CN103059949A - Catalytic cracking gasoline desulfurization method - Google Patents
Catalytic cracking gasoline desulfurization method Download PDFInfo
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Abstract
The invention discloses a catalytic cracking gasoline desulfurization method. The method consists of: subjecting the effluent from a catalytic cracking main fractionating tower top to stepped cooling so as to obtain light fractions and heavy fractions, after stable absorption, subjecting the light fractions to alkali-free deodorization, letting the deodorized light fractions and catalytic diesel oil enter a disulfide fractionating tower together, 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 from cooling, then passing the mixture through a hydrogenation protection reactor and a hydrodesulfurization reactor in order, 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 refining processing method of a kind of light hydrocarbons, more specifically say a kind of catalytically cracked gasoline sulfur method, especially reduce the catalytically cracked gasoline mercaptan sulfur content, produce the method for clean gasoline.
Technical background
Along with the increasingly stringent of fast development and the environmental requirement of automotive industry, the production of low-sulfur, super low sulfur clean gasoline has become petroleum refining industry's development inexorable trend.From the formation of the present gasoline pool of China, the catalytically cracked gasoline component accounts for 75% ~ 80%.And the sulphur content of catalytically cracked gasoline is the highest to the contribution rate of the sulphur content in China's gasoline pool usually at 100 ~ 2000 μ g/g, reaches more than 98%.And, along with the raw material of catalyzed cracking processing to the heaviness future development, will cause the sulphur content in the catalytically cracked gasoline further to increase.Therefore, the catalytically cracked gasoline desulfurization just becomes the gordian technique that must solve in the 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 and add being combined with of hydrogen pretreatment, catalytically cracked gasoline aftertreatment and this this dual mode.Although these technology can reduce sulphur content and olefin(e) centent significantly, because must be saturated in a large number with having high-octane olefin component in hydrogenation process, cause the loss of octane number of gasoline products very large, and the device working cost is higher.
EP0940464 discloses a kind of processing method of catalytically cracked gasoline desulfurization, with catalytically cracked gasoline cut into gently, in, weigh three kinds of cuts, the first bed that last running at first enters the fixed-bed reactor with two beds carries out hydrogenating desulfurization, and its desulfurization afterreaction product and middle cut are mixed in the first bed outlet and enter the second bed and enter hydrodesulfurization reaction.The method is not all the basis with the sulphur content of the cut of the different boiling range scopes of catalytically cracked gasoline, different fractions carries out the hydrogenating desulfurization of different depths, be conducive to reduce the sulphur content of product gasoline, but hydrogenation process olefin saturated rate is higher, causes the product gasoline loss of octane number excessive.
US5399258 discloses a kind of gasoline modifying method, and behind first paragraph process hydrogenation desulfurization and denitrogenation, the olefins hydrogenation, the intermediate product that obtains directly enters second segment and carries out the octane value recovering reaction.The temperature of reaction of first paragraph is higher, and is fair with the temperature of reaction of second segment.Because the temperature of reaction of first paragraph is too high, causes final product to produce a large amount of mercaptan sulfurs, temperature is higher, and the mercaptan sulfur of generation is more.
CN101492606A provides a kind of FCC gasoline hydrodesulfurizationmethod method that produces the low thioalcohol product, and the hydrocarbon stream that will comprise sulfide is fed to the catalytic distillation reactor with one or more hydrodesulfurizationreaction reaction zone; Hydrogen is fed to the catalytic distillation reactor; Simultaneously in the catalytic distillation reactor: hydrocarbon stream is fractionated into last running and lighting end; Make hydrogen contact to form H with lighting end
2The lighting end that S and sulphur content are lowered; Recovery is as lighting end, the H of overhead product
2S and hydrogen; Reclaim last running; Overhead product is heated to 500 ℉ ~ 700 ℉; Overhead product and the hydrogen of heating are fed to the 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 are to form light ends fractionation and to comprise H
2The cut of S and hydrogen; The part of light ends fractionation is recycled to the catalytic distillation reactor.The method can effectively reduce the thio-alcohol sulphur in the product gasoline, but the operation more complicated, control is difficult for stable.
USP6024865 discloses a kind of gasoline alkylation desulfuration method, first gasoline is divided into light, weigh two cuts, carry out respectively again alkylated reaction, reach the purpose of desulfurization.The method is regulated alkylation conditions for the sulfide kind that contains in the gasoline fraction, lighting end utilizes the alkene that self contains to carry out alkylated reaction under comparatively gentle condition, and last running is comparatively being carried out alkylated reaction under the exacting terms by alkene or the alcohol that adds C3-C5.But reaction process is comparatively complicated, and adding alkene or alcohol has also increased operation easier.
CN101220295A is catalytically cracked gasoline and diesel oil coupled desulfurization device and method, the method is by a thiophenic sulfur alkylation reactor, sulphur in the catalytically cracked gasoline is shifted as in the high boiling sulfide, then enter together sulphur with catalytic cracking diesel oil and shift separation column, cat head obtains the gasoline that sulphur shifts, and the sulfur-containing diesel of extracting out at the bottom of the tower removes the diesel fuel desulfurization device.This processing method realizes that by alkylated reaction the sulphur in the gasoline shifts, but the degree of depth of gasoline desulfur is limited, and need to attract diesel oil from the catalytic cracking diesel oil storage tank, special separation column is set behind the petrol and diesel oil Product mix with catalytic cracking fractionation part again petrol and diesel oil is separated, the energy consumption of device and the corresponding rising of investment.
Dissimilar catalytic cracking unit all is comprised of reaction-regeneration system, fractionating system and absorption-stable system.Fractionating system mainly is the catalytic cracking main fractionating tower, and the high-temperature oil gas that reaction-regeneration system comes is divided into different products in main fractionating tower, and the main fractionating tower cat head goes out rich gas and raw gasline; Side line is extracted solar oil, heavy gas oil and recycle stock from top to bottom successively out; Extract catalytically cracked oil at the bottom of the tower out.Absorbing-stabilizing system mainly is comprised of absorption tower, desorption tower and stabilizer tower, 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 that catalytic cracking obtains (comprising dry gas, liquefied gas, gasoline, diesel oil) all needs through just sending as the market sale product after the hydrotreatment (mainly being hydrogenating desulfurization).Stable gasoline wherein is the main source of motor spirit, and catalytic cracking stable gasoline desulfurization technology then is the gordian technique of clean gasoline production.
In the existing catalytic cracking stable gasoline desulfurization technology, mostly be that sulphur content according to the catalytic cracking stable gasoline becomes with cut and heavily is the trend that incremental distributes, sulphur mainly concentrates in the last running, particularly〉sulphur content of 90 ℃ of last running obviously increases; And olefin(e) centent heavily is the formula distribution trend that falls progressively with the cut change, alkene mainly concentrates in the lighting end, particularly〉olefin(e) centent of 90 ℃ of last running obviously reduces, alkene is enriched in＜characteristic in 90 ℃ of lighting ends, in order to guarantee gasoline octane rating loss reduction after the desulfurization of catalytic cracking stable gasoline, usually the technology that adopts is: the catalytic cracking stable gasoline of catalytic cracking stable gasoline or process alkali-free sweetening is divided into lighting end gasoline and last running gasoline by certain cut point, lighting end gasoline carries out mercaptan removal to be processed, heavy naphtha carries out hydrogenating desulfurization, and then the two mixing is gone to gasoline mediation pond as product gasoline.The gasoline that prior art satisfies sulphur content＜150 μ g/g or sulphur content＜50 μ g/g for production is feasible, but along with environmental regulation improving constantly quality of gasoline upgrading requirement, production sulphur content＜10 μ g/g, particularly mercaptan sulfur content＜5 μ g/g super low sulfur clean gasolines have been trend of the times.Though existing technology can satisfy production requirement, the severity of producing 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.Particularly change into high boiling disulphide through lower boiling mercaptan sulfur in the catalytic cracking stable gasoline behind the alkali-free sweetening, in the weight gasoline splitter, be difficult to the mercaptan sulfur of light gasoline fraction is removed, then affected mercaptan sulfur and the total sulfur content of blend gasoline.
During current refining of petroleum is produced, catalytic cracking unit and refining catalytic gasoline device are two covering devices independently separately, the stable gasoline that catalytic cracking unit is produced is sent to the tank field, extracted out by pump again and send naphtha-treating plant to, produce the clean gasoline product that meets the demands with the sulphur content and the olefin(e) centent that reduce wherein.In this Production Flow Chart, catalytically cracked gasoline may touch oxygen, causes wherein sulfide, alkene and oxygen reaction to generate various coking precursors, causes naphtha-treating plant interchanger and reactor bed top coking phenomenon.In addition, the catalytic diesel oil of catalytic cracking unit, slurry oil also are carrying devices after cooling.It is longer to form production process route, and the work flow plant energy consumption is higher.And the heat of catalytic cracking process is relatively rich, is commonly used to occur the steam that the refinery needs, but most of heat below 300 ℃ can not take full advantage of, and has also increased the device cooling load.
Therefore, catalytic cracking unit and Gasoline hydrofining unit are combined more closely, utilize existing process production techniques, the sulphur content that the realizes catalytically cracked gasoline requirement that touches the mark realizes that particularly the mercaptan sulfur content of light gasoline fraction satisfies index request; And the fully reasonable utilization of heat between implement device, the unit consumption of energy of reduction device, the economic benefit of increase device, the clean gasoline product of producing the gasoline quality index that satisfies 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 catalytically cracked gasoline sulfur method, especially reduce the 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 the qualified clean gasoline product of sulphur and olefin(e) centent, and can obviously reduce the production equipment energy consumption, increases the economic benefit of catalytically cracked gasoline desulfurizer.
The method of catalytically cracked gasoline desulfurization provided by the invention may further comprise the steps:
(1) catalytic cracking main fractionating tower cat head effluent obtains lighting end, last running through behind the gradient cooling, and the cut point between described lighting end and the last running is 70 ℃ ~ 80 ℃;
(2) catalytic cracking device absorption stabilizing system is removed in the lighting end that obtains from step (1), and resulting stable gasoline enters the alkali-free sweetening unit and carries out the deodorization processing, removes mercaptan sulfur wherein;
(3) lighting end and the hot diesel oil of catalytic cracking that remove behind the mercaptan from step (2) gained enter the disulphide separation column together, obtain the petroleum naphtha product from fractionator overhead, and gasoline in the lateral line withdrawal function from the fractionation Tata is extracted the diesel oil carrying device out at the bottom of the tower; Doing of described petroleum naphtha is 45 ℃ ~ 60 ℃, and doing of middle gasoline is 75 ℃ ~ 95 ℃;
(4) gasoline enters the hydrogenation protecting reactor with after last running that step (1) obtains mixes in step (3) gained, carries out the diolefine saturated reaction;
(5) reaction effluent of step (4) enters hydrodesulphurisatioreactors reactors behind heat exchange or heat temperature raising, carries out the depth-selectiveness hydrogenating desulfurization;
(6) reaction effluent of step (5) enters gas-liquid separator and separates, and the gained product liquid mixes with step (3) gained petroleum naphtha through after the air lift, obtains clean gasoline product or blend component.
According to catalytically cracked gasoline sulfur method of the present invention, the described catalytic cracking unit of step (1) comprises various types of catalytic cracking unit, such 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 oil catalytic cracking (MGD) device etc.Described main fractionating tower comprises the main fractionating tower of all process units of above-mentioned catalytic cracking family.
Alkali-free sweetening described in the step (2) can adopt technology well known in the art.Condition such as alkali-free sweetening is generally: reactor operating pressure 0.1 ~ 1.0MPa, 20 ℃ ~ 70 ℃ of temperature of reaction, charging air speed 0.5 ~ 2.0h
-1, air flow quantity/inlet amount volume ratio is 0.1 ~ 1.0.Catalyst system therefor and promotor are this area catalyzer commonly used, can select the commercial goods or are prepared according to the knowledge of this area.
Absorbing-stabilizing system described in the step (2) is the absorption stabilization element of all process units of the described catalytic cracking of step (1) family.
The feeding manner of the described disulphide separation column of step (3) is generally, and lighting end enters from tower bottom, and the hot diesel oil of catalytic cracking enters from the tower middle part.The sideline product that the hot diesel oil of catalytic cracking described here can be introduced for the catalytic cracking main fractionating tower also can be the catalytic cracking diesel oil of introducing before air cooler, and doing of diesel oil distillate is generally 330 ~ 380 ℃.The temperature of the hot diesel oil of catalytic cracking is generally 60 ℃ ~ 290 ℃, preferred 100 ℃ ~ 160 ℃.The endpoint control of disulphide fractionator overhead light gasoline fraction is 45 ℃ ~ 60 ℃, is preferably 50 ℃ ~ 55 ℃; Middle gasoline fraction endpoint control is 75 ℃ ~ 95 ℃, is preferably 80 ℃ ~ 85 ℃.Lighting end is through behind the alkali-free sweetening, and the mercaptan that wherein contains is oxidized to heavier disulphide, enters in the fractionation process of disulphide separation column in the heavier middle gasoline and diesel oil distillate.
In the step (4), gasoline mixes with the last running that step (1) obtains in the gained, with after hydrogen mixes, carries out heat exchange with the hydrodesulfurization reaction effluent again.
The reaction conditions of the described hydrogenation protecting reactor of step (4) is: reaction pressure 1.0 MPa ~ 4.0 MPa, preferred 1.5 MPa ~ 2.0 MPa; 120 ℃ ~ 220 ℃ of reaction temperature ins, preferred 150 ℃ ~ 200 ℃; Volume space velocity 1.0h
-1~ 10.0 h
-1, preferred 4.0h
-1~ 8.0 h
-1Hydrogen to oil volume ratio 30: 1 ~ 300: 1, preferred 50: 1 ~ 200: 1.
Beds in the described hydrogenation protecting reactor is single bed or dual bed, described catalyzer diolefin hydrocatalyst for saturating.Hydrocatalyst for saturating is with Al
2O
3Be carrier, with group vib metal such as Mo and/or W, group VIII metal such as Co and/or Ni are reactive metal, take P and K as auxiliary agent.Also can adopt the saturated various commercial catalysts of selective hydrogenation, such as the Gasoline Hydrotreating Catalysts such as SHT-1, FH-40C of Fushun Petrochemical Research Institute's development, or by the existing method preparation in this area.
As required can also be at a certain proportion of one or more protective materials of the top grating of hydrogenation protecting catalyst reactor bed, the volume ratio of protective material and hydrocatalyst for saturating is 0.2 ~ 2, preferred 0.5 ~ 1.Selected protective material cording has larger specific surface area and porosity, such as FBN-02, the FBN-03 series Bird's Nest protective material of Fushun Petrochemical Research Institute's development, perhaps by the preparation of this area ordinary method.
The reaction conditions of the described hydrodesulphurisatioreactors reactors of step (5) is: reaction pressure 1.0 MPa ~ 4.0 MPa, preferred 1.5 MPa ~ 2.0 MPa; 200 ℃ ~ 300 ℃ of reaction temperature ins, preferred 250 ℃ ~ 280 ℃; Volume space velocity 1.0h
-1~ 10.0 h
-1, preferred 2.0h
-1~ 5.0 h
-1Hydrogen to oil volume ratio 100: 1 ~ 700: 1, preferred 250: 1 ~ 350: 1.
Described hydrodesulphurisatioreactors reactors comprises at least two beds, has cold hydrogen to inject at adjacent catalyst bed interlayer and arranges.Different beds can the grading loading Hydrobon catalyst.Preferred Hydrobon catalyst is for loading on unformed Al
2O
3And/or the group vib metal on the pure aluminium silicate carrier such as Mo and/or W, and/or group VIII metal Co and/or Ni non-precious metal catalyst, also can select the various commercial catalysts such as selective hydrodesulfurization or deep desulfurization olefin hydrocarbon reduction, FGH-11, FGH-21, FGH-31 such as Fushun Petrochemical Research Institute's development, the gasoline hydrogenation catalysts such as RSDS-1 of Beijing Research Institute of Petro-Chemical Engineering development, perhaps the existing method by this area prepares.
Wherein in step (5), after step (4) gained reaction effluent heats up through the process furnace heating or with 345 ℃ ~ 500 ℃ high temperature slurry oil heat exchange that the catalytic cracking main fractionating tower is drawn, namely reach the feeding temperature of hydrodesulphurisatioreactors reactors.Preferably utilize the high temperature slurry oil of catalytic cracking fractionating tower to carry out the heat exchange intensification to the hydrogenating desulfurization charging, can save a hydrodesulfurization reaction charging process furnace, save facility investment and running cost.
In step (6), the reaction effluent of step (5) can be first before entering gas-liquid separator carries out heat exchange with the mixture of middle gasoline and last running and hydrogen and lowers the temperature.The hydrogen-rich gas that gas-liquid separator obtains enters the desulphurization of recycle hydrogen tower after removing the liquid phase of carrying secretly through cyclone separator.Desulphurization of recycle hydrogen adopts amine liquid solvent adsorption method, and described amine liquid is organic bases, and is more with alcamines, Monoethanolamine MEA BASF (MEA) commonly used, diethanolamine (DEA), diisopropanolamine (DIPA) (DIPA), one or more in the N methyldiethanol amine (MDEA).In the desulphurization of recycle hydrogen tower, inject poor amine liquid from thionizer top, extract rich amine liquid carrying device recycling utilization at the bottom of the tower out; Mix with the external new hydrogen of device after removing recycle hydrogen behind the hydrogen sulfide and boosting through compressor, as mixed hydrogen for device.Hydrogen sulfide content behind the described desulphurization of recycle hydrogen in the recycle hydrogen is preferred 0 ~ 50 μ L/L of 0 ~ 300 μ L/L.
The described gas-liquid separator of step (6) is realized the gas-liquid separation of hydrogenating desulfurization product, and control condition is: 40 ℃ ~ 50 ℃ of temperature, pressure 1.0 MPa ~ 4.0 MPa, preferred 1.5 MPa ~ 2.0 MPa.
The present invention is by arranging the gradient cooling device at catalytic cracking main fractionating tower cat head, obtain lighting end and the last running of specific boiling range scope, then alkali-free sweetening and hydrogenating desulfurization unit are introduced respectively in the lighting end and the last running that obtain, thereby hydro-refining unit and catalytic cracking unit main fractionating tower are combined.Then the disulphide separation column is introduced in lighting end behind the alkali-free sweetening and the next thermocatalysis diesel oil of catalytic cracking unit main fractionating tower, remove easily green coke material of the petroleum naphtha mid-boiling point is relatively high behind the alkali-free sweetening disulphide and trace by fractionation, significantly reduce the total sulfur content of gasoline in cat head petroleum naphtha and a small amount of side line.At last the cat head last running of catalytic cracking main fractionating tower with come among autospasy disulphide separation column a small amount of the gasoline direct hot feed to the gasoline selective hydrodesulfurizationmodification unit, and utilize the high temperature slurry oil of catalytic cracking heat affluence to be the gasoline selective hydrodesulfurizationmodification heat supply, make it carry out under optimum conditions hydrogenating desulfurization.Treated gasoline behind the hydrogenation blends device with disulphide fractionator overhead petroleum naphtha and goes to gasoline products mediation system after air lift removes hydrogen sulfide.
Compared with prior art, catalytically cracked gasoline sulfur method of the present invention has the following advantages:
(1) carries out gradient cooling at catalytic cracking main fractionating tower cat head, obtain the gasoline fraction of different boiling range scopes, saved catalytically cracked gasoline weight gasoline Cutting Tap, reduced plant investment, reduced plant energy consumption.
(2) catalytic cracking main fractionating tower and gasoline hydrodesulfurizationmethod device organically combine, reduce the chance that contacts with oxygen of catalytically cracked gasoline, reduce the possibility of gasoline sweetener interchanger and the coking of reactor bed top, be conducive to prolong the gasoline hydrogenation device cycle of operation.
(3) by the disulphide separation column is set, the heat that utilizes the hot diesel oil of high temperature to carry is realized mass transfer, the heat transfer of lighting end and diesel oil distillate, remove easily green coke material of the petroleum naphtha mid-boiling point is relatively high behind the alkali-free sweetening disulphide and trace, significantly reduce the total sulfur content of cat head petroleum naphtha and middle gasoline.The mercaptan sulfur content that has not only guaranteed light gasoline fraction is very low, has reduced sulphur content in the middle gasoline and the content of coking precursor, has also realized taking full advantage of of catalytic cracking heat.
(4) the hydrogenating desulfurization unit arranges guard reactor, utilizes catalyzer and protectant rational gradation composition, has guaranteed the long-term operation of device.
(5) by utilizing the charging of catalytic cracking high temperature slurry oil heating hydrodesulphurisatioreactors reactors, even can cancel hydrodesulfurization reaction charging process furnace, the coking of having avoided the hydrogenating desulfurization charging to cause in process furnace local heating inequality, can also take full advantage of the heat of catalytic cracking unit affluence, reduce the whole energy consumption of gasoline sweetener.
(6) load, the boiling range scope by gasoline fraction in the control disulphide fractionation Tata or go what of gasoline fraction amount in the selective hydrodesulfurization unit, can satisfy the index request that the different standards gasoline products is produced, thereby increased the turndown ratio of device, realized device benefit goal maximization production.
(7) by the hydrogen sulfide content in the desulphurization of recycle hydrogen tower controlled circulation hydrogen that arranges in the selective hydrogenation unit, effectively reduced the mercaptan resynthesis, thereby guaranteed that the mercaptan sulfur content in the treated gasoline meets the demands.
(8) the inventive method technical process is simple, turndown ratio is large, tooling cost is low, can significantly reduce sulphur content and olefin(e) centent in the catalytically cracked gasoline, especially reduce the mercaptan sulfur content in the gasoline, produce the low-sulfur and the super low-sulfur oil that satisfy Europe V or state V specification gasoline, and the loss of octane number of gasoline is minimum.
Description of drawings
Fig. 1 is the block diagram of a kind of catalytically cracked gasoline sulfur method of the present invention.
Wherein 1 is catalytic cracking reaction oil gas, and 2 are the catalytic cracking main fractionating tower, and 3 is the one-level water cooler; 4 is secondary coolers, and 5 are lighting end, and 6 are catalytic cracking absorption stabilization element; 7 is the alkali-free sweetening unit, and 8 are the catalytic cracking rich gas, and 9 is the disulphide separation column; 10 is catalytic cracking diesel oil, and 11 is middle gasoline, and 12 are last running; 13 for diesel oil goes out device, and 14 is catalytically cracked oil, and 15 are hydrogenating desulfurization unit raw material surge tank; 16 is guard reactor; 17 is hydrodesulphurisatioreactors reactors, and 18 is gas-liquid separator, and 19 is the desulphurization of recycle hydrogen tower; 20 is poor amine liquid; 21 is rich amine liquid, and 22 is circulating hydrogen compressor, 23 hydrogen make-up; 24 is stripping tower; 25 cat head hydrogen sulfide and small molecules hydro carbons, 26 are refining heavy petrol, 27 is petroleum naphtha; 28 go to the hydrogenating desulfurization unit for middle gasoline, and 29 are in harmonious proportion for middle gasoline removes product.
Embodiment
In conjunction with Fig. 1, the technical process of sulfur method of the present invention is:
Enter catalytic cracking main fractionating tower 2 from the high-temperature oil gas 1 of catalytic cracking reaction-regeneration system rapidly and carry out fractionation, cat head is extracted＜220 ℃ rich gas and gasoline fraction out, pass through successively cat head one-level water cooler 3, cat head secondary coolers 4, control cooler outlet temperature at different levels and obtain successively last running 12, lighting end 5 and catalytic cracking rich gas 8.Lighting end 5 is sent to catalytic cracking absorption-stabilization element 6 and is obtained stable gasoline, and stable gasoline enters alkali-free sweetening unit 7, and removing wherein, mercaptan enters disulphide separation column 9 bottoms by the heat exchange intensification.The high temperature diesel oil 10 that attracts from catalytic cracking main fractionating tower 2 enters disulphide separation column 9 middle and lower parts.Extract refining petroleum naphtha 27 out from the disulphide fractionator overhead and send to the product mediation; Extract the middle gasoline fraction 11 of certain boiling range scope out from tower, send to product according to need of production one tunnel and be in harmonious proportion 29, the selective hydrodesulfurization unit is sent on another road.In the disulphide separation column, the heat that utilizes hot diesel oil to carry is realized mass transfer, the heat transfer of gasoline lighting end and diesel oil distillate, remove easily green coke material of gasoline lighting end mid-boiling point is relatively high behind the alkali-free sweetening disulphide and trace, significantly reduce the total sulfur content of cat head petroleum naphtha and middle gasoline.
The last running 12 that the middle gasoline fraction 28 that the disulphide separation column is extracted out and the cooling of catalytic cracking main fractionating tower cat head one-level obtain enters selective hydrodesulfurization unit raw material oil surge tank 15 together; after pump boosts, mix with hydrogen and be warmed up to 150 ℃ ~ 180 ℃ by heat exchange and enter guard reactor 16; it is saturated that diolefine in the blend gasoline charging is obtained, and prevents that the diene polymerization coking affects the device cycle of operation under the high temperature.The guard reactor reaction effluent enters hydrogenation main reactor 17 after high temperature slurry oil 14 heat exchange with catalytic cracking are warmed up to 230 ℃ ~ 280 ℃, carry out the depth-selectiveness hydrogenating desulfurization.Reaction effluent enters gas-liquid separator 18 after the heat exchange cooling, separator top gas phase recycle hydrogen enters desulphurization of recycle hydrogen tower 19 after the gas-liquid separation after taking off liquid, inject poor amine liquid 20 on desulphurization of recycle hydrogen tower 19 tops, rich amine liquid 21 is extracted the carrying device recycling utilization out at the bottom of tower.Recycle hydrogen after the desulfurization is mixed into the selective hydrodesulfurization systemic circulation with the external hydrogen make-up 23 of device and uses after circulating hydrogen compressor 22 boosts; Separator bottom oil phase enters stripping tower 24 behind heat temperature raising, from removed overhead hydrogen sulfide and small molecules hydro carbons 25.The petroleum naphtha 27 that the refining heavy petrol 26 that removes hydrogen sulfide is extracted out with disulphide separation column 9 cats head at the bottom of stripping tower 24 towers mixes as gasoline blend component carrying device.
Below by specific embodiment technical scheme of the present invention is described in further detail.
Embodiment all adopts technical process shown in Figure 1.Wherein the 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.
Process FCC catalytically cracked gasoline, production super low sulfur clean gasoline by technical process shown in Figure 1.
FCC catalysis obtains lighting end and last running after splitting reaction oil gas process main fractionating tower cat head gradient cooling, and the character light, last running that FCC catalytic cracking main fractionating tower cat head obtains sees Table 1.
That table 1 FCC catalytic cracking main fractionating tower cat head obtains is light, the character of last running
| Project | Lighting end | Last running |
| Density (20 ℃), g/cm 3 | 0.6875 | 0.7394 |
| Sulphur content, μ g/g | 122 | 683 |
| RON | 95.2 | 92.6 |
| Boiling range (ASTM D 86), ℃ | ? | ? |
| 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 the alkali-free sweetening unit behind the stable absorption unit, remove mercaptan sulfur.The alkali-free sweetening condition is: pressure 0.6MPa, 40 ℃ of temperature, volume space velocity 2.0h
-1, gas-oil ratio (air/lighting end) 0.7.
Lighting end behind the alkali-free sweetening and catalytic cracking diesel oil enter the disulphide separation column together, through obtaining refining light gasoline fraction and middle gasoline fraction after the fractionation.Alkali-free sweetening lighting end and catalytic cracking diesel oil cut character see Table 2.Refining light gasoline fraction and middle gasoline fraction character see Table 3.
Lighting end behind 2 alkali-free sweetenings and catalytic cracking diesel oil cut character
| Project | Lighting end behind the alkali-free sweetening | FCC catalytic cracking diesel oil cut |
| Density (20 ℃), g/cm 3 | 0.6881 | 0.8400 |
| Sulphur, μ g/g | 122 | 9800 |
| Mercaptan sulfur, μ g/g | ＜5 | — |
| RON | 95.7 | — |
| Boiling range (ASTM D 86), ℃ | ? | ? |
| IBP/10% | 32/38 | 178/208 |
| 30%/50% | 42/51 | 238/258 |
| 70%/90% | 63/78 | 300/340 |
| 95%/ FBP | 86/94 | —/360 |
The refining light gasoline fraction of table 3 and middle gasoline fraction character
| Project | Refining petroleum naphtha | Middle gasoline |
| Density (20 ℃), g/cm 3 | 0.6667 | 0.7080 |
| Sulphur, μ g/g | 5 | 230 |
| Mercaptan sulfur, μ g/g | ＜5 | — |
| RON | 95.7 | 93.1 |
| Boiling range (ASTM D 86), ℃ | ? | ? |
| IBP/10% | 28/30 | 61/64 |
| 30%/50% | 33/36 | 67/70 |
| 70%/90% | 40/42 | 74/77 |
| 95%/ FBP | 47/49 | 81/85 |
The last running that the middle gasoline that the disulphide separation column is extracted out and catalytic cracking main fractionating tower cat head obtain enters the selective hydrodesulfurization unit together, by hydrogenation protecting reactor and hydrodesulphurisatioreactors reactors, carries out deep desulfuration successively, obtains refining heavy naphtha.Hydrogenation protecting catalyst and Hydrobon catalyst are that the processing condition of hydrogenating desulfurization unit are listed in table 4.
Table 4 hydrogenating desulfurization cell process condition
| | Embodiment | 1 |
| Reactor | Protection/desulfurization | |
| Stock oil | Middle gasoline+last running | |
| Catalyzer | FH-40C/FGH-31 | |
| Reactor inlet temperature, ℃ | 165/260 | |
| The 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 refining petroleum naphtha mix as treated gasoline blend component carrying device.Refining heavy naphtha and blended gasoline character see Table 5.
The refining heavy naphtha of table 5 and mixing treated gasoline character
| Project | Hydrogenated heavy gasoline | Blended gasoline |
| Density (20 ℃), g/cm 3 | 0.7305 | 0.7182 |
| Sulphur, μ g/ |
10 | 9 |
| Mercaptan sulfur, μ g/g | <5 | <5 |
| RON | 90.2 | 92.8 |
| Boiling range (ASTM D 86), ℃ | ? | ? |
| 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, producing the clean gasoline sulphur content only is 9 μ g/g, mercaptan sulfur content＜5 μ g/g, and octane value only loses 1.4 units than the full cut of FCC.
Embodiment 2
Process MIP catalytically cracked gasoline, production super low sulfur clean gasoline by technical process shown in Figure 1.
Behind the MIP catalytic cracking reaction oil gas process main fractionating tower cat head gradient cooling, obtain lighting end and last running, the character light, last running that MIP catalytic cracking main fractionating tower cat head obtains sees Table 6.
Table 6 MIP catalytic cracking main fractionating tower cat head is light, last running character
| Project | Lighting end | Last running |
| Ratio, % | 29.49 | 70.51 |
| Density (20 ℃), g/cm 3 | 0.6772 | 0.7375 |
| Sulphur content, μ g/g | 118 | 680 |
| RON | 95.6 | 92.8 |
| Boiling range (ASTM D-86), ℃ | ? | ? |
| 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 the alkali-free sweetening unit after absorbing stabilization element, remove mercaptan sulfur.The alkali-free sweetening condition is: pressure 0.7MPa, 35 ℃ of temperature, volume space velocity 2.0h
-1, gas-oil ratio (air/lighting end) 0.9.
Lighting end behind the alkali-free sweetening and catalytic cracking diesel oil enter the disulphide separation column together, through obtaining refining petroleum naphtha and middle gasoline after the fractionation.
Lighting end behind the alkali-free sweetening and catalytic cracking diesel oil character see Table 7, and refining light gasoline fraction and middle gasoline fraction character see Table 8.
Lighting end behind table 7 alkali-free sweetening and catalytic cracking diesel oil character
| Project | The alkali-free sweetening lighting end | MIP catalytic cracking diesel oil cut |
| Density (20 ℃), g/cm 3 | 0.6878 | 0.9400 |
| Sulphur, μ g/g | 118 | 9846 |
| Mercaptan sulfur, μ g/g | ＜5 | — |
| RON | 95.6 | — |
| Boiling range (ASTM D 86), ℃ | ? | ? |
| IBP/10% | 28/37 | 180/208 |
| 30%/50% | 42/53 | 237/259 |
| 70%/90% | 60/79 | 302/349 |
| 95%/ FBP | 87/96 | —/365 |
The refining petroleum naphtha of table 8 divides and middle gasoline property
| Project | Refining petroleum naphtha | Middle gasoline |
| Density (20 ℃), g/cm 3 | 0.6667 | 0.7080 |
| Sulphur, μ g/g | 5 | 230 |
| Mercaptan sulfur, μ g/g | ＜2 | — |
| RON | 95.7 | 93.3 |
| Boiling range (ASTM D 86), ℃ | ? | ? |
| IBP/10% | 28/30 | 62/65 |
| 30%/50% | 33/36 | 68/70 |
| 70%/90% | 40/42 | 75/78 |
| 95%/ FBP | 47/49 | 82/85 |
The last running that the middle gasoline that the disulphide separation column is extracted out and preliminary fractionator obtain enters the selective hydrodesulfurization unit together, by hydrogenation protecting reactor and hydrodesulphurisatioreactors reactors, carries out deep desulfuration successively, obtains refining heavy naphtha.Hydrogenation protecting reactor and hydrodesulphurisatioreactors reactors are that the processing condition of hydrogenating desulfurization unit are listed in table 9.
Table 9 hydrodesulfurization condition
| | Embodiment | 1 |
| Reactor | Protection/desulfurization | |
| Stock oil | Middle gasoline+last running | |
| Catalyzer | FH-40C/FGH-31 | |
| Reactor inlet temperature, ℃ | 155/252 | |
| The 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 refining petroleum naphtha mix as treated gasoline blend component carrying device.Refining heavy petrol and the rear treated gasoline character that is in harmonious proportion see Table 10.
The refining heavy petrol of table 10 and treated gasoline character
| Project | Hydrogenated heavy gasoline | Treated gasoline after being in harmonious proportion |
| Density (20 ℃), g/cm 3 | 0.7305 | 0.7182 |
| Sulphur, μ g/ |
10 | 9 |
| Mercaptan sulfur, μ g/g | <5 | <5 |
| RON | 90.8 | 92.9 |
| Boiling range (ASTM D 86), ℃ | ? | ? |
| 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, the MIP sulfur content of catalytic cracking gasoline is reduced to 9 μ g/g, mercaptan sulfur content＜5 μ g/g.Octane value only loses 1.7 units than the full cut of FCC.
Comparative example 1
Stock oil is with embodiment 1, and full distillation gasoline at first carries out alkali-free sweetening, and the alkali-free sweetening condition is with embodiment 1.After the deodorization full cut through prefractionation obtain＜80 ℃ of lighting ends and 80 ℃ of last running.80 ℃ of last running carry out hydrogenating desulfurization, processing condition are listed in table 11.
Refining last running and lighting end after the hydrogenating desulfurization are mixed to get clean gasoline.Character is listed in table 12.
Table 11 hydrodesulfurization condition
| | Embodiment | 1 |
| Reactor | Protection/desulfurization | |
| Stock oil | Middle gasoline+last running | |
| Catalyzer | FH-40C/FGH-31 | |
| Temperature of reaction, ℃ | 178/282 | |
| The 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 | The FCC stable gasoline | Blended gasoline |
| Density (20 ℃), 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), ℃ | ? | ? |
| 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, the method that adopts Comparative Examples 1 to provide, the FCC sulfur content of catalytic cracking gasoline is reduced to 9 μ g/g from 520 μ g/g, mercaptan sulfur content＜5 μ g/g, and loss of octane number is 3.4 units.
And among the inventive method embodiment 1, reaching same sulphur content, loss of octane number only has 1.4 units; Compare with comparative example 1, because a small amount of easily green coke material that utilizes thermocatalysis diesel oil to remove to claim in the alkali-free sweetening process, therefore the steady running cycle of device has obtained prolongation among the embodiment 1.Be generally 6 ~ 8 months the running period of comparative example 1, and can reach 10 ~ 16 months the running period of the embodiment of the invention 1.Compare with comparative example 1, the present invention will prolong running period more than 80%.Compare with comparative example 1 equally, owing to supplying hydrogenating desulfurization unit process charging, heats the heat that utilizes catalytic cracking high temperature slurry oil affluence among the embodiment 1, catalytic cracking main fractionating tower cat head gradient cooling obtains lighting end gasoline and last running gasoline, realized the heat integration of catalytic cracking unit and hydrodesulfurization unit, significantly reduce plant energy consumption, can save energy 30% ~ 50%.Also reduce weight gasoline Cutting Tap, saved plant investment, reduced operation easier.
Claims (13)
1. catalytically cracked gasoline sulfur method may further comprise the steps:
(1) catalytic cracking main fractionating tower cat head effluent obtains lighting end, last running through behind the gradient cooling, and the cut point between described lighting end and the last running is 70 ℃ ~ 80 ℃;
(2) catalytic cracking device absorption stabilizing system is removed in the lighting end that obtains from step (1), and resulting stable gasoline enters the alkali-free sweetening unit and carries out the deodorization processing, removes mercaptan sulfur wherein;
(3) lighting end and the hot diesel oil of catalytic cracking that remove behind the mercaptan from step (2) gained enter the disulphide separation column together, obtain the petroleum naphtha product from fractionator overhead, and gasoline in the lateral line withdrawal function from the fractionation Tata is extracted the diesel oil carrying device out at the bottom of the tower; Doing of described petroleum naphtha is 45 ℃ ~ 60 ℃, and doing of middle gasoline is 75 ℃ ~ 95 ℃;
(4) gasoline enters the hydrogenation protecting reactor with after last running that step (1) obtains mixes in step (3) gained, carries out the diolefine saturated reaction;
(5) step (4) gained reaction effluent enters hydrodesulphurisatioreactors reactors, carries out the depth-selectiveness hydrogenating desulfurization;
(6) reaction effluent of step (5) enters gas-liquid separator and separates, and the gained product liquid mixes with step (3) gained petroleum naphtha through after the air lift, obtains clean gasoline product or blend component.
2. in accordance with the method for claim 1, it is characterized in that the described catalytic cracking unit of step (1) comprises one or more in 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 and the diesel oil catalytic cracking unit.
3. in accordance with the method for claim 1, it is characterized in that the alkali-free sweetening condition described in the step (2) is: reactor operating pressure 0.1 ~ 1.0MPa, 20 ℃ ~ 70 ℃ of temperature of reaction, charging air speed 0.5 ~ 2.0h
-1, air flow quantity/inlet amount volume ratio is 0.1 ~ 1.0.
4. in accordance with the method for claim 1, it is characterized in that the feeding manner of the described disulphide separation column of step (3) is, lighting end enters from tower bottom, and the hot diesel oil of catalytic cracking enters from the tower middle part.
5. in accordance with the method for claim 1, it is characterized in that the hot diesel oil of described catalytic cracking is the sideline product introduced of catalytic cracking main fractionating tower or the catalytic cracking diesel oil introduced before the air cooler.
6. in accordance with the method for claim 5, it is characterized in that doing of diesel oil distillate is 330 ~ 380 ℃, the temperature of diesel oil distillate is 60 ℃ ~ 290 ℃.
7. in accordance with the method for claim 1, it is characterized in that doing of described disulphide fractionator overhead light gasoline fraction is 50 ℃ ~ 55 ℃.
8. in accordance with the method for claim 1, it is characterized in that doing of lighting end described in the step (1) is 80 ℃ ~ 85 ℃, doing of the described middle gasoline fraction of step (3) is 80 ℃ ~ 95 ℃.
9. in accordance with the method for claim 1, it is characterized in that in the step (4), gasoline mixes with the last running that step (1) obtains in the gained, with after hydrogen mixes, carry out heat exchange with the hydrodesulfurization reaction effluent again.
10. in accordance with the method for claim 1, it is characterized in that the reaction conditions of the described hydrogenation protecting reactor of step (4) is: reaction pressure 1.0 MPa ~ 4.0 MPa, 120 ℃ ~ 220 ℃ of reaction temperature ins, volume space velocity 1.0h
-1~ 10.0 h
-1, hydrogen to oil volume ratio 30: 1 ~ 300: 1.
11. in accordance with the method for claim 1, it is characterized in that dose the hydrogen protective material in that the upper cycle of hydrogenation protecting catalyst reactor bed is equipped, the volume ratio of hydrogenation protecting agent and hydrocatalyst for saturating is 0.2 ~ 2.
12. in accordance with the method for claim 1, it is characterized in that the reaction conditions of the described hydrodesulphurisatioreactors reactors of step (5) is: reaction pressure 1.0 MPa ~ 4.0 MPa, 200 ℃ ~ 300 ℃ of reaction temperature ins, volume space velocity 1.0h
-1~ 10.0 h
-1, hydrogen to oil volume ratio 100: 1 ~ 700: 1.
13. in accordance with the method for claim 1, it is characterized in that, in step (5), after step (4) gained reaction effluent heats up through process furnace heating or with 345 ℃ ~ 500 ℃ high temperature slurry oil heat exchange that the catalytic cracking main fractionating tower is drawn, namely reach the feeding temperature of hydrodesulphurisatioreactors reactors.
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| CN103571536A (en) * | 2013-09-17 | 2014-02-12 | 中国石油大学(华东) | Device and method for producing clean gasoline and increasing propylene yield through catalytic cracking and hydrogenation |
| CN105462607A (en) * | 2016-01-13 | 2016-04-06 | 山东联星能源集团有限公司 | Combined process for catalytic and cracked gasoline desulfurization |
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