CN103571534A - Device and method for producing clean gasoline by combining catalytic cracking and hydrofining - Google Patents
Device and method for producing clean gasoline by combining catalytic cracking and hydrofining Download PDFInfo
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Abstract
The invention discloses a device and method for producing clean gasoline by combining catalytic cracking and hydrofining. The device comprises a reaction-regeneration system, a fractionating system, an absorption stable system and a hydrofining unit. The method comprises the following steps: adding a gasoline fractionating tower to the top of a catalytic cracking fractionating tower to divide crude gasoline into a light fraction and a heavy fraction, wherein the heavy fraction gasoline enters the hydrofining unit for selective hydrogenation desulfurization, and one part of the light fraction gasoline enters the absorption stable system to obtain stable light gasoline, and the other part of the light fraction gasoline directly returns to a reaction area at the upper part of a catalytic cracking second riser reactor to be modified under a mild condition; and blending the stable light gasoline and the modified heavy gasoline to obtain the product of clean gasoline. By adopting the method, the catalytic cracking gasoline is efficiently modified, and the catalyst-oil ratio of a catalytic cracking device can be increased to promote the conversion of heavy petroleum hydrocarbon; and meanwhile, the load and energy consumption of the absorption stable system are reduced, the synergistic effect between the two devices of catalytic cracking and hydrofining is enhanced, and the processing cost is lowered.
Description
Technical field
The present invention relates to catalytic conversion process and the hydrotreatment process of petroleum hydrocarbon, particularly relate to the method for catalytically cracked gasoline being carried out to catalyzed conversion and hydrofining associating upgrading, belong to petrochemical technology field, be specifically related to a kind of device and method that utilizes catalytic cracking and hydrofining combination producing clean gasoline.
Background technology
Although the octane value of alkene is higher, chemical property is active, NO in volatilize rear and atmosphere
xmixing is irradiated and can be formed poisonous photo-chemical smog through solar ultraviolet, and atmosphere is caused to severe contamination; On the other hand, the diolefine especially due to alkene with conjugated structure is extremely unstable, easily in engine oil inlet system, nozzle and cylinder, forms colloid settling, affects motor efficiency and work-ing life, and can increase the particle content in tail gas.And the SO producing after sulphides burn
xnot only direct atmosphere pollution, causes the formation of acid rain, but also can make the poisoning of catalyst inactivation in vehicle exhaust transmodulator, the content of HCN, CO and NOx in increase tail gas.Therefore, in European Union, the U.S., Japan, Australia and the national gasoline standard such as Russian, all alkene and sulphur content are made to strict restriction, for example in Europe V gasoline standard, sulphur content is less than 10 μ g/g, olefin(e) centent is less than 18 vol.%, in U.S. gasoline standard, sulphur content is less than 30 μ g/g, and olefin(e) centent is less than 10 vol.%, and in Japanese gasoline standard, sulphur content is less than 50 μ g/g, olefin(e) centent is less than 10 vol.%, and world fuel standards the 4th class has been made the regulation without sulphur especially.
China's oil resource is mostly low-sulfur oil, but shortage of resources, and import be mostly high-sulfur, sulfur-bearing, heavy crude.The high-sulfur crude oil processing ratio of 2010 Nian, CNPCs and Sinopec two companies of large group reaches 35% left and right.Being the in poor quality of raw material on the one hand, is the increasingly stringent of gasoline environmental-protection index on the other hand.From 2014, the whole nation was by state of enforcement's IV gasoline standard, and sulphur content is less than 50 μ g/g, and olefin(e) centent is less than 28 vol.% , China, and catalytic gasoline provides the blend component of gasoline product nearly 80%, but had also introduced sulphur and the alkene that surpasses 90% simultaneously.The in poor quality of raw material has not only improved the sulphur content of catalytic gasoline, also makes content of olefin in gasoline increase simultaneously, and the olefin(e) centent of China's catalytic gasoline, generally at 40 ~ 60 vol.%, far can not meet the requirement of gasoline standard at present.Therefore, the key of present stage raising China quality of gasoline will reduce olefin(e) centent and the sulphur content of catalytically cracked gasoline exactly.
Though to raw material add hydrogen pretreatment can significantly reduce catalytically cracked gasoline sulphur content in today of gasoline environmental-protection index increasingly stringent, catalytic cracking adopts the raw material after hydrotreatment to be also difficult to produce qualified gasoline products, must carry out later stage upgrading to catalytic gasoline.Main modifying catalytically cracked gasoline technology has catalytic cracking " original position " modification technology and back end hydrogenation to process modification technology at present.
The MGD technique (CN1279270A) of Research Institute of Petro-Chemical Engineering's exploitation and patent US5846403, US4051013 etc. are by the olefin(e) centent with reduction catalytic gasoline at riser tube bottom freshening stable gasoline, but the alkene range of decrease is still limited when freshening amount is larger, and yield of gasoline loss is serious, the adaptable multieffect double lift pipe catalytic cracking FDFCC technique (CN1401741A) of Luoyang Petrochemical engineering corporation exploitation, alkene technology (CN1465662A falls in the FCC gasoline subsidiary riser upgrading of Chinese Petroleum Univ.'s exploitation, CN1465663A, CN1458227A, CN1511927A, CN1498949A, CN1498950A etc.) and patent CN1244569A, US3784463 etc. carry out upgrading by setting up independent reactor to gasoline, gasoline upgrading effect is improved, but increased facility investment, and gasoline is direct and high temperature, high activity regenerated catalyzer contact reacts, cracking loss is serious, the MIP technique (CN1237477A) of Research Institute of Petro-Chemical Engineering exploitation be dense bed reaction zone by the enlarged-diameter of connecting to increase bed density of catalyst and to extend the reaction times to promote that hydrogen transfer reactions reduces content of olefin in gasoline, but also can make diesel oil density increase simultaneously.Research is found, if only freshening is rich in the lighting end gasoline of alkene, the upgrading efficiency that not only can improve gasoline also can significantly reduce energy consumption, for this reason patent CN1557916A by increase a rectifying tower by stable gasoline be cut into gently, last running, will after lighting end freshening upgrading, be in harmonious proportion with last running gasoline again.Above-mentioned patent does not all relate to that catalytically cracked gasoline is light, the differentiated treatment problem of last running, does not relate to after freshening gasoline the adjustment measure that should make catalytic cracking fractionation and absorption-stable system yet.
Catalytic cracking " original position " modification technology is more effective for reducing content of olefin in gasoline, as MIP, FDFCC, the technology such as SRFCC all can meet requirement and the gasoline octane rating that olefin(e) centent is less than 28 vol.% and not reduce, but catalytic cracking " original position " is even if modification technology adopts sulfur-lowing catalyst, desulfurization degree is generally also less than 30%, be difficult to the desulfurization degree that reaches higher, and research shows that the sulphur major part reducing in gasoline is not removed but has transferred in diesel oil distillate.Therefore, catalytic gasoline also needs to adopt other sulfur method.
Hydrofining is one of main means of current upgrading catalytic gasoline, in hydrodesulfurization process, alkene also can be by saturated, although this is conducive to reduce content of olefin in gasoline, also just because of high-octane alkene by saturated for low-octane alkane particularly normal paraffin just caused the significantly reduction of unifining process gasoline octane rating.In order to reduce the saturated of alkene, the selective hydrogenation desulfurization process such as SCANfining technique of the Prime G+ technique of IFP (IFP) exploitation and the exploitation of ExxonMobil company all can be realized more than 99% desulfurization degree under low olefin saturated rate, but due to this process unsaturated olefin, therefore the catalytic gasoline that is only applicable to gasoline ,Dui China high olefin content of low olefin-content cannot be suitable for.By alkene distribution and sulfur distribution in gasoline are analyzed and found that in gasoline, most alkene concentrates in lighting end, and most sulphur is enriched in last running.In order to reduce as much as possible the loss of octane number of gasoline in hydrodesulfurization process, patent US5770047, US7731836B2, WO1994/022980A1, CN145666A, CN1621495A, CN101294106A, CN102041085A, CN101275085A, CN101508910A, CN101508911A, CN101845321A, CN102199448A, CN101368111A etc. all propose preferentially catalytic cracking stable gasoline to be cut into gently, last running, mainly catalytically cracked gasoline last running is carried out to hydrogenating desulfurization, isomerization, the processing such as aromizing, the saturated gasoline octane rating that causes that alkene occurs this lighting end gasoline of just having avoided being rich in alkene in hydrogenation process significantly reduces.But above patent all relates to, to being rich in the petroleum naphtha of alkene, do not fall olefin treated, this just makes last running gasoline in hydrogenation process, need the olefin saturated rate that reaches certain just can make final product gasoline reach the requirement of up-to-date gasoline standard.Also have a problem be exactly above patent be all that catalytic cracking stable gasoline is cut, this catalytic gasoline has just very likely passed through cutting twice so, thereby has increased energy consumption and facility investment.Patent CN101294108A propose catalytic cracking production separation system to catalytic gasoline carry out gently, the separation of last running, again last running is carried out to hydrofining, but do not relate to the improvement of absorption-stable system flow process and carry out upgrading to being rich in the petroleum naphtha of alkene, not relating to the system, coupled to catalytic cracking and two processes of hydrofining yet.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of device and method that utilizes catalytic cracking and hydrofining combination producing clean gasoline.
The device of catalytic cracking provided by the invention and hydrofining combination producing clean gasoline, comprises reaction-regeneration system rapidly, fractionating system, and absorption-stable system and hydrofining unit,
Wherein, reaction-regeneration system rapidly comprises riser reactor, finish separator and catalyst regenerator, the upper end of described riser reactor is communicated with finish separator, bottom-up pre-lift gas entrance, catalyst feeds and the raw gasline lighting end opening for feed of being provided with successively of riser reactor, the solid phase outlet of finish separator is communicated with catalyst regenerator, and catalyst regenerator is communicated with the catalyst feeds of riser reactor by regenerator sloped tube;
Fractionating system comprises separation column, gasoline splitter, the first separating tank and the second separating tank, the gaseous phase outlet of finish separator is communicated with entrance at the bottom of the tower of separation column, the gaseous phase outlet of fractionator overhead is by being provided with the pipeline of condenser and the gas phase entrance of gasoline splitter is communicated with, the lighting end outlet of gasoline splitter tower top is communicated with the entrance of the first separating tank by being provided with the pipeline of condenser, and the last running outlet at the bottom of gasoline splitter tower is communicated with the hydrofining reactor entrance of hydrofining unit by pipeline; The first separating tank oil phase outlet is communicated with the liquid phase entrance on the raw gasline lighting end opening for feed of riser reactor and the absorption tower of absorption-stable system respectively by pipeline; The gaseous phase outlet of the first separating tank is communicated with the entrance of the second separating tank by being provided with the pipeline of rich gas compressor and condenser; The gaseous phase outlet of the second separating tank is communicated with the gas phase entrance on the absorption tower of absorption-stable system, and the oil phase outlet of the second separating tank is communicated with the desorption tower entrance of absorption-stable system;
Described absorption-stable system comprises absorption tower, desorption tower, reabsorber and stabilizer tower, the liquid phase entrance on described absorption tower is communicated with the outlet of the oil phase of described the first separating tank, the gas phase entrance on absorption tower is communicated with the gaseous phase outlet of described the second separating tank, the gaseous phase outlet on absorption tower is communicated with the gas phase entrance of reabsorber by pipeline, and the liquid-phase outlet on absorption tower is communicated with the entrance of the second separating tank by pipeline; The entrance of desorption tower is communicated with the oil phase outlet of described the second separating tank by pipeline, and the gaseous phase outlet of desorption tower is communicated with the entrance of the second separating tank by pipeline, and the liquid-phase outlet of desorption tower is communicated with stabilizer tower entrance by pipeline; Reabsorber liquid-phase outlet is communicated with the upper feeding mouth of separation column by pipeline; The gaseous phase outlet of stabilizer tower is communicated with the 3rd separating tank by being provided with the pipeline of condenser, and the 3rd separating tank separation obtains non-condensable gas and liquefied gas, obtains stablizing petroleum naphtha at the bottom of stabilizer tower;
Described hydrofining unit comprises hydrofining reactor, and the entrance of hydrofining reactor is communicated with the last running outlet at the bottom of described gasoline splitter tower by being provided with the pipeline of condenser, the outlet output last running gasoline of hydrofining reactor.
As optimal technical scheme, described riser reactor is unistage type riser reactor, bottom-up pre-lift gas entrance, catalyst feeds, stock oil opening for feed, turning oil opening for feed and the raw gasline lighting end opening for feed of being provided with of described riser reactor.
As optimal technical scheme, described riser reactor is two-part riser reactor, comprise the first riser reactor and the second riser reactor, the upper end of described the first riser reactor is communicated with finish separator, the upper end of described the second riser reactor is communicated with finish separator, the bottom-up pre-lift gas entrance that is provided with of the first riser reactor, catalyst feeds and stock oil opening for feed, the bottom-up pre-lift gas entrance that is provided with of the second riser reactor, catalyst feeds, turning oil opening for feed and raw gasline lighting end opening for feed, the solid phase outlet of finish separator is communicated with catalyst regenerator, catalyst regenerator is communicated with the catalyst feeds of the first riser reactor and the catalyst feeds of the second riser reactor respectively by regenerator sloped tube.
As optimal technical scheme, described hydrofining unit at least comprises a hydrofining reactor, a high-pressure separator and a circulating hydrogen compressor, the entrance of described hydrofining reactor is communicated with the last running outlet at the bottom of described gasoline splitter tower, the outlet of hydrofining reactor is communicated with high-pressure separator, the gaseous phase outlet of high-pressure separator is communicated with the entrance of circulating hydrogen compressor by pipeline, the outlet of circulating hydrogen compressor is communicated with the entrance of hydrofining reactor by pipeline, the liquid-phase outlet of high-pressure separator obtains refining last running gasoline, take-off equipment.
As optimal technical scheme, the gaseous phase outlet of separation column reflux inlet, recycle stock outlet, heavy gas oil outlet, solar oil outlet, upper feeding mouth, trim the top of column entrance and fractionator overhead at the bottom of bottom is upwards provided with slurry oil outlet, lower opening for feed, tower successively, the solar oil outlet of separation column is communicated with the liquid phase entrance of reabsorber.
As optimal technical scheme, the last running outlet at the bottom of gasoline splitter tower is also communicated with the trim the top of column entrance of separation column by pipeline.
As optimal technical scheme, the first separating tank oil phase outlet is also communicated with the liquid phase entrance of gasoline splitter tower top by pipeline.
As optimal technical scheme, described riser reactor is combined reactor, it consists of pre lift zone, conveying bed reaction zone and fast bed reaction zone from bottom to up, pre lift zone height accounts for 5% ~ 20% of total reactor height, carry bed reaction zone height to account for 30 ~ 60% of riser reactor total height, its diameter is 1.0 ~ 2.0 times of pre lift zone diameter; Fast bed reaction zone height accounts for 20 ~ 50% of riser reactor height, and its diameter is 1.5 ~ 5.0 times of conveying bed reaction zone diameter; Wherein, pre lift zone is provided with pre-lift gas entrance and catalyst feeds from bottom to up, carries bed reaction zone to be provided with from bottom to up stock oil opening for feed and turning oil opening for feed, and fast bed reaction zone is provided with raw gasline lighting end opening for feed.
As optimal technical scheme, described the second riser reactor is combined reactor, it consists of pre lift zone, conveying bed reaction zone and fast bed reaction zone from bottom to up, pre lift zone height accounts for 5% ~ 20% of total reactor height, carry bed reaction zone height to account for 10 ~ 40% of riser reactor total height, its diameter is 1.0 ~ 2.0 times of pre lift zone diameter; Fast bed reaction zone height accounts for 30 ~ 60% of riser reactor height, and its diameter is 1.5 ~ 5.0 times of conveying bed reaction zone diameter; Wherein, pre lift zone is provided with pre-lift gas entrance and catalyst feeds from bottom to up, carries bed reaction zone to be provided with turning oil opening for feed, and fast bed reaction zone is provided with raw gasline lighting end opening for feed.
As optimal technical scheme, the liquid-phase outlet of stabilizer tower is also communicated with the supplementary absorption agent entrance of absorption tower tower top by pipeline.
The invention provides the method that said apparatus carries out catalytic cracking and hydrofining combination producing clean gasoline, comprise the steps:
1) catalytic cracking
Between the stock oil opening for feed of riser reactor and turning oil opening for feed, be stock oil reaction zone, turning oil opening for feed and raw gasline lighting end opening for feed top are turning oil reaction zone, and raw gasline lighting end opening for feed top is petroleum naphtha reaction zone;
Fresh feed oil is preheated to after 150 ~ 300 ℃, from stock oil opening for feed injecting lift pipe reactor, with from catalyst regenerator out, the high-temperature regenerated catalyst that elevates through pre-lift gas contacts in stock oil reaction zone, carry out catalytic cracking reaction, reaction conditions is: 500 ~ 570 ℃ of temperature of reaction, agent oil quality is than 5 ~ 12, reaction times 1.0 ~ 2.0 s, reaction pressure 0.1 ~ 0.4 Mpa;
Turning oil heat exchange to 200 ~ 380 ℃, from turning oil opening for feed, enter riser reactor, in turning oil reaction zone contact reacts, reaction conditions is: 480 ~ 550 ℃ of temperature of reaction with the catalyzer coming from stock oil reaction zone, agent oil quality is than 20 ~ 40, reaction times 1.0 ~ 2.0 s;
The oil-phase component flowing out from the oil phase outlet of the first separating tank is preheated to 40 ~ 200 ℃, from the raw gasline lighting end opening for feed of riser reactor, inject, contact in petroleum naphtha reaction zone with the catalyzer coming from turning oil reaction zone, carry out catalytic cracking reaction, by the conversion of olefines in raw gasline lighting end, be isoparaffin and aromatic hydrocarbons, reaction conditions: 450 ~ 520 ℃ of temperature of reaction, agent oil quality is than 20 ~ 40, reaction times 1.0 ~ 5.0 s, reaction pressure 0.1 ~ 0.4 Mpa;
Reaction mass enters finish separator from riser reactor, and reclaimable catalyst enters catalyst regenerator coke burning regeneration after the stripping stage stripping of finish separator, and oil gas enters separation column from the gaseous phase outlet of finish separator;
2) fractionation and hydrogenation:
After separation column fractionation, gas-phase product enters gasoline splitter and is split into raw gasline lighting end and raw gasline last running; The hydrofining reactor that raw gasline last running enters hydrofining reaction unit contacts and carries out hydrogenation reaction with hydrogenation catalyst, obtains last running gasoline; Raw gasline lighting end enters the first separating tank after condensation, in the first separating tank after separation, the raw gasline lighting end opening for feed of oil-phase component part injecting lift pipe reactor, a part enters absorption tower as absorption agent, and gas phase composition enters the second separating tank after rich gas compressor compression and condensation;
3) absorb, stablize:
The gas phase composition that the second separating tank separation obtains enters absorption tower and absorbs, and oil-phase component enters desorption tower; Oil-phase component at the bottom of absorbing tower is introduced the second separating tank again and is carried out separation after condensation, and absorption tower tower top obtains gas phase composition and enters reabsorber; The gas phase composition of desorption tower tower top is introduced the second separating tank and is carried out separation after condensation, and the oil-phase component at the bottom of desorption tower tower enters stabilizer tower; At the bottom of the tower of reabsorber, liquid composition passes back into the upper feeding mouth of separation column;
Stabilizer tower top gaseous phase composition enters the 3rd separating tank after condensation, and separation obtains non-condensable gas and liquefied gas; At the bottom of stabilizer tower tower, liquid phase is for to stablize petroleum naphtha, and itself and last running gasoline are proportionally mixed to get clean gasoline.
The invention provides the method that said apparatus carries out catalytic cracking and hydrofining combination producing clean gasoline, comprise the steps:
1) catalytic cracking:
Between the turning oil opening for feed of the second riser reactor and raw gasline lighting end opening for feed, be turning oil reaction zone, raw gasline lighting end opening for feed top is petroleum naphtha reaction zone;
The fresh feed oil that will be preheated to 150 ~ 300 ℃ injects from the stock oil opening for feed of the first riser reactor, contact and carry out catalytic cracking reaction with the high-temperature regenerated catalyst coming from catalyst regenerator, reaction conditions is: 450 ~ 520 ℃ of temperature of reaction, agent oil quality is than 4 ~ 12, reaction pressure 0.1 ~ 0.4 Mpa, reaction times 0.8 ~ 2.0 s; Reacted oil gas enters finish separator with catalyzer and carries out the separated of finish; Catalyzer enters catalyst regenerator coke burning regeneration after stripping stage stripping, and oil gas enters separation column from the gaseous phase outlet of finish separator;
The turning oil of heat exchange to 200 ~ 380 ℃ injects the turning oil reaction zone of the second riser reactor from turning oil opening for feed, turning oil with from catalyst regenerator out, the high-temperature regenerated catalyst that elevates through pre-lift gas contacts and carries out catalytic cracking reaction in turning oil reaction zone, reaction conditions is: 540 ~ 600 ℃ of temperature of reaction, agent oil quality is than 8 ~ 20, reaction pressure 0.1 ~ 0.4 MPa, reaction times 0.5 ~ 1.5 s; After reaction, enter petroleum naphtha reaction zone;
The oil-phase component flowing out from the oil phase outlet of the first separating tank is preheated to 40 ~ 200 ℃ of raw gasline lighting end opening for feeds from the second riser reactor and injects, contact with the catalyzer coming from turning oil reaction zone and carry out catalytic cracking reaction and contact and carry out catalytic cracking reaction in petroleum naphtha reaction zone, reaction conditions is: 450 ~ 520 ℃ of temperature of reaction, agent oil quality is than 10 ~ 30, reaction pressure 0.1 ~ 0.4 MPa, reaction times 1 ~ 5.0 s; Reacted oil gas enters finish separator with catalyzer and carries out the separated of finish; Reclaimable catalyst enters catalyst regenerator coke burning regeneration after stripping stage stripping, and oil gas enters separation column from the gaseous phase outlet of finish separator;
2) fractionation and hydrogenation:
After separation column fractionation, gas-phase product enters gasoline splitter and is split into raw gasline lighting end and raw gasline last running; Raw gasline last running enters hydrofining reactor and carries out hydrogenation reaction, obtains last running gasoline; Raw gasline lighting end enters the first separating tank after condensation, in the first separating tank after separation, an oil-phase component part is injected the raw gasline lighting end opening for feed of the second riser reactor, a part enters absorption tower as absorption agent, and gas phase composition enters the second separating tank after rich gas compressor compression and condensation;
3) absorb, stablize:
The gas phase composition that the second separating tank separation obtains enters absorption tower and absorbs, and oil-phase component enters desorption tower; Oil-phase component at the bottom of absorbing tower is introduced the second separating tank and is carried out separation after condensation, and absorption tower tower top obtains gas phase composition and enters reabsorber; The gas phase composition of desorption tower tower top is introduced the second separating tank and is carried out separation after condensation, and the oil-phase component at the bottom of desorption tower tower enters stabilizer tower; At the bottom of the tower of reabsorber, liquid composition passes back into separation column;
Stabilizer tower top gaseous phase composition enters the 3rd separating tank after condensation, and separation obtains non-condensable gas and liquefied gas; At the bottom of stabilizer tower tower, liquid phase is for to stablize petroleum naphtha, and itself and last running gasoline are proportionally mixed to get clean gasoline.
As optimal technical scheme, separation column upwards obtains slurry oil, recycle stock, heavy gas oil and solar oil successively from bottom, solar oil injects the liquid phase entrance of reabsorber as absorption agent, and one of them of slurry oil and recycle stock or its mixture add the second riser reactor as turning oil.
As optimal technical scheme, the raw gasline last running that gasoline splitter obtains, a part enters hydrofining reactor and carries out hydrogenation reaction, and a part refluxes and enters separation column, at the bottom of a part passes back into the tower of gasoline splitter.
As optimal technical scheme, the oil-phase component that the first separating tank separation obtains, the raw gasline lighting end opening for feed of part injecting lift pipe reactor, a part enters the liquid phase entrance on absorption tower as absorption agent, and some flows into gasoline splitter tower top by back of pipeline.
Preferably, the catalyzer of step 1) catalytic cracking at least comprises one or more mixture of amorphous silicon aluminium catalyzer or molecular sieve catalyst or other type catalyst.
Further preferably, the catalyzer of step 1) catalytic cracking is that Y zeolite accounts for the catalyzer that the ratio of active ingredient is greater than 50%.
As optimal technical scheme, step 2) described hydrogenation catalyst can be the mixed catalyst of the polyfunctional catalyst arbitrary proportions such as catalyst for selectively hydrodesulfurizing or catalyst for selectively hydrodesulfurizing and isomery/aromizing, also above-mentioned two kinds of catalyzer can be seated in respectively in the different beds position of a reactor or the different reactor of series connection.
Preferably, in gasoline splitter, light and heavy fractions cutting temperature is 60 ~ 120 ℃.
As optimal technical scheme, at the bottom of the slurry oil outlet material partial reflux at the bottom of separation column tower enters separation column tower; At the bottom of last running outlet material partial reflux at the bottom of gasoline splitter tower enters gasoline splitter tower; At the bottom of liquid-phase outlet material partial reflux at the bottom of desorption tower tower enters desorption tower tower; At the bottom of at the bottom of stabilizer tower tower, liquid-phase outlet material partial reflux enters stabilizer tower tower.
By above technical scheme, the present invention at least tool has the following advantages:
1. owing to only having part lighting end gasoline to enter absorption-stable system, and stable petroleum naphtha has good assimilation effect, can reduce the load of absorption-stable system, reduces energy consumption;
2. be rich in the lighting end gasoline of alkene by catalytic cracking process upgrading, increased on the one hand the agent-oil ratio of cycle oil solid/liquid/gas reactions, promoted the conversion of heavy raw oil, the reactions such as hydrogen transference, isomerization and aromizing can occur on catalytic cracking an acidic catalyst is thereby that isoparaffin that octane value is higher and aromatic hydrocarbons can guarantee that gasoline octane rating does not reduce in the olefin(e) centent that reduces gasoline by conversion of olefines to petroleum naphtha on the other hand, it is low that this process is compared hydrogenation process running cost, and loss of octane number is little;
3. for the feature of China's gasoline high olefin content, after lighting end content of olefin in gasoline significantly reduces, also just significantly reduced the requirement to olefin saturated rate in hydro-upgrading process of last running gasoline, therefore last running gasoline adopts selective hydrodesulfurization can reach the requirement of state's IV gasoline standard, has overcome the deficiency of selective hydrodesulfurization technology aspect reduction content of olefin in gasoline.In addition reduced, the saturated loss of octane number also just having reduced in gasoline hydrogenation process of hydrogenation of alkene;
4. two processes of catalytic cracking and hydrofining that have been coupled are integrated into twice gasoline cutting process once, have further reduced energy consumption.
In sum, adopt the present invention not only can improve the feed stock conversion of catalytic cracking unit, reduce the cracking loss of gasoline upgrading process, obtain more petrol and diesel oil product, also can reduce loss of octane number, reduction hydrogen consumption and the system energy consumption of gasoline hydrofinishing process.It is little that the method device is changed, and simplified existing procedure, invests littlely, is easy to industrializing implementation.
Accompanying drawing explanation
Fig. 1 is device embodiment mono-schematic diagram of catalytic cracking of the present invention and hydrofining combination producing clean gasoline.
Fig. 2 is device embodiment bis-schematic diagram of catalytic cracking of the present invention and hydrofining combination producing clean gasoline.
Fig. 3 is device embodiment tri-schematic diagram of catalytic cracking of the present invention and hydrofining combination producing clean gasoline.
Fig. 4 is device embodiment tetra-schematic diagram of catalytic cracking of the present invention and hydrofining combination producing clean gasoline.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, can be implemented, but illustrated embodiment is not as a limitation of the invention so that those skilled in the art can better understand the present invention also.
Embodiment 1: two-part riser reactor
As shown in Figure 1, the device of the catalytic cracking that the present embodiment provides and hydrofining combination producing clean gasoline, comprises reaction-regeneration system rapidly, fractionating system, hydrofining unit and absorption-stable system,
Wherein, reaction-regeneration system rapidly comprises riser reactor, finish separator and catalyst regenerator,
Riser reactor is two-part riser reactor, comprise the first riser reactor 10 and the second riser reactor 11, the upper end of the first riser reactor 10 is communicated with finish separator 12, the upper end of the second riser reactor 11 is communicated with finish separator 12, the bottom-up pre-lift gas entrance 103 that is provided with of the first riser reactor 10, catalyst feeds 102 and stock oil opening for feed 101, the bottom-up pre-lift gas entrance 114 that is provided with of the second riser reactor 11, catalyst feeds 113, turning oil opening for feed 111 and raw gasline lighting end opening for feed 112, the solid phase outlet of finish separator 12 is communicated with catalyst regenerator 13, catalyst regenerator 13 is communicated with the catalyst feeds 102 of the first riser reactor 10 and the catalyst feeds 113 of the second riser reactor 11 respectively by pipeline.When processing inferior raw material coke yield is higher, the too much heat producing while burning in order to take away, can arrange external warmer 130 at catalyst regenerator 13.Finish separator 12 comprises that gas-solid settlement separator 122(bottom establishes stripping stage 125), efficient air solid separator 123 and settling vessel top revolve 124, the upper end outlet of the first riser reactor 10 and the second riser reactor 11 is communicated with efficient air solid separator 123, gas-solid settlement separator 122 and efficient air solid separator 123 revolve 124 with settling vessel top respectively and are communicated with, settling vessel top is revolved 124 gaseous phase outlet 121 and the solid phases that are provided with finish separator and is exported, 124 further separation oil and gas and catalyzer are revolved on settling vessel top, multilayer chev(e)ron baffle is housed in stripping stage conventionally and from bottom, passes into overheated steam and will be adsorbed on oil gas stripping catalyzer out.
Fractionating system comprises separation column 20, gasoline splitter 21, the first separating tank 22 and the second separating tank 23, the gaseous phase outlet 121 of finish separator is communicated with entrance 201 at the bottom of the tower of separation column 20, the gaseous phase outlet 202 of fractionator overhead is by being provided with the pipeline of condenser and the opening for feed 211 of gasoline splitter 21 is communicated with, the lighting end outlet 212 of gasoline splitter tower top is by being provided with the pipeline of condenser and the entrance 221 of the first separating tank 22 is communicated with, last running outlet 213 at the bottom of gasoline splitter 21 towers is communicated with hydrofining reactor 30 and fractionator overhead reflux inlet 204 by pipeline, the first separating tank 22 oil phase outlets 222 are communicated with the raw gasline lighting end opening for feed 112 of the second riser reactor 11 and the liquid phase entrance 401 on absorption tower 40 respectively by pipeline, the gaseous phase outlet 223 of the first separating tank 22 is communicated with the entrance of the second separating tank 23 by being provided with the pipeline of rich gas compressor 24 and condenser 25, the gaseous phase outlet 231 of the second separating tank is communicated with the gas phase entrance 402 on absorption tower 40, and the oil phase outlet 232 of the second separating tank is communicated with the entrance 411 of the desorption tower 41 of absorption-stable system, separation column 20 is upwards provided with the gaseous phase outlet 202 of slurry oil outlet 205, recycle stock outlet 206, heavy gas oil outlet 207, solar oil outlet 208 and fractionator overhead successively from bottom, the solar oil outlet 208 of separation column is communicated with the liquid phase entrance 423 of reabsorber 42 by pipeline 200, last running outlet 213 at the bottom of gasoline splitter 21 towers is also communicated with reflux inlet at the bottom of the trim the top of column entrance 204 of separation column 20 and the tower of gasoline splitter 21 respectively by pipeline, the first separating tank 22 oil phase outlets 222 are also communicated with the trim the top of column entrance 214 of gasoline splitter 21 by pipeline.
Hydrofining unit comprises hydrofining reactor 30, high-pressure separator 33 and circulating hydrogen compressor 34, the entrance 301 of hydrofining reactor 30 is communicated with the last running outlet 213 at the bottom of gasoline splitter tower by being provided with the pipeline of condenser 31, the outlet 302 of hydrofining reactor 30 is communicated with high-pressure separator 33 by being provided with the pipeline of condenser 32, the gaseous phase outlet of high-pressure separator 33 is communicated with circulating hydrogen compressor 34, and circulating hydrogen compressor 34 outlets are communicated with the entrance 301 of hydrofining reactor 30 by pipeline; The liquid-phase outlet of high-pressure separator 33 obtains refining last running gasoline.
Absorption-stable system comprises absorption tower 40, desorption tower 41, reabsorber 42 and stabilizer tower 43, the liquid phase entrance 401 on absorption tower 40 is communicated with the oil phase outlet 222 of the first separating tank 22, the gas phase entrance 402 on absorption tower 40 is communicated with the gaseous phase outlet 231 of the second separating tank 23, the gaseous phase outlet 403 on absorption tower 40 is communicated with the gas phase entrance 421 of reabsorber 42 by pipeline, and the liquid-phase outlet 404 on absorption tower 40 is communicated with the entrance of the second separating tank 23 by pipeline; The entrance 411 of desorption tower 41 is communicated with the oil phase outlet 232 of the second separating tank 23 by pipeline, the gaseous phase outlet 412 of desorption tower 41 is communicated with the entrance of the second separating tank 23 by pipeline, and the liquid-phase outlet 413 of desorption tower 41 is communicated with stabilizer tower 43 entrances 431 by pipeline; Reabsorber 42 liquid-phase outlets are communicated with the liquid phase entrance 203 of separation column 20 by pipeline 420; The gaseous phase outlet 432 of stabilizer tower 43 is communicated with the 3rd separating tank 45 by being provided with the pipeline of condenser 44, and the 3rd separating tank 45 separation obtain non-condensable gas 451 and liquefied gas 452, and the liquid-phase outlet 433 of stabilizer tower 43 obtains stablizing petroleum naphtha; The liquid-phase outlet 413 of desorption tower 41 is also communicated with desorption tower 41 bottom reflux inlets by pipeline; The liquid-phase outlet 433 of stabilizer tower 43 also by pipeline, supplements absorption agent entrance 405 respectively with the tower top on absorption tower 40 and stabilizer tower 43 bottom reflux inlets are communicated with; The liquid-phase outlet 404 on absorption tower 40 and the gaseous phase outlet 412 of desorption tower 41 are respectively by pipeline and be connected to pipeline communication the second separating tank 23 entrances, between rich gas compressor 24 and condenser 25; Liquefied gas 452 partial reflux enter the tower top of stabilizer tower 43.
Use the catalytic cracking of said apparatus and the method for hydrofining combination producing clean gasoline to be summarized as follows:
In conjunction with Fig. 1, the brief description of the process of the present embodiment is as follows: be preheated to the stock oil opening for feed 101 that the fresh heavy raw oil of 150 ~ 300 ℃ enters the first riser reactor 10 after high-temperature vapor atomization, regenerated catalyst from catalyst regenerator 13 is delivered to catalyst feeds 102 by regenerator sloped tube, by high-temperature regenerated catalyst, (catalyzer is conventional catalytic cracking catalyst from pre-lift gas entrance 103 for pre-lift steam or lifting dry gas, one or more the mixture that at least comprises amorphous silicon aluminium catalyzer or molecular sieve catalyst or other type catalyst, the catalyzer that the ratio that preferred shape-selective molecular sieve accounts for active ingredient is greater than 50%, active 50 ~ 75) elevate, in the first riser reactor 10, catalyzer and stock oil carry out contact reacts, 450 ~ 520 ℃ of this temperature of reaction, agent oil quality is than (being the mass ratio of catalyzer and stock oil) 4 ~ 12, under pressure 0.1 ~ 0.4 Mpa condition, react 0.8 ~ 2.0 s.After reaction, mix products enters gas-solid settlement separator 122 and settling vessel top and revolves 123 and carry out the separated of finish, oil gas enters separation column 20 from the gaseous phase outlet 121 of finish separator, coked catalyst enters stripping stage 125 through gas-solid settlement separator 122, enters catalyst regenerator 13 coke burning regenerations after stripping.
The turning oil self-circulation oil opening for feed 111(of heat exchange to 200 ~ 380 ℃ is generally recycle stock, wherein a kind of or its combination of slurry oil or heavy oil) enter the turning oil reaction zone of the second riser reactor, from catalyst regenerator 13, by regenerator sloped tube, be delivered to catalyst feeds 113, by high-temperature regenerated catalyst, (catalyzer is conventional catalytic cracking catalyst from pre-lift gas entrance 114 for pre-lift steam or lifting dry gas, one or more the mixture that at least comprises amorphous silicon aluminium catalyzer or molecular sieve catalyst or other type catalyst) elevate, turning oil and catalyzer are in turning oil reaction zone 116 contact reactss, 540 ~ 600 ℃ of temperature of reaction, agent oil quality is than 8 ~ 20, reaction pressure 0.1 ~ 0.4 MPa, reaction times 0.5 ~ 1.5 s, after reaction, enter petroleum naphtha reaction zone 115.
The oil-phase component (being mainly raw gasline lighting end) that the first separating tank 22 of fractionating system flows out is preheating to 40 ~ 200 ℃, enter the petroleum naphtha reaction zone 115 of the second riser reactor 11 that the second riser reactor 11 enters from raw gasline lighting end opening for feed 112, with the catalyzer from turning oil reaction zone 116, in petroleum naphtha reaction zone, 115 carry out contact reacts, in 450 ~ 520 ℃ of temperature of reaction, agent-oil ratio (mass ratio of catalyzer and petroleum naphtha charging) 10 ~ 30, under pressure 0.1 ~ 0.4 MPa condition, react after 1.0 ~ 5.0 s, entering efficient air solid separator 123 and settling vessel top revolves 124 and carries out the separated of finish, the oil gas obtaining after separation enters separation column 20 with main reaction oil gas after mixing.Reclaimable catalyst enters stripping stage 125 through gas-solid settlement separator 122, enters catalyst regenerator 13 coke burning regenerations after stripping.The regenerated catalyst that 130 pairs of the heat collectors that can increase regenerated catalyst when coke yield is higher enter reactive system carries out heat-obtaining cooling.
The light fractions of FCC naphtha that needs upgrading is at separation column 20 tower tops, to increase gasoline splitter 21 to realize.From the gaseous phase outlet 121 of finish separator oil gas out, enter separation column 20, after fractionation, separation column is isolated slurry oil (slurry oil outlet 205), recycle stock (recycle stock outlet 206), heavy gas oil (heavy gas oil outlet 207), solar oil (solar oil outlet 208) from lower to upper successively.By the gaseous phase outlet 202 at separation column 20 tops oil gas out, after condenser condenses is cooling, entered that gasoline splitter 21 carries out gently, the cutting of last running.The oil gas that the gaseous phase outlet 212 of gasoline splitter 21 tower tops flows out is further cooled to and after 40 ℃, enters the first separating tank 22 and carry out the separation of oil-water-gas through condenser.Water of condensation self-condensation water out 224 dischargers, the raw gasline lighting end that condensation is got off is flowed out from oil phase outlet 222, a part refluxes as the top of gasoline splitter 21, the raw gasline lighting end opening for feed 112 that a part is returned to the second riser reactor carries out catalytic cracking reaction, and the liquid phase entrance 401 of another part self-absorption tower enters the concrete allocation proportion of absorption tower 40(and can select according to actual needs).From uncooled oil gas out the first separating tank 22, from gaseous phase outlet 223, flow out after rich gas compressor 24 compressions, condenser 25 condensations, enter the second separating tank 23.
The lighting end of part raw gasline enters absorption tower 40 as absorption agent from liquid phase entrance 401, enters the second separating tank 23(high pressure separating tank together with the gas after the stripping gas (flowing out from gaseous phase outlet 412) that absorption tower 40 ends oil (flowing out from liquid-phase outlet 404) come with desorption tower 41 tower tops and rich gas compressor 24 compress after condenser 25 is cooling) carry out the separation of oil-water-gas.Sewage is discharged from sewage outlet 233, and condensed oil (discharging from oil phase outlet 232) enters desorption tower 41, and non-condensable gas (discharging from gaseous phase outlet 231) enters the gas phase entrance 402 on absorption tower 40.Absorption tower 40 top gas (discharging from gaseous phase outlet 403) enter reabsorber 42, and the absorption agent of reabsorber is the solar oil from separation column solar oil outlet 208.From reabsorber 42 tower tops, obtain dry gas (main component comprises: hydrogen, methane, ethane, ethene), at the bottom of tower, rich absorbent oil discharges from liquid-phase outlet 422 the liquid phase entrance 203 that enters separation column 20.At the bottom of desorption tower, oil is discharged and is entered stabilizer tower 43 from liquid-phase outlet 413.At the bottom of stabilizer tower, obtaining stablizing petroleum naphtha discharges from liquid-phase outlet 433, the tower top that flows into absorption tower as the supplementary absorption agent on absorption tower 40 through the cooling rear portion of condenser condenses supplements absorption agent entrance 405, a part as gasoline blend component 434 take-off equipments as gasoline blend component.Stablize tower top oil gas and discharge and after condenser 44 condensing coolings, enter the 3rd separating tank 45 from gaseous phase outlet 432, isolate non-condensable gas 451(and be mainly C2, C3) and liquefied gas 244(be mainly C3, C4).
At the bottom of gasoline splitter 21 towers, raw gasline last running is discharged from last running outlet 213, and a part refluxes as the top of separation column 20, and another part enters hydrofining reactor 30 after supercooler 31 is further cooling.Heavy naphtha after hydro-upgrading enters high-pressure separator 33 after water cooler 32 condensing coolings, and non-condensable gas (discharging from gaseous phase outlet 333) enters circulating hydrogen compressor 34, and compression cycle hydrogen enters hydrofining reactor after mixing with raw gasline last running.High-pressure separator 33 liquid-phase outlets obtain refining last running gasoline 304 take-off equipments as gasoline blend component.Gasoline blend component 434 obtains clean gasoline product after being in harmonious proportion with refining last running gasoline 304.
Embodiment 2:
Device of the present invention is shown in Fig. 2, and its structure is substantially the same manner as Example 1, and difference is, the combined reactor of the second riser reactor employing fast bed and conveying bed.As shown in Figure 2, the second riser reactor consists of pre lift zone, conveying bed reaction zone and fast bed reaction zone from bottom to up, and specific design requires as follows: total reactor height is 30 ~ 60m; Pre lift zone height accounts for 5% ~ 20% of total reactor height, carries bed reaction zone height to account for 30 ~ 60% of total reactor height, and its diameter is 1.0 ~ 2.0 times of pre lift zone diameter; Fast bed reaction zone height accounts for 20 ~ 50% of riser reactor height, and its diameter is 1.5 ~ 5.0 times of conveying bed reaction zone diameter; Wherein, pre lift zone is provided with pre-lift gas entrance 114 and catalyst feeds 113 from bottom to up, carries bed reaction zone to be provided with turning oil opening for feed 111, and fast bed reaction zone is provided with raw gasline lighting end opening for feed 112.
Fast bed is positioned at the top of carrying bed, and for the upgrading reaction of petroleum naphtha, fast bed can improve the bed density of catalyst of gasoline reaction zone, extends the gasoline upgrading time, promotes conversion of olefines in petroleum naphtha, further reduces the olefin(e) centent of petroleum naphtha.
Embodiment 3: unistage type riser reactor
As shown in Figure 3, the device of the catalytic cracking that the present embodiment provides and hydrofining combination producing clean gasoline, similar to embodiment 1, difference is that the riser reactor of the reaction-regeneration system of the present embodiment is unistage type riser reactor.
Knot Fig. 3, the difference of stream oriented device is described below:
The upper end of riser reactor 11 ' is communicated with finish separator 12 ', bottom-up pre-lift gas entrance 114 ', catalyst feeds 113 ', stock oil opening for feed 101 ', turning oil opening for feed 111 ' and the raw gasline lighting end opening for feed 112 ' of being provided with of riser reactor 11 ', the solid phase outlet of finish separator 12 ' is communicated with catalyst regenerator 13, and catalyst regenerator 13 is communicated with the catalyst feeds 113 ' of riser reactor 11 ' by pipeline;
Finish separator 12 ' comprises that gas-solid settlement separator 122 ' (stripping stage 125 ' is established in bottom), efficient air solid separator 123 ' push up and revolve 124 ' with settling vessel, efficient air solid separator 123 ' is communicated with the upper end outlet of riser reactor 11 ', efficient air solid separator 123 ' revolves 124 ' with settling vessel top and is communicated with, and settling vessel top is revolved 124 ' gaseous phase outlet 121 ' and the solid phase that is provided with finish separator and exported.
The gaseous phase outlet 121 ' of finish separator is communicated with 201 and is communicated with the gas phase entrance of separation column 20, the oil phase outlet 222 of the first separating tank 22 is communicated with the raw gasline lighting end opening for feed 112 ' of riser reactor 11 ' by pipeline.
The rest part structure of the present embodiment device is with embodiment 1.
Use the catalytic cracking of said apparatus and the technique of hydrofining combination producing clean gasoline to be summarized as follows:
At stock oil opening for feed 101 ', inject the fresh feed oil that is preheated to 150 ~ 300 ℃ of temperature, from the regenerated catalyst of catalyst regenerator 13, by regenerator sloped tube, be delivered to catalyst feeds 113 ', by high-temperature regenerated catalyst, (catalyzer is conventional catalytic cracking catalyst from pre-lift gas entrance 114 ' for pre-lift steam or lifting dry gas, one or more the mixture that at least comprises amorphous silicon aluminium catalyzer or molecular sieve catalyst or other type catalyst, the catalyzer that the ratio that preferred Y zeolite accounts for active ingredient is greater than 50%, active 50 ~ 75), stock oil and catalyzer are in stock oil reaction zone 116 ' contact reacts, reaction conditions is: 500 ~ 550 ℃ of temperature of reaction, agent oil quality is than (mass ratio of catalyzer and stock oil) 5 ~ 12, reaction times 1.0 ~ 2.0 s, reaction pressure 0.1 ~ 0.4 Mpa, after reaction, enter petroleum naphtha reaction zone.
Turning oil heat exchange to 200 ~ 380 ℃, from turning oil opening for feed, enter riser reactor, in turning oil reaction zone contact reacts, reaction conditions is: 480 ~ 550 ℃ of temperature of reaction with the catalyzer coming from stock oil reaction zone, agent oil quality is than 20 ~ 40, reaction times 1.0 ~ 2.0 s;
Part raw gasline lighting end (from the oil phase outlet 222 of the first separating tank 22) is preheated to 40 ~ 200 ℃ of temperature, the raw gasline lighting end opening for feed 112 ' of injecting lift pipe reactor, raw gasline lighting end with from the catalyzer of stock oil reaction zone in petroleum naphtha reaction zone 115 ' contact reacts, 450 ~ 520 ℃ of temperature of reaction, agent oil quality is than 20 ~ 40, reaction times 1.0 ~ 5.0 s, reaction pressure 0.1 ~ 0.4 Mpa.
Reacted oil gas enters finish separator 12 ' with catalyzer and carries out the separated of finish; Reclaimable catalyst enters revivifier coke burning regeneration after high-temperature vapor stripping; Reaction oil gas enters separation column 20.
The rest part operation of this technique is with embodiment 1.
Embodiment 4:
Device of the present invention is shown in Fig. 4, and its structure is substantially the same manner as Example 3, and difference is, the combined reactor of riser reactor employing conveying bed and fast bed.As shown in Figure 4, riser reactor consists of pre lift zone, conveying bed reaction zone and fast bed reaction zone from bottom to up, and specific design requires as follows: total reactor height is 10 ~ 40m; Pre lift zone height accounts for 5% ~ 20% of total reactor height, carries bed reaction zone height to account for 10 ~ 40% of total reactor height, and its diameter is 1.0 ~ 2.0 times of pre lift zone diameter; Fast bed reaction zone height accounts for 30 ~ 60% of riser reactor height, and its diameter is 1.5 ~ 5.0 times of conveying bed reaction zone diameter; Wherein, pre lift zone is provided with pre-lift gas entrance 114 ', catalyst feeds 113 ' from bottom to up, carry bed reaction zone to be provided with from bottom to up stock oil opening for feed 101 ' and turning oil opening for feed 111 ', fast bed reaction zone is provided with raw gasline lighting end opening for feed 112 '.
Fast bed is positioned at the top of carrying bed, and for the upgrading reaction of petroleum naphtha, fast bed can improve the bed density of catalyst of gasoline reaction zone, extends the gasoline upgrading time, promotes conversion of olefines in petroleum naphtha, further reduces the olefin(e) centent of petroleum naphtha.
Embodiment 5:
For verifying part effect of the present invention, on catalytic cracking riser pilot plant, carried out petroleum naphtha freshening upgrading test (technical process as described in Example 1), the catalyzer of catalyst cracker is certain refinery heavy oil catalytically cracking equipment poiser, active ingredient is Y zeolite, the stock oil of the first riser reactor 10 is CGO, and character is listed in table 1.The charging of the turning oil opening for feed 111 of the second riser reactor 11 is the heavy oil fraction (recycle stock and slurry oil) obtaining after true boiling point distillation cuts out petrol and diesel oil cut in separation column 20.The freshening ratio that passes back into the raw gasline lighting end (cutting temperature is 70 ℃, and wherein lighting end accounts for 45 wt.%) of the raw gasline lighting end opening for feed 112 of the second riser reactor 11 from the first separating tank 22 accounts for 54% of two sections of turning oil inlet amounies; On hydrofining pilot plant, carried out the hydrofining test of heavy petrol, Hydrobon catalyst is catalyst for selective hydrodesulfurizationof of gasoline, and active ingredient is Co-Mo, and operational condition and experimental result are listed in table 2.
Comparative example 1:
For effect of the present invention is better described, on catalytic cracking riser pilot plant, carried out not carrying out the conventional two-stage riser fluid catalytic cracking test of petroleum naphtha freshening operation, be that fractionating system is not established gasoline splitter, all raw gasline all enters absorbing-stabilizing system, at the bottom of stabilizer tower, obtain stable gasoline, on riser reactor without petroleum naphtha opening for feed.It is certain refinery heavy oil catalytically cracking equipment poiser (with embodiment 5) that experiment adopts catalyzer, the first riser tube raw material is CGO, and the second riser tube raw material is the heavy oil fraction that after one section of reaction, product liquid obtains after true boiling point distillation cuts out petrol and diesel oil cut; On hydrofining pilot plant, carried out the hydrofining test of full distillation gasoline, Hydrobon catalyst is catalyst for selective hydrodesulfurizationof of gasoline, and active ingredient is Co-Mo, and operational condition and experimental result are listed in table 2.
As can be seen from Table 2, adopt after the present invention, heavy oil conversion rate improves nearly 4 percentage points, and petrol and diesel oil yield improves nearly 1 percentage point, and liquid yield (liquefied gas+gasoline+diesel oil) improves 2.2 percentage points.In embodiment 5, due to the alkene in petroleum naphtha, on catalytic cracking catalyst, there is the reactions such as hydrogen transference, isomerization and aromizing, reduced the olefin(e) centent of gasoline and be translated into isoparaffin and the aromatic component with higher octane.And content of olefin in gasoline will exceed 16 percentage points in comparative example 1, due to full distillation gasoline is carried out to hydrofining, being difficult to avoid the active high small molecules end alkene of partial hydrogenation saturated is low-octane normal paraffin, has therefore reduced the overall octane value of gasoline.
Table 1 stock oil character
Table 2 operational condition and experimental result contrast
The above embodiment is only the preferred embodiment for absolutely proving that the present invention lifts, and protection scope of the present invention is not limited to this.Being equal to that those skilled in the art do on basis of the present invention substitutes or conversion, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. a device for catalytic cracking and hydrofining combination producing clean gasoline, is characterized in that, comprises reaction-regeneration system rapidly, fractionating system, and absorption-stable system and hydrofining unit,
Wherein, reaction-regeneration system rapidly comprises riser reactor, finish separator and catalyst regenerator, the upper end of described riser reactor is communicated with finish separator, bottom-up pre-lift gas entrance, catalyst feeds, heavy oil feed mouth and the raw gasline lighting end opening for feed of being provided with successively of riser reactor, the solid phase outlet of finish separator is communicated with catalyst regenerator, and catalyst regenerator is communicated with the catalyst feeds of riser reactor by regenerator sloped tube;
Fractionating system comprises separation column, gasoline splitter, the first separating tank and the second separating tank, the gaseous phase outlet of finish separator is communicated with entrance at the bottom of the tower of separation column, the gaseous phase outlet of fractionator overhead is by being provided with the pipeline of condenser and the gas phase entrance of gasoline splitter is communicated with, the lighting end outlet of gasoline splitter tower top is communicated with the entrance of the first separating tank by being provided with the pipeline of condenser, and the last running outlet at the bottom of gasoline splitter tower is communicated with the hydrofining reactor entrance of hydrofining unit by pipeline; The first separating tank oil phase outlet is communicated with the liquid phase entrance on the raw gasline lighting end opening for feed of riser reactor and the absorption tower of absorption-stable system respectively by pipeline; The gaseous phase outlet of the first separating tank is communicated with the entrance of the second separating tank by being provided with the pipeline of rich gas compressor and condenser; The gaseous phase outlet of the second separating tank is communicated with the gas phase entrance on the absorption tower of absorption-stable system, and the oil phase outlet of the second separating tank is communicated with the desorption tower entrance of absorption-stable system;
Described absorption-stable system comprises absorption tower, desorption tower, reabsorber and stabilizer tower, the liquid phase entrance on described absorption tower is communicated with the outlet of the oil phase of described the first separating tank, the gas phase entrance on absorption tower is communicated with the gaseous phase outlet of described the second separating tank, the gaseous phase outlet on absorption tower is communicated with the gas phase entrance of reabsorber by pipeline, and the liquid-phase outlet on absorption tower is communicated with the entrance of the second separating tank by pipeline; The entrance of desorption tower is communicated with the oil phase outlet of described the second separating tank by pipeline, and the gaseous phase outlet of desorption tower is communicated with the entrance of the second separating tank by pipeline, and the liquid-phase outlet of desorption tower is communicated with stabilizer tower entrance by pipeline; Reabsorber liquid-phase outlet is communicated with the upper feeding mouth of separation column by pipeline; The gaseous phase outlet of stabilizer tower is communicated with the 3rd separating tank by being provided with the pipeline of condenser, and the 3rd separating tank separation obtains non-condensable gas and liquefied gas, obtains lighting end gasoline at the bottom of stabilizer tower;
Described hydrofining unit comprises hydrofining reactor, and the entrance of hydrofining reactor is communicated with the last running outlet at the bottom of described gasoline splitter tower by being provided with the pipeline of condenser, the outlet output last running gasoline of hydrofining reactor.
2. device according to claim 1, it is characterized in that, described riser reactor is unistage type riser reactor, bottom-up pre-lift gas entrance, catalyst feeds, stock oil opening for feed, turning oil opening for feed and the raw gasline lighting end opening for feed of being provided with of described riser reactor.
3. device according to claim 1, it is characterized in that, described riser reactor is two-part riser reactor, comprise the first riser reactor and the second riser reactor, the upper end of described the first riser reactor is communicated with finish separator, the upper end of described the second riser reactor is communicated with finish separator, the bottom-up pre-lift gas entrance that is provided with of the first riser reactor, catalyst feeds and stock oil opening for feed, the bottom-up pre-lift gas entrance that is provided with of the second riser reactor, catalyst feeds, turning oil opening for feed and raw gasline lighting end opening for feed, the solid phase outlet of finish separator is communicated with catalyst regenerator, catalyst regenerator is communicated with the catalyst feeds of the first riser reactor and the catalyst feeds of the second riser reactor respectively by regenerator sloped tube.
4. according to the device described in claim 1 ~ 3 any one, it is characterized in that, described hydrofining unit at least comprises a hydrofining reactor, one high-pressure separator and a circulating hydrogen compressor, the entrance of described hydrofining reactor is communicated with the last running outlet at the bottom of described gasoline splitter tower, the outlet of hydrofining reactor is communicated with high-pressure separator, the gaseous phase outlet of high-pressure separator is communicated with the entrance of circulating hydrogen compressor by pipeline, the outlet of circulating hydrogen compressor is communicated with the entrance of hydrofining reactor by pipeline, the liquid-phase outlet of high-pressure separator obtains refining last running gasoline, take-off equipment.
5. device according to claim 4, it is characterized in that, the gaseous phase outlet of separation column reflux inlet, recycle stock outlet, heavy gas oil outlet, solar oil outlet, upper feeding mouth, trim the top of column entrance and fractionator overhead at the bottom of bottom is upwards provided with slurry oil outlet, lower opening for feed, tower successively, the solar oil outlet of separation column is communicated with the liquid phase entrance of reabsorber; Last running outlet at the bottom of gasoline splitter tower is also communicated with the trim the top of column entrance of separation column by pipeline; The first separating tank oil phase outlet is also communicated with the liquid phase entrance of gasoline splitter tower top by pipeline; The liquid-phase outlet of stabilizer tower is also communicated with the supplementary absorption agent entrance of absorption tower tower top by pipeline.
6. device according to claim 2, it is characterized in that, described riser reactor is combined reactor, it consists of pre lift zone, conveying bed reaction zone and fast bed reaction zone from bottom to up, pre lift zone height accounts for 5% ~ 20% of total reactor height, carry bed reaction zone height to account for 30 ~ 60% of riser reactor total height, its diameter is 1.0 ~ 2.0 times of pre lift zone diameter; Fast bed reaction zone height accounts for 20 ~ 50% of riser reactor height, and its diameter is 1.5 ~ 5.0 times of conveying bed reaction zone diameter; Wherein, pre lift zone is provided with pre-lift gas entrance and catalyst feeds from bottom to up, carries bed reaction zone to be provided with from bottom to up stock oil opening for feed and turning oil opening for feed, and fast bed reaction zone is provided with raw gasline lighting end opening for feed.
7. device according to claim 3, it is characterized in that, described the second riser reactor is combined reactor, it consists of pre lift zone, conveying bed reaction zone and fast bed reaction zone from bottom to up, pre lift zone height accounts for 5% ~ 20% of total reactor height, carry bed reaction zone height to account for 10 ~ 40% of riser reactor total height, its diameter is 1.0 ~ 2.0 times of pre lift zone diameter; Fast bed reaction zone height accounts for 30 ~ 60% of riser reactor height, and its diameter is 1.5 ~ 5.0 times of conveying bed reaction zone diameter; Wherein, pre lift zone is provided with pre-lift gas entrance and catalyst feeds from bottom to up, carries bed reaction zone to be provided with turning oil opening for feed, and fast bed reaction zone is provided with raw gasline lighting end opening for feed.
8. device carries out the method for catalytic cracking and hydrofining combination producing clean gasoline according to claim 2, it is characterized in that, comprises the steps:
1) catalytic cracking
Between the stock oil opening for feed of riser reactor and turning oil opening for feed, be stock oil reaction zone, turning oil opening for feed and raw gasline lighting end opening for feed top are turning oil reaction zone, and raw gasline lighting end opening for feed top is petroleum naphtha reaction zone;
Fresh feed oil is preheated to after 150 ~ 300 ℃, from stock oil opening for feed injecting lift pipe reactor, with from catalyst regenerator out, the high-temperature regenerated catalyst that elevates through pre-lift gas contacts in stock oil reaction zone, carry out catalytic cracking reaction, reaction conditions is: 500 ~ 570 ℃ of temperature of reaction, agent oil quality is than 5 ~ 12, reaction times 1.0 ~ 2.0 s, reaction pressure 0.1 ~ 0.4 Mpa;
Turning oil heat exchange to 200 ~ 380 ℃, from turning oil opening for feed, enter riser reactor, in turning oil reaction zone contact reacts, reaction conditions is: 480 ~ 550 ℃ of temperature of reaction with the catalyzer coming from stock oil reaction zone, agent oil quality is than 20 ~ 40, reaction times 1.0 ~ 2.0 s;
The oil-phase component flowing out from the oil phase outlet of the first separating tank is preheated to 40 ~ 200 ℃, from the raw gasline lighting end opening for feed of riser reactor, inject, contact in petroleum naphtha reaction zone with the catalyzer coming from turning oil reaction zone, carry out catalytic cracking reaction, by the conversion of olefines in raw gasline lighting end, be isoparaffin and aromatic hydrocarbons, reaction conditions: 450 ~ 520 ℃ of temperature of reaction, agent oil quality is than 20 ~ 40, reaction times 1.0 ~ 5.0 s, reaction pressure 0.1 ~ 0.4 Mpa;
Reaction mass enters finish separator from riser reactor, and reclaimable catalyst enters catalyst regenerator coke burning regeneration after the stripping stage stripping of finish separator, and oil gas enters separation column from the gaseous phase outlet of finish separator;
2) fractionation and hydrogenation:
After separation column fractionation, gas-phase product enters gasoline splitter and is split into raw gasline lighting end and raw gasline last running; The hydrofining reactor that raw gasline last running enters hydrofining reaction unit contacts and carries out hydrogenation reaction with hydrogenation catalyst, obtains last running gasoline; Raw gasline lighting end enters the first separating tank after condensation, in the first separating tank after separation, the raw gasline lighting end opening for feed of oil-phase component part injecting lift pipe reactor, a part enters absorption tower as absorption agent, and gas phase composition enters the second separating tank after rich gas compressor compression and condensation;
3) absorb, stablize:
The gas phase composition that the second separating tank separation obtains enters absorption tower and absorbs, and oil-phase component enters desorption tower; Oil-phase component at the bottom of absorbing tower is introduced the second separating tank again and is carried out separation after condensation, and absorption tower tower top obtains gas phase composition and enters reabsorber; The gas phase composition of desorption tower tower top is introduced the second separating tank and is carried out separation after condensation, and the oil-phase component at the bottom of desorption tower tower enters stabilizer tower; At the bottom of the tower of reabsorber, liquid composition passes back into the upper feeding mouth of separation column;
Stabilizer tower top gaseous phase composition enters the 3rd separating tank after condensation, and separation obtains non-condensable gas and liquefied gas; At the bottom of stabilizer tower tower, liquid phase is for to stablize petroleum naphtha, and itself and last running gasoline are proportionally mixed to get clean gasoline.
9. described in claim 3, device carries out the method for catalytic cracking and hydrofining combination producing clean gasoline, it is characterized in that, comprises the steps:
1) catalytic cracking:
Between the turning oil opening for feed of the second riser reactor and raw gasline lighting end opening for feed, be turning oil reaction zone, raw gasline lighting end opening for feed top is petroleum naphtha reaction zone;
The fresh feed oil that will be preheated to 150 ~ 300 ℃ injects from the stock oil opening for feed of the first riser reactor, contact and carry out catalytic cracking reaction with the high-temperature regenerated catalyst coming from catalyst regenerator, reaction conditions is: 450 ~ 520 ℃ of temperature of reaction, agent oil quality is than 4 ~ 12, reaction pressure 0.1 ~ 0.4 Mpa, reaction times 0.8 ~ 2.0 s; Reacted oil gas enters finish separator with catalyzer and carries out the separated of finish; Catalyzer enters catalyst regenerator coke burning regeneration after stripping stage stripping, and oil gas enters separation column from the gaseous phase outlet of finish separator;
The turning oil of heat exchange to 200 ~ 380 ℃ injects the turning oil reaction zone of the second riser reactor from turning oil opening for feed, turning oil with from catalyst regenerator out, the high-temperature regenerated catalyst that elevates through pre-lift gas contacts and carries out catalytic cracking reaction in turning oil reaction zone, reaction conditions is: 540 ~ 600 ℃ of temperature of reaction, agent oil quality is than 8 ~ 20, reaction pressure 0.1 ~ 0.4 MPa, reaction times 0.5 ~ 1.5 s; After reaction, enter petroleum naphtha reaction zone;
The oil-phase component flowing out from the oil phase outlet of the first separating tank is preheated to 40 ~ 200 ℃ of raw gasline lighting end opening for feeds from the second riser reactor and injects, contact with the catalyzer coming from turning oil reaction zone and carry out catalytic cracking reaction and contact and carry out catalytic cracking reaction in petroleum naphtha reaction zone, reaction conditions is: 450 ~ 520 ℃ of temperature of reaction, agent oil quality is than 10 ~ 30, reaction pressure 0.1 ~ 0.4 MPa, reaction times 1 ~ 5.0 s; Reacted oil gas enters finish separator with catalyzer and carries out the separated of finish; Reclaimable catalyst enters catalyst regenerator coke burning regeneration after stripping stage stripping, and oil gas enters separation column from the gaseous phase outlet of finish separator;
2) fractionation and hydrogenation:
After separation column fractionation, gas-phase product enters gasoline splitter and is split into raw gasline lighting end and raw gasline last running; Raw gasline last running enters hydrofining reactor and carries out hydrogenation reaction, obtains last running gasoline; Raw gasline lighting end enters the first separating tank after condensation, in the first separating tank after separation, an oil-phase component part is injected the raw gasline lighting end opening for feed of the second riser reactor, a part enters absorption tower as absorption agent, and gas phase composition enters the second separating tank after rich gas compressor compression and condensation;
3) absorb, stablize:
The gas phase composition that the second separating tank separation obtains enters absorption tower and absorbs, and oil-phase component enters desorption tower; Oil-phase component at the bottom of absorbing tower is introduced the second separating tank and is carried out separation after condensation, and absorption tower tower top obtains gas phase composition and enters reabsorber; The gas phase composition of desorption tower tower top is introduced the second separating tank and is carried out separation after condensation, and the oil-phase component at the bottom of desorption tower tower enters stabilizer tower; At the bottom of the tower of reabsorber, liquid composition passes back into separation column;
Stabilizer tower top gaseous phase composition enters the 3rd separating tank after condensation, and separation obtains non-condensable gas and liquefied gas; At the bottom of stabilizer tower tower, liquid phase is for to stablize petroleum naphtha, and itself and last running gasoline are proportionally mixed to get clean gasoline.
10. method according to claim 8 or claim 9, it is characterized in that, separation column upwards obtains slurry oil, recycle stock, heavy gas oil and solar oil successively from bottom, solar oil injects the liquid phase entrance of reabsorber as absorption agent, and one of them of slurry oil and recycle stock or its mixture add the second riser reactor as turning oil; The raw gasline last running that gasoline splitter obtains, a part enters hydrofining reactor and carries out hydrogenation reaction, and a part refluxes and enters separation column, at the bottom of a part passes back into the tower of gasoline splitter; The oil-phase component that the first separating tank separation obtains, the raw gasline lighting end opening for feed of a part of injecting lift pipe reactor, a part enters the liquid phase entrance on absorption tower as absorption agent, and some flows into gasoline splitter tower top by back of pipeline.
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