flue gas take heat out of to increase, and the heat-obtaining amount reduces.
4, the catalyzer used of cold shock is cold regenerated catalyst, cold half regenerated catalyst or from the living catalyzer for the treatment of coldly of gasoline upgrading system, help to improve the catalyst activity of heavy oil riser tube second reaction zone, promote the carrying out of secondary reactions such as hydrogen transference, isomerization, aromizing, reduce the productive rate of coke and gas, thereby improve the productive rate raising that gasoline and light gold-plating divide, gasoline octane rating reduces oil product alkene and foreign matter content.
5, because of the regenerator temperature reduces, the catalytic cracking process thermal response is reduced, regenerator gives the hydrothermal deactivation that promotes section at riser tube and alleviates.
6, high regeneration temperature, high solvent-oil ratio are specially adapted to the super stable molecular sieve Application of Catalyst.
7, compare with technology such as mixing temperature control techniques, notes terminators, heat-obtaining potential temperature height of the present invention, Btu utilization is more reasonable.
8, use the present invention, do not influence the use of other technologies, as with the existing close heat-obtaining of section mutually technology, the terminator implantttion technique, multiple feeds etc. are common to use better effects if.
Compared with prior art, heavy oil is after catalytic convention design of the present invention, and the alkene volume content can reduce by 10～40 volume percentage points, and octane value (RON) improves 0.5～5 unit, and the sulphur content in the gasoline reduces by 10～30% (weight).Inferior patrol is after catalytic convention design of the present invention, and the alkene volume content reduces by 10～60 volume percentage points, and octane value (RON) improves 0.5～40 unit, and the sulphur content in the gasoline reduces by 10～50% (weight).
The method applied in the present invention compared with prior art, its effect that reduces the gasoline olefin volume content is more remarkable, have the characteristics that improve gasoline octane rating, reduce its oil product foreign matter content concurrently, have workable, simple and flexible, widely used advantage simultaneously.
Description of drawings
Accompanying drawing 1-4: be the canonical schema of catalytic conversion of heavy oil device of the present invention.
Describe the present invention in detail below in conjunction with accompanying drawing, accompanying drawing is drawn for the present invention is described, does not constitute the restriction to any embodiment of the present invention's design.
Implement separately
Accompanying drawing 1 is the canonical schema of the independent catalytic conversion of heavy oil device of implementing.
As shown in Figure 1: method for catalytic conversion of heavy oil of the present invention and device thereof comprise settling vessel 1, and the heavy oil riser reactor comprises pre-lifting zone 4, first reaction zone 3, second reaction zone 2, revivifier 5, subsidiary riser 6.Be provided with reclaimable catalyst transfer lime 7 and control valve 20 between the stripping stage 1A of revivifier 5 and settling vessel 1 and be communicated with revivifier 5 and stripping stage 1A, reclaimable catalyst is transported to revivifier 5.Heavy oil riser reactor middle part (joint portion of first reaction zone 3, second reaction zone 2) is connected with subsidiary riser 6.
Revivifier is provided with in 3 or outside heat removing equipment, i.e. catalyst cooler, 35A, 35B, 35C are fluidizing medium such as air, water, steam etc., and 37A, 37B, 37C are the heat-obtaining medium, comprise water, steam, various oil products etc.Catalyst cooler-A is mainly used in the temperature of reaction of regulating first reaction zone, makes it remain on optimum value.Catalyst cooler-B is mainly used in the temperature of reaction of regulating second reaction zone, makes it remain on optimum value.Catalyst cooler-C (not drawing among the figure) is mainly used in the adjusting regenerator temperature, makes it remain on optimum value.
According to processing requirement, catalyst cooler-A, catalyst cooler-C can not establish yet, hot regenerated catalyst directly enters first reaction zone without cooling, and regenerator temperature is by regulating catalyst cooler-B fluidizing medium and comprise the flow of air, steam etc. and returning the catalytic amount of revivifier or control by the thermal equilibrium of reaction-regeneration system.
Be the convenient temperature that enters heavy oil riser reactor first reaction zone of controlling, hot regenerated catalyst transfer lime (comprising control valve) can be set directly to link to each other with the pre-lifting zone 4 of heavy oil riser reactor, cold regenerated catalyst directly links to each other with the pre-lifting zone 4 of heavy oil riser reactor through promoting medium 32 lifting mixture transfer limes (comprising control valve) in the pre-lifting zone 4 of heavy oil riser reactor with hot regenerated catalyst, and cold regenerated catalyst reaches balanced with hot regenerated catalyst in the pre-lifting zone 4 of heavy oil riser reactor temperature after 32 liftings of lifting medium mix.Many other operating devices and control method also can be arranged certainly, do not constitute restriction any embodiment of the present invention's design.
Temperature for convenient control riser reactor second reaction zone 2, hot regenerated catalyst transfer lime (comprising control valve) can be set directly link to each other with the pre-lifting zone of subsidiary riser, cold regenerated catalyst reaches balanced with hot regenerated catalyst in the pre-lifting zone of subsidiary riser temperature after 30 liftings of lifting medium mix.Many other operating devices and control method also can be arranged certainly, do not constitute restriction any embodiment of the present invention's design.
Above-mentioned catalyst cooler can be connected as a single entity with revivifier, also can link to each other with revivifier by pipeline.
Behind the lifting medium 30 and mixture of catalysts and reaction oil gas and mixture of catalysts hybrid cooling from subsidiary riser from first reaction zone 3, enter heavy oil riser reactor second reaction zone 2, mainly carry out secondary reactions such as hydrogen transference, isomerization, aromizing, further reduce alkene and sulphur content, boosting of octane rating.Main operational condition is as follows: temperature of reaction 350～620 ℃ of (preferred 450～530 ℃), absolute pressures are 0.11～0.4MPa, 0.5～30 second duration of contact (preferred 1～5 second).
Reaction oil gas and mixture of catalysts from second reaction zone 2 enter settling vessel 1, carry out oil gas and catalyst separating, oil gas enters fractionation, absorbing-stabilizing system carries out fractionation and LPG reclaims, and obtains comprising the product and the unconverted oil of catalytically cracked gasoline.
Reclaimable catalyst is behind the stripping stage 1A of settling vessel 1 stripping, enter revivifier 5 by reclaimable catalyst transfer lime 7 and control valve 20, in the presence of oxygen-containing gas 38 (comprising air etc.), behind coke burning regeneration, divide two-way to enter catalyst cooler 8A and catalyst cooler 8B, the two-way cold regenerated catalyst with or do not mix respectively and recycle with hot regenerated catalyst.
The decanting point of above-mentioned gas or liquid cold shock agent 34 can be in the upstream or the downstream of cold catalyzer decanting point, or the subsidiary riser ingress, with the temperature of convenient each reaction zone of control, or forms another reaction zone.
Joint Implementation
Accompanying drawing 2～4 is the canonical schema of the catalytic conversion of heavy oil device of Joint Implementation.
Accompanying drawing 2 is the canonical schema (shared subsequent reactions and separation system) of the catalytic conversion of heavy oil device of Joint Implementation.Riser 6.Be provided with reclaimable catalyst transfer lime 7 and control valve 20 between the stripping stage 1A of revivifier 5 and settling vessel 1 and be communicated with revivifier 5 and stripping stage 1A, reclaimable catalyst is transported to revivifier 5.Heavy oil riser reactor middle part (joint portion of first reaction zone 3, second reaction zone 2) is connected with gasoline rising pipe reactor 6.
Revivifier is provided with in 3 or outside heat removing equipment, i.e. catalyst cooler, 35A, 35B, 35C are fluidizing medium such as air, water, steam etc., and 37A, 37B, 37C are the heat-obtaining medium, comprise water, steam, various oil products etc.Catalyst cooler-A is mainly used in the temperature of reaction of regulating first reaction zone, makes it remain on optimum value.Catalyst cooler-B is mainly used in the temperature of reaction of regulating second reaction zone, makes it remain on optimum value.Catalyst cooler-C (not drawing among the figure) is mainly used in the adjusting regenerator temperature, makes it remain on optimum value.
According to processing requirement, catalyst cooler-A, catalyst cooler-C can not establish yet, hot regenerated catalyst directly enters first reaction zone without cooling, and regenerator temperature is by regulating catalyst cooler-B fluidizing medium and comprise the flow of air, steam etc. and returning the catalytic amount of revivifier or control by the thermal equilibrium of reaction-regeneration system.
Be the convenient temperature that enters riser reactor first reaction zone of controlling, hot regenerated catalyst transfer lime 9A (comprising control valve 22A) is set links to each other with the pre-lifting zone 4 of heavy oil riser reactor, cold regenerated catalyst reaches balanced with hot regenerated catalyst in the pre-lifting zone 4 of heavy oil riser reactor temperature after 32 liftings of lifting medium mix.Many other operating devices and control method also can be arranged certainly, do not constitute restriction any embodiment of the present invention's design.
Be the convenient temperature that enters heavy oil riser reactor second reaction zone of controlling, hot regenerated catalyst transfer lime 9B (comprising control valve 22B) is set links to each other with the pre-lifting zone of gasoline rising pipe, cold regenerated catalyst reaches balanced with hot regenerated catalyst in the pre-lifting zone of gasoline rising pipe reactor temperature after 30 liftings of lifting medium mix.Hot regenerated catalyst transfer lime 9B (comprising control valve 22B) also can cancel.Many other operating devices and control method also can be arranged certainly, do not constitute restriction any embodiment of the present invention's design.
Above-mentioned catalyst cooler can be connected as a single entity with revivifier, also can link to each other with revivifier by pipeline.
From the reaction product of gasoline rising pipe and mixture of catalysts and from entering heavy oil riser reactor second reaction zone 2 behind the reaction oil gas of first reaction zone 3 and the mixture of catalysts hybrid cooling, mainly carry out secondary reactions such as hydrogen transference, isomerization, aromizing, further reduce alkene and sulphur content, boosting of octane rating.Main operational condition is as follows: temperature of reaction 350-620 ℃ of (preferred 450-530 ℃), absolute pressure are 0.11～0.4Mpa, 0.5～30 second duration of contact (preferred 1-5 second).
Reaction oil gas and mixture of catalysts from second reaction zone 2 enter settling vessel 1, carry out oil gas and catalyst separating, oil gas enters fractionation, absorbing-stabilizing system carries out fractionation and LPG reclaims, and obtains comprising the product and the unconverted oil of catalytically cracked gasoline.
Reclaimable catalyst is behind the stripping stage 1A of settling vessel 1 stripping, enter revivifier 5 by reclaimable catalyst transfer lime 7 and control valve 20, in the presence of oxygen-containing gas 38 (comprising air etc.), behind coke burning regeneration, divide two-way to enter catalyst cooler 8A and catalyst cooler 8B, the two-way cold regenerated catalyst with or do not mix respectively and recycle with hot regenerated catalyst.
The decanting point of above-mentioned gas or liquid cold shock agent 34 can with the temperature of convenient each reaction zone of control, or form another reaction zone in the upstream or the downstream of cold catalyzer decanting point.
Accompanying drawing 3 is the canonical schema (setting up subsequent separation system separately) of the catalytic conversion of heavy oil device of Joint Implementation.
As shown in Figure 3: method for catalytic conversion of heavy oil of the present invention and device thereof comprise heavy oil settling vessel 1, and petrol sediment bulb 18, heavy oil riser reactor comprise pre-lifting zone 4, first reaction zone 3, second reaction zone 2, revivifier 5, gasoline rising pipe 6.Be provided with reclaimable catalyst transfer lime 7 and control valve (not drawing among the figure) between the stripping stage 1A of revivifier 5 and settling vessel 1 and be communicated with revivifier 5 and heavy oil settling vessel 1 stripping stage 1A, reclaimable catalyst is transported to revivifier 5.Being provided with reclaimable catalyst transfer lime 15 and control valve 23 is connected heavy oil riser reactor middle part (joint portion of first reaction zone 3, second reaction zone 2) with the stripping stage 18A of settling vessel 18.Control valve 23 is to control the flow of the reclaimable catalyst that cold shock uses for convenience and the concrete controlling elements that is provided with, and many other operating devices and control method also can be arranged certainly, does not constitute the restriction to any embodiment of the present invention's design.
Revivifier is provided with in 3 or outside heat removing equipment, i.e. catalyst cooler, 35A, 35B, 35C are fluidizing medium such as air, water, steam etc., and 37A, 37B, 37C are the heat-obtaining medium, comprise water, steam, various oil products etc.Catalyst cooler-A is mainly used in the temperature of reaction of regulating first reaction zone, makes it remain on optimum value.Catalyst cooler-B is mainly used in the temperature of reaction of regulating second reaction zone, makes it remain on optimum value.Catalyst cooler-C (not drawing among the figure) is mainly used in the adjusting regenerator temperature, makes it remain on optimum value.
According to processing requirement, catalyst cooler-A, catalyst cooler-C can not establish yet, hot regenerated catalyst directly enters first reaction zone without cooling, and regenerator temperature is by regulating catalyst cooler-B fluidizing medium and comprise the flow of air, steam etc. and returning the catalytic amount of revivifier or control by the thermal equilibrium of reaction-regeneration system.
Be the convenient temperature that enters heavy oil riser reactor first reaction zone of controlling, hot regenerated catalyst transfer lime (comprising control valve) can be set link to each other with the pre-lifting zone 4 of heavy oil riser reactor, cold regenerated catalyst reaches balanced with hot regenerated catalyst in the pre-lifting zone 4 of heavy oil riser reactor temperature after 32 liftings of lifting medium mix.Many other operating devices and control method also can be arranged certainly, do not constitute restriction any embodiment of the present invention's design.
Temperature for convenient control gasoline rising pipe reactor, hot regenerated catalyst transfer lime 9B (comprising control valve 22B) is set links to each other with the pre-lifting zone of gasoline rising pipe reactor, cold regenerated catalyst reaches balanced with hot regenerated catalyst in the pre-lifting zone of gasoline rising pipe reactor temperature after 30 liftings of lifting medium mix.Hot regenerated catalyst transfer lime 9B (comprising control valve 22B) also can cancel.Many other operating devices and control method also can be arranged certainly, do not constitute restriction any embodiment of the present invention's design.
Above-mentioned catalyst cooler can be connected as a single entity with revivifier, also can link to each other with revivifier by pipeline.
Enter heavy oil riser reactor first reaction zone 3 behind heavy oil feedstock 33 and the regenerated catalyst hybrid cooling from the pre-lifting zone 4 of heavy oil riser reactor, under catalytic cracking condition, react, main operational condition is as follows: temperature of reaction 400-650 ℃ of (preferred 520-600 ℃), absolute pressure are 0.11～0.4MPa, 0.05～5 second duration of contact (preferred 0.1-3 second), catalyzer is generally 3～10, preferred 5～8 with the raw material weight ratio.
Behind the catalyst mixture of gasoline rising pipe and reaction oil gas and mixture of catalysts hybrid cooling from first reaction zone 3, enter heavy oil riser reactor second reaction zone 2, mainly carry out secondary reactions such as hydrogen transference, isomerization, aromizing, further reduce alkene and sulphur content, boosting of octane rating.Main operational condition is as follows: temperature of reaction 350-620 ℃ of (preferred 450-530 ℃), absolute pressure are 0.11～0.4MPa, 0.5～30 second duration of contact (preferred 1-5 second).
Enter settling vessel 18 from the reactant flow of gasoline rising pipe 6 and carry out oil gas and catalyst separating, oil gas enters fractionation separately, absorbing-stabilizing system carries out fractionation and LPG reclaims, and obtains comprising the product and the unconverted oil of catalytically cracked gasoline; Or with after oil gas from settling vessel 1 mixes, enter shared fractionation, absorbing-stabilizing system carries out fractionation and LPG reclaims.
Reclaimable catalyst is behind the stripping stage 1A of settling vessel 1 stripping, enter revivifier 5 by reclaimable catalyst transfer lime 7 and control valve (not shown), in the presence of oxygen-containing gas 38 (comprising air etc.), behind coke burning regeneration, divide two-way to enter catalyst cooler 8A and catalyst cooler 8B, the two-way cold regenerated catalyst with or do not mix respectively and recycle with hot regenerated catalyst.
The decanting point of above-mentioned gas or liquid cold shock agent 34 can with the temperature of convenient each reaction zone of control, or form another reaction zone in the upstream or the downstream of cold catalyzer decanting point.
Accompanying drawing 4 is the canonical schema (setting up subsequent separation system separately) of the catalytic conversion of heavy oil device of Joint Implementation.
As shown in Figure 4: method for catalytic conversion of heavy oil of the present invention and device thereof comprise heavy oil settling vessel 1, and petrol sediment bulb 18, heavy oil riser reactor comprise pre-lifting zone 4, first reaction zone 3, second reaction zone 2, revivifier 5, gasoline rising pipe 6.Be provided with reclaimable catalyst transfer lime 7 and control valve (not drawing among the figure) between the stripping stage 1A of revivifier 5 and settling vessel 1 and be communicated with revivifier 5 and stripping stage 1A, reclaimable catalyst is transported to revivifier 5.Heavy oil riser reactor middle part (joint portion of first reaction zone 3, second reaction zone 2) is connected with the stripping stage 18A of settling vessel 18.Settling vessel 1 is connected by upflow tube 17 with settling vessel 18.Upflow tube 17 and control valve 23 are to control the flow of the reclaimable catalyst that cold shock uses for convenience and the concrete controlling elements that is provided with, and many other operating devices and control method also can be arranged certainly, do not constitute the restriction to any embodiment of the present invention's design.
Revivifier is provided with 2 outside heat removing equipment, i.e. catalyst cooler, 35A, 35B are fluidizing medium such as air, water, steam etc.37A, 37B is the heat-obtaining medium, comprises water, steam, various oil products etc.Catalyst cooler-A is mainly used in the adjusting regenerator temperature, makes it remain on optimum value.Regenerator temperature is by regulating catalyst cooler-B fluidizing medium and comprise the flow of air, steam etc. and returning the catalytic amount of revivifier or control by the thermal equilibrium of reaction-regeneration system.Catalyst cooler-B is mainly used in the temperature of reaction of regulating second reaction zone, makes it remain on optimum value.
According to processing requirement, catalyst cooler can be set be mainly used in the temperature of reaction of regulating riser reactor first reaction zone, make it remain on optimum value.
Hot regenerated catalyst links to each other with the pre-lifting zone 4 of heavy oil riser reactor by hot regenerated catalyst transfer lime 9A.The temperature of revivifier 5 is controlled by the flow of adjusting fluidizing medium 35A (comprising air, steam etc.) and the flow of the lifting medium 36A (comprising air, steam etc.) on the cold regenerated catalyst return tube 12A.Control valve 22A controls the flow of hot regenerated catalyst and the concrete controlling elements that is provided with for convenience, and many other operating devices and control method also can be arranged certainly, does not constitute the restriction to any embodiment of the present invention's design.
Be the convenient temperature that enters riser reactor first reaction zone of controlling, catalyst cooler can be set link to each other with the pre-lifting zone 4 of regenerated catalyst (comprising control valve) and heavy oil riser reactor, cold regenerated catalyst reaches balanced with hot regenerated catalyst in the pre-lifting zone 4 of heavy oil riser reactor temperature after 32 liftings of lifting medium mix.Many other operating devices and control method also can be arranged certainly, do not constitute restriction any embodiment of the present invention's design.
Temperature for convenient control gasoline rising pipe reactor, hot regenerated catalyst transfer lime (comprising control valve) can be set link to each other with the pre-lifting zone of gasoline rising pipe reactor, cold regenerated catalyst reaches balanced with hot regenerated catalyst in the pre-lifting zone of service hoisting pipe reactor temperature after 30 liftings of lifting medium mix.Many other operating devices and control method also can be arranged certainly, do not constitute restriction any embodiment of the present invention's design.
Above-mentioned catalyst cooler can be connected as a single entity with revivifier, also can link to each other with revivifier by pipeline.
Behind the catalyst mixture of gasoline rising pipe and reaction oil gas and mixture of catalysts hybrid cooling from first reaction zone 3, enter heavy oil riser reactor second reaction zone 2, mainly carry out secondary reactions such as hydrogen transference, isomerization, aromizing, further reduce alkene and sulphur content, boosting of octane rating.Main operational condition is as follows: temperature of reaction 350-620 ℃ of (preferred 450-530 ℃), absolute pressure are to contact under 0.11～0.4MPa condition, 0.5～30 second duration of contact (preferred 1-5 second).
Enter settling vessel 18 from the reactant flow of gasoline rising pipe 6 and carry out oil gas and catalyst separating, oil gas enters fractionation separately, absorbing-stabilizing system carries out fractionation and LPG reclaims, and obtains comprising the product and the unconverted oil of catalytically cracked gasoline; Or with after oil gas from settling vessel 1 mixes, enter shared fractionation, absorbing-stabilizing system carries out fractionation and LPG reclaims.
From the reclaimable catalyst of settling vessel 18 stripping section 18A by reclaimable catalyst transfer lime 15 and control valve 23 all or part of with mix from the reaction oil gas of first reaction zone 3 and mixture of catalysts after enter heavy oil riser reactor second reaction zone 2; Perhaps partly or entirely import heavy oil settling vessel 1 by upflow tube 17.
Reaction oil gas and mixture of catalysts from second reaction zone 2 enter settling vessel 1, carry out oil gas and catalyst separating, oil gas separately or with enter fractionation after oil gas from settling vessel 18 mixes, absorbing-stabilizing system carries out fractionation and LPG recovery, obtains comprising the product and the unconverted oil of catalytically cracked gasoline.
Reclaimable catalyst is behind the stripping stage 1A of settling vessel 1 stripping, enter revivifier 5 by reclaimable catalyst transfer lime 7 and control valve (not shown), in the presence of oxygen-containing gas 38 (comprising air etc.), behind coke burning regeneration, divide two-way to enter catalyst cooler 8A and catalyst cooler 8B, the two-way cold regenerated catalyst with or do not mix respectively and recycle with hot regenerated catalyst.
The decanting point of above-mentioned gas or liquid cold shock agent 34 can with the temperature of convenient each reaction zone of control, or form another reaction zone in the upstream or the downstream of cold catalyzer decanting point.
Example 1
For verifying effect of the present invention, adopting the trade mark of raw material shown in technical process shown in Figure 1, the processing condition shown in the table 2, the table 1 and Chang Ling refinery catalyst plant production is the catalyzer of GOR-C, and test-results is listed in table 3.
Table 1
| Logistics | Long residuum |
| Density, the API degree | 15.0 |
| Density, 20/4 ℃ | 0.96 |
| Carbon residue | 10％(Wt) |
| Sulphur content | 0.6％(Wt) |
| Nitrogen content | 2000PPm |
| Pitch | 4.5％(Wt) |
In table 2, the option A of prior art adopts conventional heavy oil catalytic cracking process technology: the temperature of revivifier beds is 700 ℃, and temperature of reaction is 560 ℃.Material temperature is 240 ℃, and catalystoil ratio is 8.0.Therefore, the temperature difference of regenerator and raw material is 460 ℃.The option A of prior art has following deficiency:
(1) 240 ℃ material temperature is quite low to the cracking that contains the residual oil raw material.
(2) although the temperature of revivifier satisfies the regeneration requirement, temperature is too high when contacting with raw material, occurs thermally splitting easily.
Be to be understood that, the embodiment of table 2 limits anything but, because unlike the prior art, illustrates among the solution of the present invention B, any combination of catalyst recirculation amount all can be determined between two standpipes, replaces the catalystoil ratio of being determined by force by device thermal equilibrium so that guarantee the catalystoil ratio that reacts required.Because identical reason, in option b, can select any feeding temperature, and to catalystoil ratio without any detrimentally affect.In an embodiment, select 360 ℃.Because for the raw material of present embodiment, 360 ℃ approaching in the top temperature that thermally splitting may occur.
Table 2
| Sequence number | Parameter | The prior art option A | The present invention program B |
| ??1 | The riser tube temperature of reaction, ℃ | ????560 | ????- |
| / the first reaction zone temperature of reaction ℃ | ????- | ????560 | |
| ??2 | The second reaction zone temperature of reaction, ℃ | ????- | ????480 |
| ??3 | Feeding temperature, ℃ | ????240 | ????360 |
| ??4 | Regeneration temperature, ℃ | ????700 | ????720 |
| ??5 | Go into the catalyst temperature of subsidiary riser, ℃ | ????- | ????400 |
| ??6 | The temperature of subsidiary riser, ℃ | ????- | ????400 |
| ??7 | The catalyst mixture temperature, ℃ | ????700 | ????650 |
| ??8 | The catalyst charge temperature difference, ℃ | ????450 | ????287 |
| ??9 | The first reaction zone catalystoil ratio, weight by weight | ????8.0 | ????8.0 |
Table 3
| Product | The prior art option A | The present invention program B |
| H 2S???????％ | ????0.6 | ????0.8 |
| Fuel gas % | ????7.0 | ????5.6 |
| LPG???????％ | ????11.5 | ????11.8 |
| Gasoline % | ????38.0 | ????39.7 |
| Light cycle oil % | ????16.1 | ????16.0 |
| Clarified oil % | ????16.1 | ????16.1 |
| Coke % | ????10.7 | ????10.0 |
| Add up to | ????100.0 | ????100.0 |
| Gasoline | ||
| Olefin(e) centent % | ????59.8 | ????32.6 |
| Aromaticity content % | ????12.6 | ????19.8 |
| Sulphur content PPm | ????187 | ????142.8 |
| Octane value RON | ????89.6 | ????90.2 |
Implement 2
For verifying effect of the present invention, adopt technical process shown in Figure 4, adopt processing condition shown in the table 4 and the heavy oil feedstock shown in the table 1, inferior patrol is a catalytically cracked gasoline, catalyzer is GOR-C.Test-results is listed in table 5.
In table 4, the option A of prior art adopts conventional heavy oil catalytic cracking process technology: the temperature of revivifier beds is 700 ℃, and temperature of reaction is 560 ℃.Material temperature is 240 ℃, and catalystoil ratio is 8.0.Therefore, the temperature difference of regenerator and raw material is 460 ℃.The option A of prior art has following deficiency:
(1) 240 ℃ material temperature is quite low to the cracking that contains the residual oil raw material.
(2) although the temperature of revivifier satisfies the regeneration requirement, temperature is too high when contacting with raw material, occurs thermally splitting easily.
Table 4
| Sequence number | Parameter | The prior art option A | The present invention program B |
| ??1 | The riser tube temperature of reaction, ℃ | ????560 | ????- |
| First reaction zone temperature ℃ | ????- | ????560 | |
| ??2 | Second reaction zone temperature, ℃ | ????- | ????500 |
| ??3 | Feeding temperature, ℃ | ????240 | ????360 |
| ??4 | Regeneration temperature, ℃ | ????700 | ????720 |
| ??5 | The spent agent temperature of gasoline rising pipe, ℃ | ????- | ????400 |
| ??6 | The temperature of reaction of gasoline rising pipe, ℃ | ????- | ????400 |
| ??7 | The catalyst mixture temperature, ℃ | ????700 | ????650 |
| ??8 | The catalyst charge temperature difference, ℃ | ????450 | ????287 |
| ??9 | The riser tube catalystoil ratio, weight by weight | ????8.0 | ????- |
| ??10 | The first reaction zone catalystoil ratio, weight by weight | ????- | ????8.0 |
| ??11 | The gasoline rising pipe catalystoil ratio, weight by weight | ????5.0 | ????5.0 |
Table 5
| Product | The prior art option A | The present invention program B | ||
| The heavy oil riser tube | Gasoline rising pipe | |||
| H 2S???????％ | ????0.6 | ??0.8 | ||
| Fuel gas % | ????7.0 | ??5.8 | ????????0.49 | |
| LPG???????％ | ????11.5 | ??12.8 | ????????2.12 | |
| Gasoline % | ????38.0 | ??40.8 | ????????92.68 | |
| Light cycle oil % | ????16.1 | ??14.2 | ????????4.31 | |
| Clarified oil % | ????16.1 | ??15.4 | ||
| Coke % | ????10.7 | ??10.3 | ????????0.40 | |
| Add up to | ????100.0 | ??100.0 | ????????100.00 | |
| Gasoline | Before the upgrading | Behind the upgrading | ||
| Olefin(e) centent % | ????59.8 | ??31.5 | Benchmark | ????-30.5 |
| Aromaticity content % | ????12.6 | ??20.6 | Benchmark | ????+11.5 |
| Sulphur content PPm | ????187 | ??130.0 | Benchmark | ????-40.8 |
| Octane value RON | ????89.6 | ??90.5 | Benchmark | ????+1.2 |
Claims (12)
1, a kind of heavy crude hydro carbons catalysis conversion method and device thereof, it is characterized in that: technological process may further comprise the steps:
(1) the heavy oil petroleum hydrocarbon raw material be less than or equal to the cyclic regeneration catalyst mix of regenerator temperature from the temperature of pre-lifting zone after enter the heavy oil riser reactor that has two reaction zones at least, in 400～650 ℃ of temperature of reaction, absolute pressure is that 0.11～0.4Mpa, duration of contact are 0.05～5 second, and catalyzer and raw material weight are than being to carry out primary first-order equation under 3～10 the condition;
(2) step (1) primary first-order equation product and mixture of catalysts enter second reaction zone behind riser tube and cold shock agent hybrid cooling, are 0.11～0.4Mpa, duration of contact to be to carry out secondary reaction under 0.5～30 second the condition in 350～620 ℃ of temperature of reaction, absolute pressure;
(3) step (2) secondary reaction product and catalyst mixture enter settling vessel along riser tube, carry out separating of catalyzer and oil gas, isolated reclaimable catalyst enters revivifier behind the stripping stage stripping, burn under the condition of 650～800 ℃ of regeneration temperatures, the catalyzer after the regeneration recycles through cooling or without returning riser reactor after cooling off.
(4) part with step (3) directly enters without the refrigerative hot regenerated catalyst; Perhaps a part is cooled to 200～720 ℃ cold regenerated catalyst through catalyst cooler A and directly enters; Perhaps their are mixed obtaining the mixed regeneration catalyzer that temperature is lower than regenerator temperature and enter the pre-lifting zone of heavy oil riser reactor, and then enter first reaction zone;
(5) part of step (3) is cooled to 200～720 ℃ cold regenerated catalyst through catalyst cooler B and enters subsidiary riser or gasoline rising pipe (having or do not have fluidized-bed reactor) after another part mixes without the refrigerative hot regenerated catalyst; Perhaps directly do not enter described subsidiary riser or gasoline rising pipe (having or do not have fluidized-bed reactor), be mixed into second reaction zone as cold shock agent and reaction product and the mixture of catalysts of leaving first reaction zone with the described cold regenerated catalyst of hot regenerated catalyst blended.
2, in accordance with the method for claim 1 and the device, it is characterized in that: the regenerated catalyst that its step (5) enters gasoline rising pipe mixes with the inferior patrol of full cut or narrow fraction, in 300～650 ℃ of temperature of reaction, absolute pressure is 0.11～0.4Mpa, duration of contact to be that 0.5～50 second, catalyzer and inferior patrol weight ratio are to react under 1～50 the condition, and reaction product and mixture of catalysts directly enter second reaction zone as the cold shock agent; Or enter settling vessel and carry out oil gas and catalyst separating.
3, according to claim 1 and 2 described method and devices thereof, it is characterized in that described revivifier is provided with one, two or more interior or outside heat removing equipment, it is catalyst cooler, described catalyst cooler is characterized in that being provided with one, two or more catalyst outlet, one of them is used to carry cold regenerated catalyst to return revivifier, and another or two are respectively applied for and carry cold regenerated catalyst to be circulated to one or two riser tube (reactor).
4, according to claim 1,2,3 described method and devices thereof, it is characterized in that: the reaction product of the reaction product of its bad gasoline and mixture of catalysts and heavier hydrocarbon feeds and mixture of catalysts enter same settling vessel or enter two settling vessels respectively, carry out catalyzer and gas-oil separation, when setting up two settling vessels separately, the reclaimable catalyst after finishing gasoline and transforming not stripping or separately behind the stripping all or part of heavy oil riser tube that enters do the cold shock agent; Perhaps not stripping or separately behind the stripping all or part of overflow enter another settling vessel; The all or part of revivifier that enters behind the perhaps independent stripping.
5, according to claim 1,2,3,4 described method and devices thereof, the reaction product that it is characterized in that described gasoline fraction and catalyzer separate and the stripping facility is provided with separately; Or it is shared with the reaction product and the mixture of catalysts of heavier hydrocarbon feeds, separating and stripping facility when being provided with separately of the reaction product of gasoline fraction and catalyzer, finish after gasoline fraction transforms reclaimable catalyst not stripping or separately behind the stripping all or part of heavy oil riser tube that enters do the cold shock agent; Perhaps partly or entirely enter settling vessel through overflow.
6, according to described method of claim 1～5 and device thereof, it is characterized in that:
The main operational condition of described first reaction zone is: temperature of reaction is that 520～600 ℃, duration of contact are 0.1～3 second, and catalyzer is 5～8 with the raw material weight ratio;
The main operational condition of described second reaction zone is: temperature of reaction is that 450～530 ℃, duration of contact are 1～5 second;
The main operational condition of described gasoline rising pipe is: temperature of reaction is that 400～560 ℃, duration of contact are that 1～15 second, catalyzer are 2～20 with the raw material weight ratio;
The described regeneration temperature of claim 1 step (3) is 680～760 ℃;
The described cold regenerated catalyst of claim 1 step (4) is 300～500 ℃;
The described cold regenerated catalyst of claim 1 step (5) is 300～600 ℃.
7, in accordance with the method for claim 1 and device, it is characterized in that: the described heavy crude hydro carbons of its step (1) comprises a kind of, two kinds and the two or more mixtures in the oil product of long residuum, vacuum residuum, straight-run gas oil, wax tailings, shale oil, synthetic oil, crude oil, coal tar, recycle stock, slurry oil, glue asphalt oil, heavy gas oil.
8, in accordance with the method for claim 1 and the device, it is characterized in that: described catalyzer comprises amorphous silicon aluminium catalytic cracking catalyst or molecular sieve catalyst cracking catalyst.
9, in accordance with the method for claim 1 and device, it is characterized in that: described gaseous state or liquid cold shock agent be water, comprise the oil product of gasoline, recycle stock, clarified oil and comprise cold regenerated catalyst, treat coldly living catalyzer, a kind of, two or more mixture in the catalyzer of cold half regenerated catalyst.
10, in accordance with the method for claim 2 and device, it is characterized in that: the inferior patrol of described full cut or narrow fraction is a kind of, two or more the blend gasoline that comprises in the gasoline of straight-run spirit, condensate oil, catalytically cracked gasoline, pressure gasoline, visbreaking gasoline, coker gasoline, cracking ethylene preparation gasoline.
11, in accordance with the method for claim 1 and device, it is characterized in that: in the described heavy crude hydro carbons of its step (1)＞500 ℃ component concentration is 30～100%.
12, according to claim 1,9 described methods, it is characterized in that: the decanting point of described gaseous state or liquid cold shock agent can be in the upstream of cold catalyzer decanting point, downstream or in the ingress of subsidiary riser.
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