CN103059955B - Method for producing clean gasoline from catalytic cracking gasoline - Google Patents
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Abstract
The invention discloses a method for producing clean gasoline from catalytic cracking gasoline. The method comprises: leading a light fraction lateral line from a stabilization tower middle part of a catalytic cracking absorption-stabilization unit, and conducting light and heavy fraction cutting separation on crude gasoline to obtain light fractions and heavy fractions; subjecting light fractions to alkali-free deodorization, letting the deodorized light fractions and hydrocarbon-rich diesel oil from the absorption-stabilization unit enter a disulfide fractionating tower, thus obtaining light gasoline from the fractionating tower top and extracting medium gasoline from a fractionating tower middle lateral line, mixing the medium gasoline with the heavy fractions obtained at the stabilization tower bottom of the absorption-stabilization unit, then passing the mixture through a hydrogenation protection reactor and a hydrodesulfurization reactor in order, then subjecting the hydrogenated liquid product to gas stripping, and mixing the product with the refined light gasoline, thus obtaining a clean gasoline product or a blending component. The method provided in the invention not only can decrease the mercaptan sulfur content and the total sulfur content of catalytic cracking gasoline, produce a clean gasoline product with qualified sulfur and olefin content, but also can significantly reduce the energy consumption of production equipment and increase the economic benefits of a catalytic cracking gasoline desulfurization device.
Description
Technical field
The present invention relates to the processing method that a kind of light hydrocarbons is refining, be more particularly a kind of method that clean gasoline produced by catalytically cracked gasoline, especially reduce catalytically cracked gasoline mercaptan sulfur content, produce the method for clean gasoline.
Technical background
Along with the fast development of automotive industry and the increasingly stringent of environmental requirement, the production of low-sulfur, super low sulfur clean gasoline has become petroleum refining industry's development inexorable trend.From the formation of the current gasoline pool of China, catalytically cracked gasoline component accounts for 75% ~ 80%.And the sulphur content of catalytically cracked gasoline is usually at 100 ~ 2000 μ g/g, the highest to the contribution rate of the sulphur content in China's gasoline pool, reach more than 98%.And, along with the raw material of catalyzed cracking processing is to heaviness future development, increase causing the sulphur content in catalytically cracked gasoline further.Therefore, catalytically cracked gasoline desulfurization just becomes the gordian technique that must solve in Technology for Producing Clean Gasoline.
The technology of existing reduction sulfur content of catalytic cracking gasoline is a lot, roughly can be summed up as catalytically cracked material weighted BMO spaces, being combined of catalytically cracked gasoline aftertreatment and this this two kinds of modes.Although these technology can reduce sulphur content and olefin(e) centent significantly, due to must be saturated in a large number by having high-octane olefin component in hydrogenation process, cause the loss of octane number of gasoline products very large, and plant running costly.
EP0940464 discloses a kind of processing method of catalytically cracked gasoline desulfurization, catalytically cracked gasoline is cut into gently, in, weigh three kinds of cuts, the first bed that first last running enter the fixed-bed reactor with two beds carries out hydrogenating desulfurization, and after its desulfurization, reaction product and middle cut export to be mixed at the first bed and enter the second bed and enter hydrodesulfurization reaction.The method is based on the sulphur content difference of the cut of the different boiling range scope of catalytically cracked gasoline, different fractions carries out the hydrogenating desulfurization of different depths, be conducive to the sulphur content reducing product gasoline, but hydrogenation process olefin saturated rate is higher, causes product gasoline loss of octane number excessive.
US5399258 discloses a kind of gasoline modifying method, and first paragraph is after hydrogenation desulfurization and denitrogenation, olefins hydrogenation, and the intermediate product obtained directly enters second segment and carries out octane value recovering reaction.The temperature of reaction of first paragraph is higher, maintains an equal level with the temperature of reaction of second segment.Because the temperature of reaction of first paragraph is too high, cause final product to produce a large amount of mercaptan sulfur, temperature is higher, and the mercaptan sulfur of generation is more.
CN101492606A provides a kind of FCC gasoline hydrodesulfurizationprocess process producing low thioalcohol product, the hydrocarbon stream comprising sulfide is fed to the catalytic distillation reactor with one or more hydrodesulfurizationreaction reaction zone; Hydrogen is fed to catalytic distillation reactor; Simultaneously in catalytic distillation reactor: hydrocarbon stream is fractionated into last running and lighting end; Hydrogen is made to contact to form H with lighting end
2the lighting end that S and sulphur content are lowered; Reclaim as the lighting end of overhead product, H
2s and hydrogen; Reclaim last running; Overhead product is heated to 500 ℉ ~ 700 ℉; The overhead product of heating and hydrogen are fed to high-temperature low-pressure reactor, to form H
2the reaction effluent that S and sulphur content are lowered; Separating reaction effluent, H
2s and unreacted hydrogen, to form light ends fractionation and to comprise H
2the cut of S and hydrogen; A part for light ends fractionation is recycled to catalytic distillation reactor.The method effectively can reduce the thio-alcohol sulphur in product gasoline, but operation more complicated, control not easily to stablize.
USP6024865 discloses a kind of gasoline alkylation desulfuration method, first gasoline is divided into light, weigh two cuts, then carry out alkylated reaction respectively, reach the object of desulfurization.The method regulates alkylation conditions for the sulphidic species contained in gasoline fraction, the alkene that lighting end utilizes self to contain carries out alkylated reaction under comparatively gentle condition, and last running carries out alkylated reaction by the alkene of additional C3-C5 or alcohol under comparatively exacting terms.But reaction process is comparatively complicated, additional alkene or alcohol too increase operation easier.
CN101220295A is catalytically cracked gasoline and diesel oil coupled desulfurization device and method, the method is by a thiophenic sulfur alkylation reactor, by the sulphur transfer in catalytically cracked gasoline in high boiling sulfide, then sulphur transfer separation column is entered together with catalytic cracking diesel oil, tower top obtains the gasoline of sulphur transfer, and the sulfur-containing diesel extracted out at the bottom of tower removes diesel fuel desulfurization device.This processing method realizes the sulphur transfer in gasoline by alkylated reaction, but the degree of depth of gasoline desulfur is limited, and need to attract diesel oil from catalytic cracking diesel oil storage tank, again petrol and diesel oil is separated arranging special separation column after the petrol and diesel oil Product mix of catalytic cracking fractionating section, the energy consumption of device and the corresponding rising of investment.
Dissimilar catalytic cracking unit is all made up of reaction-regeneration system, fractionating system and absorption-stable system.Fractionating system is catalytic cracking main fractionating tower mainly, and the high-temperature oil gas that reaction-regeneration system comes is divided into different products in main fractionating tower, and main fractionating tower tower top goes out rich gas and raw gasline; Side line extracts solar oil, heavy gas oil and recycle stock out from top to bottom successively; Catalytically cracked oil is extracted out at the bottom of tower.Absorbing-stabilizing system, primarily of absorption tower, desorption tower and stabilizer tower composition, utilizes the method for absorption and rectifying that rich gas and raw gasline are separated into dry gas, liquefied gas and stable gasoline.Under the situation of quality product and environmental requirement increasingly stringent, the product (comprising dry gas, liquefied gas, gasoline, diesel oil) that catalytic cracking obtains all needs just can send as market products after hydrotreatment (mainly hydrogenating desulfurization).Stable gasoline is wherein the main source of motor spirit, and catalytic cracking stable gasoline desulfurization technology is then the gordian technique of clean gasoline production.
In existing catalytic cracking stable gasoline desulfurization technology, mostly become heavily in the trend incrementally distributed according to the sulphur content of catalytic cracking stable gasoline with cut, sulphur mainly concentrates in last running, and the sulphur content of particularly >90 DEG C of last running obviously increases, and olefin(e) centent becomes heavily in falling progressively formula distribution trend with cut, alkene mainly concentrates in lighting end, particularly the olefin(e) centent of >90 DEG C of last running obviously reduces, alkene is enriched in the characteristic in <90 DEG C of lighting end, in order to ensure gasoline octane rating loss reduction after the desulfurization of catalytic cracking stable gasoline, the technology of usual employing is: be divided into lighting end gasoline and last running gasoline by catalytic cracking stable gasoline or through the catalytic cracking stable gasoline of alkali-free sweetening by certain cut point, lighting end gasoline carries out mercaptan removal process, heavy naphtha carries out hydrogenating desulfurization, and then the two mixing is gone to gasoline concoction pond as product gasoline.Prior art is feasible for producing the gasoline meeting sulphur content < 150 μ g/g or sulphur content < 50 μ g/g, but what require quality of gasoline upgrading along with environmental regulation improves constantly, production sulphur content < 10 μ g/g, particularly mercaptan sulfur content < 5 μ g/g super low sulfur clean gasoline has been trend of the times.Though existing technology can meet production requirement, the severity produced will significantly rise, and the cycle of operation of device and turndown ratio will reduce, and the economic benefit of device can be had a strong impact on.In catalytic cracking stable gasoline particularly after alkali-free sweetening, lower boiling mercaptan sulfur changes into high boiling disulphide, in weight gasoline splitter, be difficult to the mercaptan sulfur of light gasoline fraction to remove, then have impact on mercaptan sulfur and the total sulfur content of blend gasoline.
During current oil refining is produced, catalytic cracking unit and refining catalytic gasoline device are respective independently two covering devices, the stable gasoline that catalytic cracking unit is produced is sent to tank field, extracted out by pump again and send naphtha-treating plant to, to reduce sulphur content wherein and olefin(e) centent produces the clean gasoline product met the demands.In this Production Flow Chart, catalytically cracked gasoline may touch oxygen, causes sulfide wherein, alkene and oxygen to react and generates various coke precursor, causes naphtha-treating plant interchanger and reactor bed top coking phenomenon.In addition, the catalytic diesel oil of catalytic cracking unit, slurry oil are also carrying devices after cooling.Form production process route longer, work flow plant energy consumption is higher.And the heat of catalytic cracking process is more rich, be commonly used to the steam that refinery's needs occur, but the heat of major part less than 300 DEG C can not make full use of, and also add device cooling load.
Therefore, catalytic cracking unit is combined more closely with Gasoline hydrofining unit, utilize existing process production techniques, the sulphur content realizing catalytically cracked gasoline touches the mark requirement, and the mercaptan sulfur content particularly realizing light gasoline fraction meets index request; And the abundant Appropriate application of heat between implement device, reduce the unit consumption of energy of device, increase the economic benefit of device, the clean gasoline product producing the gasoline quality index meeting increasingly stringent with minimum consumption has very important realistic meaning.
Summary of the invention
For the deficiencies in the prior art and real need of production, the invention provides a kind of method that clean gasoline produced by catalytically cracked gasoline, especially reduce catalytically cracked gasoline mercaptan sulfur content, produce the sulfur method of clean gasoline.The inventive method not only can reduce catalytically cracked gasoline mercaptan sulfur and total sulfur content, produces sulphur and the qualified clean gasoline product of olefin(e) centent, and can obviously reduce production equipment energy consumption, increase the economic benefit of catalytically cracked gasoline desulfurizer.
The method of clean gasoline produced by catalytically cracked gasoline provided by the invention, comprises the following steps:
(1) catalytically cracked gasoline obtains lighting end, last running in the stabilizer tower cutting of catalytic cracking unit absorption-stabilization element, and lighting end is lateral line withdrawal function from tower, and last running is extracted out at the bottom of tower.The cut point temperature of described lighting end and last running is 70 DEG C ~ 80 DEG C;
(2) lighting end obtained from step (1) goes alkali-free sweetening unit to carry out deodorization process, removes mercaptan sulfur wherein;
(3) remove the lighting end after mercaptan from step (2) gained and enter disulphide separation column together with the rich solar oil at the bottom of catalytic cracking Vapor recovery unit unit reabsorber tower, petroleum naphtha product is obtained from fractionator overhead, gasoline in lateral line withdrawal function from separation column tower, extracts poor diesel oil carrying device out at the bottom of tower; Doing of described petroleum naphtha is 45 DEG C ~ 60 DEG C, and doing of middle gasoline is 75 DEG C ~ 95 DEG C;
(4), after the last running that in step (3) gained, gasoline and step (1) obtain mixes, enter hydrogenation protecting reactor, carry out diolefine saturated reaction;
(5) reaction effluent of step (4) enters hydrodesulphurisatioreactors reactors after heat exchange or heat temperature raising, carries out depth-selectiveness hydrogenating desulfurization;
(6) reaction effluent of step (5) enters gas-liquid separator and is separated, and gained product liquid, after air lift, mixes with step (3) gained petroleum naphtha, obtains clean gasoline product or blend component.
According to catalytically cracked gasoline sulfur method of the present invention, catalytic cracking unit described in step (1) comprises various types of catalytic cracking unit, as fluid catalytic cracking (FCC), heavy oil fluid catalytic cracking (RFCC), catalytic pyrolysis (DCC), selective catalysis cracking (SCC), high-yield diesel oil catalytic cracking (MDP), voluminous isomeric olefine catalytic cracking (MIO), voluminous isomeric hydrocarbon catalytic cracking (MIP), voluminous liquefied gas and diesel catalytic cracking (MGD) device etc.Described Vapor recovery unit unit stabilizer tower is the gasoline stabilizer of the above-mentioned all process units of catalytic cracking family.
Alkali-free sweetening described in step (2) can adopt technology well known in the art.Condition as alkali-free sweetening is generally: reactor operating pressure 0.1 ~ 1.0MPa, temperature of reaction 20 DEG C ~ 70 DEG C, Feed space velocities 0.5 ~ 2.0h
-1, air flow quantity/inlet amount volume ratio is 0.1 ~ 1.0.Used catalyst and promotor are the catalyzer that this area is commonly used, and can select commercial goods or be prepared according to the knowledge of this area.
The feeding manner of the disulphide separation column described in step (3) is generally, and lighting end enters from tower bottom, and rich solar oil enters in the middle part of tower.Rich solar oil described here is catalytic cracking unit absorption-stabilization element reabsorber bottom stream, and doing of solar oil cut is generally 330 ~ 360 DEG C.The endpoint control of disulphide fractionator overhead light gasoline fraction is 45 DEG C ~ 60 DEG C, is preferably 50 DEG C ~ 55 DEG C; Middle gasoline fraction endpoint control is 75 DEG C ~ 95 DEG C, is preferably 80 DEG C ~ 85 DEG C.Lighting end is after alkali-free sweetening, and the mercaptan wherein contained is oxidized to heavier disulphide, enter in the fractionation process of disulphide separation column heavier in gasoline and diesel oil distillate.
In step (4), the last running that in gained, gasoline and step (1) obtain mixes, then after mixing with hydrogen, carries out heat exchange with hydrodesulfurization reaction effluent.
The reaction conditions of the hydrogenation protecting reactor described in step (4) is: reaction pressure 1.0 MPa ~ 4.0 MPa, preferably 1.5 MPa ~ 2.0 MPa; Reaction temperature in 120 DEG C ~ 220 DEG C, preferably 150 DEG C ~ 200 DEG C; Volume space velocity 1.0h
-1~ 10.0 h
-1, preferred 4.0h
-1~ 8.0 h
-1; Hydrogen to oil volume ratio 30: 1 ~ 300: 1, preferably 50: 1 ~ 200: 1.
Beds in hydrogenation protecting reactor is single bed or dual bed, bed filling hydrotreating catalyst, preferred diolefin hydrocatalyst for saturating.Hydrocatalyst for saturating is with Al
2o
3for carrier, with group vib metal M o and/or W, group VIII metal Co and/or Ni is active metal, with P and K for auxiliary agent.Also the various commercial catalysts that selective hydrogenation is saturated can be adopted, as Gasoline Hydrotreating Catalysts such as SHT-1, FH-40C that Fushun Petrochemical Research Institute develops, or by the existing method preparation in this area.
As required can also at the top grating of the beds of guard reactor one or more protective materials a certain proportion of, the volume ratio of protective material and hydrocatalyst for saturating is 0.2 ~ 2, preferably 0.5 ~ 1.Selected protective material cording has larger specific surface area and porosity, as FBN-02, FBN-03 series Bird's Nest protective material of Fushun Petrochemical Research Institute's development, or by the existing method preparation in this area.
The reaction conditions of the hydrodesulphurisatioreactors reactors described in step (5) is: reaction pressure 1.0 MPa ~ 4.0 MPa, preferably 1.5 MPa ~ 2.0 MPa; Reaction temperature in 200 DEG C ~ 300 DEG C, preferably 250 DEG C ~ 280 DEG C; Volume space velocity 1.0h
-1~ 10.0 h
-1, preferred 2.0h
-1~ 5.0 h
-1; Hydrogen to oil volume ratio 150: 1 ~ 450: 1, preferably 250: 1 ~ 350: 1.
Described hydrodesulphurisatioreactors reactors comprises at least two beds, has cold hydrogen to inject and arrange between bed.Different bed grading loading hydrotreating catalyst, preferred Hydrobon catalyst.Preferred Hydrobon catalyst is that load is at unformed Al
2o
3and/or the group vib metal on pure aluminium silicate carrier is as Mo and/or W, and/or group VIII metal is as Co and/or Ni non-precious metal catalyst, also the various commercial catalysts such as selective hydrodesulfurization or deep desulfurization olefin hydrocarbon reduction can be adopted, as FGH-11, FGH-21, FGH-31 of Fushun Petrochemical Research Institute's development, the gasoline hydrogenation catalysts such as the RSDS-1 of Beijing Research Institute of Petro-Chemical Engineering development, or by the existing method preparation in this area.
Wherein in step (5), step (4) gained reaction effluent, through process furnace heating or after heating up with the high temperature slurry oil heat exchange of 345 DEG C ~ 500 DEG C that catalytic cracking main fractionating tower is drawn, namely reaches the feeding temperature of hydrodesulphurisatioreactors reactors.Preferably utilize the high temperature slurry oil of catalytic cracking fractionating tower to carry out heat exchange intensification to hydrogenating desulfurization charging, a hydrodesulfurization reaction charging process furnace can be saved, save facility investment and running cost.
In step (6), the reaction effluent of step (5) first can carry out heat exchange cooling with the mixture of middle gasoline and last running and hydrogen before entering gas-liquid separator.The hydrogen-rich gas that gas-liquid separator obtains removes after the liquid phase of carrying secretly through cyclone separator and enters desulphurization of recycle hydrogen tower.Desulphurization of recycle hydrogen adopts amine liquid solvent adsorption method, and described amine liquid is organic bases, more with alcamines, conventional Monoethanolamine MEA BASF (MEA), diethanolamine (DEA), diisopropanolamine (DIPA) (DIPA), one or more in N methyldiethanol amine (MDEA).In desulphurization of recycle hydrogen tower, inject poor amine liquid from thionizer top, at the bottom of tower, extract rich amine solution carrying device recycling utilization out; Remove the new hydrogen external with device after compressor boosting of the recycle hydrogen after hydrogen sulfide to mix, as mixed hydrogen for device.Hydrogen sulfide content in described desulphurization of recycle hydrogen Posterior circle hydrogen is 0 ~ 100 ppm, preferably 0 ~ 50 ppm.
Gas-liquid separator described in step (6) realizes the gas-liquid separation of hydrogenating desulfurization product, and control condition is: temperature 40 DEG C ~ 50 DEG C, pressure 1.0 MPa ~ 4.0 MPa, preferred 1.5MPa ~ 2.0MPa.
The present invention by drawing side line in the stabilizer tower tower of catalytic cracking absorptions-stabilization element, makes that the catalytic cracked naphtha after absorption-desorb achieves gently at stabilizer tower, last running is cut, and obtains lighting end and the last running of specific boiling range scope.Then the lighting end obtained and last running are directly introduced alkali-free sweetening and hydrogenating desulfurization unit respectively, complete the refining desulfurization to catalytically cracked gasoline, thus hydro-refining unit and catalytic cracking unit main fractionating tower are combined.Disulphide separation column introduced by the rich solar oil that lighting end comes after alkali-free sweetening and at the bottom of catalytic cracking absorption-stabilization element reabsorber tower, remove the relatively high disulphide of petroleum naphtha mid-boiling point after alkali-free sweetening and the easy green coke material of trace by fractionation, significantly reduce the total sulfur content of gasoline in tower top petroleum naphtha and a small amount of side line.Finally catalytic cracking absorb-stabilization element stabilizer tower tower at the bottom of last running and come autospasy disulphide separation column a small amount of in gasoline direct hot feed to gasoline selective hydrodesulfurizationmodification unit, and utilize the high temperature slurry oil of catalytic cracking heat affluence for gasoline selective hydrodesulfurizationmodification charging heat supply, make it carry out hydrogenating desulfurization under optimum conditions.Treated gasoline after hydrogenation removes through air lift and blends device with disulphide fractionator overhead petroleum naphtha after hydrogen sulfide and remove gasoline products blending system.
Compared with prior art, the method for catalytically cracked gasoline production clean gasoline of the present invention has the following advantages:
(1) in Fcc Stabilizer tower, draw lighting end side line, achieve the cutting and separating of light, the last running of catalytic cracked naphtha, eliminate catalytically cracked gasoline weight gasoline Cutting Tap, decrease plant investment, reduce plant energy consumption.
(2) after last running at the bottom of Fcc Stabilizer tower and alkali-free sweetening through the direct hot gasoline feed hydrodesulfurization unit of lighting end of disulphide separation column, reduce the possibility that catalytically cracked gasoline contacts with oxygen, decrease the possibility of gasoline sweetener interchanger and the coking of reactor bed top, be conducive to extending the gasoline hydrogenation plant running cycle.
(3) by arranging disulphide separation column, utilize the rich solar oil of certain temperature and the mutual mass transfer of lighting end, heat transfer, thus the disulphide that after removing alkali-free sweetening, petroleum naphtha mid-boiling point is relatively high and the easy green coke material of trace, significantly reduce the total sulfur content of tower top petroleum naphtha and middle gasoline.Not only ensure that the mercaptan sulfur content of light gasoline fraction is very low, reduce the content of sulphur content in middle gasoline and coke precursor; The rich solar oil of catalytic cracking absorption-stabilization element is also made to obtain desorb, the part raw gasline wherein absorbed is made to enter into petroleum naphtha and the gasoline fraction of tower top and side line, the poor diesel oil of desorb can direct carrying device, avoids rich solar oil and again returns catalytic cracking main fractionating tower and repeat fractionation.
(4) hydrogenating desulfurization unit arranges guard reactor, utilizes catalyzer and protectant rational gradation composition, ensure that the long-term operation of device.
(5) charging by utilizing catalytic cracking high temperature slurry oil to heat hydrodesulphurisatioreactors reactors, even can cancel hydrodesulfurization reaction charging process furnace, avoid the coking that hydrogenating desulfurization charging causes in process furnace local heating inequality, the heat of catalytic cracking unit affluence can also be made full use of, reduce the overall energy consumption of gasoline sweetener.
(6) by control the load of gasoline fraction in disulphide separation column tower, boiling range scope or go gasoline fraction amount in selective hydrodesulfurization unit number, the index request that different standards gasoline products is produced can be met, thus increase the turndown ratio of device, achieve device benefit goal and maximize production.
(7) by the hydrogen sulfide content in the desulphurization of recycle hydrogen tower controlled circulation hydrogen of selective hydrogenation unit setting, effectively reduce mercaptan resynthesis, thus ensure that the mercaptan sulfur content in treated gasoline meets the demands.
(8) the inventive method technical process is simple, turndown ratio is large, tooling cost is low, significantly can reduce the sulphur content in catalytically cracked gasoline and olefin(e) centent, especially the mercaptan sulfur content in gasoline is reduced, produce the low-sulfur and super low-sulfur oil that meet Europe V or state V specification gasoline, and the loss of octane number of gasoline is minimum.Be particularly useful for catalytically cracked gasoline inferior and produce clean gasoline.
Accompanying drawing explanation
Fig. 1 is the method block diagram that clean gasoline produced by a kind of catalytically cracked gasoline of the present invention.
Wherein 1 is the raw gasline after catalytic cracking absorption-desorb, 2 is Fcc Stabilizer, 3 is alkali-free sweetening unit, 4 is lighting end, 5 is petroleum naphtha product, 6 go product to concoct for middle gasoline, 7 remove hydrogenating desulfurization unit for middle gasoline, 8 is hydrogen make-up, 9 is disulphide separation column, 10 is rich solar oil, 11 is middle gasoline, 12 is last running, 13 go out device for diesel oil, 14 is catalytically cracked oil, 15 is hydrogenating desulfurization unit raw material surge tank, 16 is guard reactor, 17 is hydrodesulphurisatioreactors reactors, 18 is reaction product knockout drum, 19 is desulphurization of recycle hydrogen tower, 20 is poor amine liquid, 21 is rich amine solution, 22 is circulating hydrogen compressor, 23 tower top hydrogen sulfide and small molecules hydro carbons, 24 is treated gasoline, 25 hydrogenating desulfurization unit stripping towers.
Embodiment
Composition graphs 1, the technical process that clean gasoline method produced by catalytically cracked gasoline of the present invention is:
The raw gasline 1 of catalytic cracking absorption-stable system after absorption-desorb enters Fcc Stabilizer 2 and carries out fractionation.Tower top extracts catalytic cracked dry gas and liquefied gas out, draws lateral line withdrawal function lighting end 4 in tower, extracts last running 12 out at the bottom of tower.Lighting end 4 enters alkali-free sweetening unit 3, and removing wherein heats up through heat exchange after mercaptan enters disulphide separation column 9 bottom.The rich solar oil 10 attracted from catalytic cracking absorption-stable system reabsorber enters disulphide separation column 9 middle and lower part.Extract refining light gasoline fraction 5 out from disulphide fractionator overhead and send to product blending; From tower, extract gasoline fraction 11 in certain boiling range scope out, send to product blending 6 according to gasoline in need of production one tunnel, in another road, gasoline 7 removes selective hydrodesulfurization unit.In disulphide separation column, utilize the mass transfer of rich solar oil and lighting end, heat transfer, remove the relatively high disulphide of gasoline lighting end mid-boiling point after alkali-free sweetening and the easy green coke material of trace, significantly reduce the total sulfur content of tower top petroleum naphtha and middle gasoline.Particularly reduce the mercaptan sulfur content in petroleum naphtha.
The middle gasoline fraction 7 that disulphide separation column is extracted out enters selective hydrodesulfurization unit raw material oil surge tank 15 together with last running 12 at the bottom of Fcc Stabilizer tower; be warmed up to 150 DEG C ~ 180 DEG C through heat exchange after mixing with hydrogen after pump boosting and enter guard reactor 16; diolefine in blend gasoline charging is obtained saturated, under preventing high temperature, diene polymerization coking affects the plant running cycle.Guard reactor reaction effluent enters hydrogenation main reactor 17 after high temperature slurry oil 14 heat exchange next with catalytic cracking is warmed up to 230 DEG C ~ 280 DEG C, carries out the selective hydrodesulfurization of the degree of depth.Reaction effluent enters gas-liquid separator 18 after heat exchange cooling, after gas-liquid separation, separator top gas phase recycle hydrogen enters desulphurization of recycle hydrogen tower 19 after de-liquid, inject poor amine liquid 20 on desulphurization of recycle hydrogen tower 19 top, rich amine solution 21 extracts carrying device recycling utilization out at the bottom of tower.Recycle hydrogen after desulfurization after circulating hydrogen compressor 22 boosts and the external hydrogen make-up 23 of device be mixed into selective hydrodesulfurization systemic circulation and use; Separator bottom oil phase enters stripping tower 25 after heat temperature raising, from removed overhead hydrogen sulfide and small molecules hydro carbons 23.The petroleum naphtha 5 that the refining heavy naphtha 24 removing hydrogen sulfide is extracted out with disulphide separation column 9 tower top at the bottom of stripping tower 25 tower mixes as gasoline blending component carrying device.
Below by specific embodiment, technical scheme of the present invention is described in further detail.
Embodiment all adopts the technical process shown in Fig. 1.Wherein alkali-free sweetening catalyzer is the AFS-12 prefabrication type catalyzer of Chinese Petroleum Univ.'s research and development.Hydrogenation protecting catalyst is the FH-40C hydrogenation catalyst of Fushun Petrochemical Research Institute's development and production, and Hydrobon catalyst is the FGH-31 hydrogenation catalyst of Fushun Petrochemical Research Institute's development and production.
Embodiment 1
By the technical process process FCC catalytically cracked gasoline shown in Fig. 1, production super low sulfur clean gasoline.
Raw gasline in stabilizer tower the cutting and separating of FCC catalytic cracking absorption-stabilization element after absorption-desorb, obtains lighting end and last running.FCC Fcc Stabilizer is separated the character of light, the last running obtained in table 1.
The character of light, the last running that table 1 FCC Fcc Stabilizer is separated
| Project | Lighting end | Last running |
| Density (20 DEG C), g/cm 3 | 0.6875 | 0.7394 |
| Sulphur content, μ g/g | 122 | 683 |
| RON | 95.2 | 92.6 |
| Boiling range (ASTM D 86), DEG C | ||
| IBP/10% | 30/35 | 79/110 |
| 30%/50% | 40/51 | 127/141 |
| 70%/90% | 59/63 | 157/188 |
| 95%/ FBP | 71/76 | 203/210 |
Lighting end enters alkali-free sweetening unit, removes mercaptan sulfur.Alkali-free sweetening condition is: pressure 0.6MPa, temperature 40 DEG C, volume space velocity 2.0h
-1, gas-oil ratio (air/lighting end) 0.7.
Lighting end after alkali-free sweetening absorbs with catalytic cracking-stablizes together with rich solar oil and enters disulphide separation column, obtains refining light gasoline fraction and middle gasoline fraction after fractionation.Alkali-free sweetening lighting end and catalytic cracking absorb-stablize rich solar oil cut character in table 2.Poor diesel oil character after refining light gasoline fraction and middle gasoline fraction and desorb is in table 3.
Lighting end after table 2 alkali-free sweetening and catalytic cracking diesel oil cut character
| Project | Lighting end after alkali-free sweetening | Absorb-stablize rich solar oil |
| Density (20 DEG C), g/cm 3 | 0.6881 | 0.8556 |
| Sulphur, μ g/g | 122 | 9800 |
| Mercaptan sulfur, μ g/g | ＜5 | — |
| RON | 95.7 | — |
| Boiling range (ASTM D 86), DEG C | ||
| IBP/10% | 32/38 | 137/196 |
| 30%/50% | 42/51 | 234/252 |
| 70%/90% | 63/78 | 291/329 |
| 95%/ FBP | 86/94 | —/343 |
Table 3 refines light gasoline fraction and middle gasoline fraction and poor diesel oil character
| Project | Refining petroleum naphtha | Middle gasoline | Poor diesel oil |
| Density (20 DEG C), g/cm 3 | 0.6667 | 0.7080 | 0.8612 |
| Sulphur, μ g/g | 5 | 230 | 9885 |
| Mercaptan sulfur, μ g/g | ＜2 | — | — |
| RON | 95.7 | 93.1 | — |
| Boiling range (ASTM D 86), DEG C | |||
| IBP/10% | 28/30 | 61/64 | 180/208 |
| 30%/50% | 33/36 | 67/70 | 237/259 |
| 70%/90% | 40/42 | 74/77 | 302/329 |
| 95%/ FBP | 47/49 | 81/85 | —/343 |
The middle gasoline that disulphide separation column is extracted out enters selective hydrodesulfurization unit together with the last running obtained at the bottom of catalytic cracking absorption-stabilization element stabilizer tower tower; successively by hydrogenation protecting reactor and hydrodesulphurisatioreactors reactors; carry out deep desulfuration, obtain refining heavy naphtha.Hydrogenation protecting catalyst and Hydrobon catalyst are that the processing condition of hydrogenating desulfurization unit list in table 4.
Table 4 hydrogenating desulfurization cell process condition
| Project | Embodiment 1 |
| Reactor | Protection/desulfurization |
| Stock oil | Middle gasoline+last running |
| Catalyzer | FH-40C/FGH-31 |
| Reactor inlet temperature, DEG C | 165/260 |
| Hydrogen dividing potential drop, MPa | 2.0/1.8 |
| Volume space velocity, h -1 | 5.0/3.0 |
| Hydrogen-oil ratio (always), v/v | 300 |
Refining heavy petrol and the mixing of refining petroleum naphtha are as treated gasoline blending component carrying device.Refining heavy naphtha and mixing treated gasoline character are in table 5.
Table 5 refines heavy naphtha and mixing treated gasoline character
| Project | Hydrogenated heavy gasoline | Blended gasoline |
| Density (20 DEG C), g/cm 3 | 0.7305 | 0.7182 |
| Sulphur, μ g/g | 10 | 9 |
| Mercaptan sulfur, μ g/g | <5 | <5 |
| RON | 90.2 | 92.8 |
| Boiling range (ASTM D 86), DEG C | ||
| IBP/10% | 62/93 | 40/58 |
| 30%/50% | 113/131 | 86/114 |
| 70%/90% | 149/179 | 138/175 |
| 95%/FBP | 191/205 | 188/202 |
Can see from embodiment 1, adopt method provided by the invention, produce clean gasoline sulphur content and be only 9 μ g/g, mercaptan sulfur content <5 μ g/g, the octane value comparatively full cut of FCC only loses 1.4 units.
Embodiment 2
By the technical process process MIP catalytically cracked gasoline shown in Fig. 1, production super low sulfur clean gasoline.
Raw gasline in stabilizer tower the cutting and separating of MIP catalytic cracking absorption-stabilization element after absorption-desorb, obtains lighting end and last running.MIP Fcc Stabilizer is separated the character of light, the last running obtained in table 6.
Table 6 MIP Fcc Stabilizer is separated the character of light, the last running obtained
| Project | Lighting end | Last running |
| Density (20 DEG C), g/cm 3 | 0.6772 | 0.7375 |
| Sulphur content, μ g/g | 118 | 680 |
| Alkene, v% | ||
| RON | 95.6 | 92.8 |
| Boiling range (ASTM D-86), DEG C | ||
| IBP/10% | 30/35 | 80/109 |
| 30%/50% | 40/49 | 125/138 |
| 70%/90% | 57/62 | 153/185 |
| 95%/ FBP | 67/73 | 197/205 |
Lighting end enters alkali-free sweetening unit, removes mercaptan sulfur.Alkali-free sweetening condition is: pressure 0.7MPa, temperature 35 DEG C, volume space velocity 2.0h
-1, gas-oil ratio (air/lighting end) 0.9.
Lighting end after alkali-free sweetening enters disulphide separation column together with the rich solar oil of catalytic cracking absorption-stabilization element, obtains refining petroleum naphtha and middle gasoline through fractionation.The rich solar oil character of lighting end after alkali-free sweetening and catalytic cracking absorption-stabilization element is in table 7, and the poor diesel oil character after refining light gasoline fraction and middle gasoline fraction and desorb is in table 8.
Lighting end after table 7 alkali-free sweetening and catalytic cracking diesel oil character
| Project | Alkali-free sweetening lighting end | MIP absorbs-stablizes rich solar oil |
| Density (20 DEG C), g/cm 3 | 0.6878 | 0.9142 |
| Sulphur, μ g/g | 118 | 9800 |
| Mercaptan sulfur, μ g/g | ＜5 | — |
| RON | 95.6 | — |
| Boiling range (ASTM D 86), DEG C | ||
| IBP/10% | 28/37 | 137/196 |
| 30%/50% | 42/53 | 234/252 |
| 70%/90% | 60/79 | 291/329 |
| 95%/ FBP | 87/96 | —/343 |
Table 8 is refined petroleum naphtha and is divided and middle gasoline and poor diesel oil character
| Project | Refining petroleum naphtha | Middle gasoline | Poor diesel oil |
| Density (20 DEG C), g/cm 3 | 0.6667 | 0.7080 | 0.9275 |
| Sulphur, μ g/g | 5 | 230 | 9874 |
| Mercaptan sulfur, μ g/g | ＜2 | - | — |
| RON | 95.7 | 93.1 | — |
| Boiling range (ASTM D 86), DEG C | |||
| IBP/10% | 28/30 | 62/65 | 180/208 |
| 30%/50% | 33/36 | 68/70 | 237/259 |
| 70%/90% | 40/42 | 75/78 | 302/329 |
| 95%/ FBP | 47/49 | 82/85 | —/343 |
Selective hydrodesulfurization unit is entered together with the middle gasoline that disulphide separation column is extracted out and the last running that obtains of catalytic cracking absorption-stabilization element stabilizer tower tower top; successively by hydrogenation protecting reactor and hydrodesulphurisatioreactors reactors; carry out deep desulfuration, obtain refining heavy naphtha.Hydrogenation protecting reactor and hydrodesulphurisatioreactors reactors are that the processing condition of hydrogenating desulfurization unit list in table 9.
Table 9 hydrodesulfurization condition
| Project | Embodiment 1 |
| Reactor | Protection/desulfurization |
| Stock oil | Middle gasoline+last running |
| Catalyzer | FH-40C/FGH-31 |
| Reactor inlet temperature, DEG C | 155/252 |
| Hydrogen dividing potential drop, MPa | 1.8/1.6 |
| Volume space velocity, h -1 | 5.0/3.0 |
| Hydrogen-oil ratio (always), v/v | 300 |
Refining heavy petrol and the mixing of refining petroleum naphtha are as treated gasoline blending component carrying device.Refining heavy petrol and mixing treated gasoline character are in table 10.
Table 10 refines heavy petrol and mixing treated gasoline character
| Project | Hydrogenated heavy gasoline | Treated gasoline after blending |
| Density (20 DEG C), g/cm 3 | 0.7305 | 0.7182 |
| Sulphur, μ g/g | 10 | 9 |
| Mercaptan sulfur, μ g/g | <5 | <5 |
| RON | 89.9 | 92.5 |
| Boiling range (ASTM D 86), DEG C | ||
| IBP/10% | 62/93 | 40/64 |
| 30%/50% | 113/131 | 86/116 |
| 70%/90% | 150/179 | 138/175 |
| 95%/FBP | 192/200 | 188/199 |
Can see from embodiment 2, adopt method provided by the invention, MIP sulfur content of catalytic cracking gasoline is reduced to 9 μ g/g, mercaptan sulfur content <5 μ g/g, and the octane value comparatively full cut of MIP gasoline only loses 1.5 units.
Comparative example 1
Stock oil is with embodiment 1, and first full distillation gasoline carries out alkali-free sweetening, and alkali-free sweetening condition is with embodiment 1.After deodorization, full cut obtains <80 DEG C of lighting end and >80 DEG C of last running through prefractionation.Hydrogenating desulfurization is carried out in >80 DEG C of last running, and processing condition list in table 11.
Refining last running after hydrogenating desulfurization and lighting end are mixed to get clean gasoline.Character lists in table 12.
Table 11 hydrodesulfurization condition
| Project | Embodiment 1 |
| Reactor | Protection/desulfurization |
| Stock oil | Middle gasoline+last running |
| Catalyzer | FH-40C/FGH-31 |
| Temperature of reaction, DEG C | 178/282 |
| Hydrogen dividing potential drop, MPa | 1.8/1.6 |
| Volume space velocity, h -1 | 5.0/3.0 |
| Hydrogen-oil ratio (always), v/v | 350 |
Table 12
| Project | FCC stable gasoline | Blended gasoline |
| Density (20 DEG C), g/cm 3 | 0.72 | 0.75 |
| Sulphur, μ g/g | 520 | 9 |
| Mercaptan sulfur, μ g/g | — | 5 |
| RON | 94.2 | 90.8 |
| Boiling range (ASTM D 86), DEG C | ||
| IBP/10% | 38/59 | 38/61 |
| 30%/50% | 89/115 | 92/101 |
| 70%/90% | 136/173 | 137/175 |
| 95%/FBP | —/200 | —/204 |
As can be seen from Table 12, adopt the method that comparative example 1 provides, with FCC catalytically cracked gasoline production sulphur content 9 μ g/g, the clean gasoline of mercaptan sulfur content <5 μ g/g, and loss of octane number is 3.4 units.
And in the inventive method embodiment 1, reach same sulphur content, loss of octane number Jin You1.4Ge unit; Compared with comparative example 1, a small amount of easily green coke material claimed in alkali-free sweetening process owing to utilizing catalytic cracking absorption-stable rich solar oil to be stripped of in embodiment 1, therefore the steady running cycle of device obtains prolongation.The running period of comparative example 1 is generally 6 ~ 8 months.And 10 ~ 16 months can be reached the running period of the embodiment of the present invention 1, compared with comparative example 1, the present invention will extend running period more than 80%.Same compared with comparative example 1, owing to utilizing the heat of catalytic cracking high temperature slurry oil affluence for hydrogenating desulfurization unit process charging heating in embodiment 1, catalytic cracking absorption-stable stabilizer tower cutting obtains lighting end gasoline and last running gasoline, achieve the heat integration of catalytic cracking unit and hydrodesulfurization unit, significantly reduce plant energy consumption, can save energy 30% ~ 50%.Meanwhile, make catalytic cracking absorption-stable rich solar oil obtain desorb, be conducive to reducing Energy Consumption in Fcc Unit.In addition, also reduce weight gasoline Cutting Tap, save plant investment, reduce operation easier.
Claims (13)
1. a method for clean gasoline produced by catalytically cracked gasoline, comprises the following steps:
(1) catalytically cracked gasoline obtains lighting end, last running in the stabilizer tower cutting of catalytic cracking unit absorption-stabilization element, and lighting end is lateral line withdrawal function from tower, and last running is extracted out at the bottom of tower; The cut point temperature of described lighting end and last running is 70 DEG C ~ 80 DEG C;
(2) lighting end obtained from step (1) goes alkali-free sweetening unit to carry out deodorization process, removes mercaptan sulfur wherein;
(3) remove the lighting end after mercaptan from step (2) gained and enter disulphide separation column together with the rich solar oil at the bottom of catalytic cracking unit absorption-stabilization element reabsorber tower, petroleum naphtha product is obtained from fractionator overhead, gasoline in lateral line withdrawal function from separation column tower, extracts poor diesel oil carrying device out at the bottom of tower; Doing of described petroleum naphtha is 45 DEG C ~ 60 DEG C, and doing of middle gasoline is 75 DEG C ~ 95 DEG C;
(4), after the last running that in step (3) gained, gasoline and step (1) obtain mixes, enter hydrogenation protecting reactor, carry out diolefine saturated reaction;
(5) reaction effluent of step (4) enters hydrodesulphurisatioreactors reactors after heat exchange or heat temperature raising, carries out depth-selectiveness hydrogenating desulfurization;
(6) reaction effluent of step (5) enters gas-liquid separator and is separated, and gained product liquid, after air lift, mixes with step (3) gained petroleum naphtha, obtains clean gasoline product or blend component.
2. in accordance with the method for claim 1, it is characterized in that, the feeding manner of the disulphide separation column described in step (3) is that lighting end enters from tower bottom, and rich solar oil enters in the middle part of tower.
3. in accordance with the method for claim 1, it is characterized in that, doing of the rich solar oil cut described in step (3) is 330 ~ 360 DEG C.
4. in accordance with the method for claim 1, it is characterized in that, the endpoint control of described disulphide fractionator overhead light gasoline fraction is 50 DEG C ~ 55 DEG C, and the endpoint control of middle gasoline fraction is 80 DEG C ~ 85 DEG C.
5. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the hydrogenation protecting reactor described in step (4) is: reaction pressure 1.0 MPa ~ 4.0 MPa, reaction temperature in 120 DEG C ~ 220 DEG C, volume space velocity 1.0h
-1~ 10.0 h
-1, hydrogen to oil volume ratio 30: 1 ~ 300: 1; The reaction conditions of the hydrodesulphurisatioreactors reactors described in step (5) is: reaction pressure 1.0 MPa ~ 4.0 MPa, reaction temperature in 200 DEG C ~ 300 DEG C, volume space velocity 1.0h
-1~ 10.0 h
-1, hydrogen to oil volume ratio 150: 1 ~ 450: 1.
6. in accordance with the method for claim 1, it is characterized in that, described in step (2), the condition of alkali-free sweetening is: reaction pressure 0.1 ~ 1.0MPa, temperature of reaction 20 DEG C ~ 70 DEG C, Feed space velocities 0.5 ~ 2.0h
-1, air flow quantity/inlet amount volume ratio is 0.1 ~ 1.0.
7. in accordance with the method for claim 1, it is characterized in that, wherein in step (5), after the high temperature slurry oil heat exchange of 345 DEG C ~ 500 DEG C that step (4) gained reaction effluent and catalytic cracking main fractionating tower are drawn heats up, namely reach the feeding temperature of hydrodesulphurisatioreactors reactors.
8. in accordance with the method for claim 1, it is characterized in that, load hydrocatalyst for saturating in described hydrogenation protecting reactor, hydrocatalyst for saturating is with Al
2o
3for carrier, with group vib metal M o and/or W, group VIII metal Co and/or Ni is active metal, with P and K for auxiliary agent.
9. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst is that load is at unformed Al
2o
3and/or the group vib metal on pure aluminium silicate carrier is as Mo and/or W, and/or group VIII metal is as Co and/or Ni non-precious metal catalyst.
10. in accordance with the method for claim 1, it is characterized in that, at one or more protective materials of top grating of hydrocatalyst for saturating bed, the volume ratio of protective material and hydrocatalyst for saturating is 0.2 ~ 2.
11. in accordance with the method for claim 1, it is characterized in that, described hydrodesulphurisatioreactors reactors comprises at least two beds, has cold hydrogen to inject and arrange between bed.
12. in accordance with the method for claim 1, it is characterized in that, mixture and the hydrogen of reaction effluent elder generation and middle gasoline and last running before entering gas-liquid separator of step (5) carry out heat exchange cooling.
13. in accordance with the method for claim 1, it is characterized in that, the catalytic cracking unit described in step (1) is fluid catalytic cracking, heavy oil fluid catalytic cracking, catalytic pyrolysis, selective catalysis cracking, high-yield diesel oil catalytic cracking, voluminous isomeric olefine catalytic cracking, voluminous isomeric hydrocarbon catalytic cracking, voluminous liquefied gas or diesel catalytic cracking unit.
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| CN101787307A (en) * | 2009-01-22 | 2010-07-28 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
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| CN101787307A (en) * | 2009-01-22 | 2010-07-28 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
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