CN103074106B - A kind of method reducing content of sulfur in gasoline - Google Patents
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Abstract
A kind of method reducing content of sulfur in gasoline, full distillation gasoline is fractionated into light gasoline fraction, middle gasoline fraction and heavy naphtha, light gasoline fraction refines the mercaptan sulfur removed wherein through alkali cleaning, middle gasoline fraction enters after the first hydrogenation unit through catalytic reforming process, middle gasoline fraction after obtaining the reformation of octane value raising, heavy naphtha enters the second hydrogenation unit, contacts carry out selective hydrodesulfurization reaction with catalyst for selectively hydrodesulfurizing.Light gasoline fraction will be refined mix with gasoline fraction middle after reformation and hydrogenated heavy gasoline cut, obtain the full distillation gasoline cut of super low sulfur.The full distillation gasoline product total sulfur content of gained is less than 10 μ g/g, and compared with full distillation gasoline raw material, octane value RON loss is less than 1.0 units.
Description
Technical field
The present invention relates to a kind of method reducing content of sulfur in gasoline, particularly one reduces sulfur content of catalytic cracking gasoline, produces the method for super low-sulfur oil.
Background technology
Along with the enhancing of human environment protection consciousness, in vehicle exhaust, objectionable impurities more and more causes the attention of people to the pollution of atmospheric environment, and countries in the world all propose increasingly strict restriction to the composition of motor spirit, especially sulphur content.European Union came into effect Europe IV automobile exhaust emission standard in 2005, require that content of sulfur in gasoline is less than 50 μ g/g, come into effect Euro V emissions on September 1st, 2009, require that content of sulfur in gasoline is less than 10 μ g/g, also plan to carry out more strict Europe VI standard at about 2014; China will implement state III gasoline standard (GB17930-2006) the end of the year 2009, require that sulphur content is not more than 150 μ g/g.Wherein, Beijing takes the lead in coming into effect on January 1st, 2008 the new provincial standard (DB11/238-2007) meeting Europe IV emission standard, requires that content of sulfur in gasoline is reduced to 50 below μ g/g.Shanghai IV standard, Guangdong IV standard that Shanghai City, Guangzhou also came into effect sulphur content be not more than 50 μ g/g respectively at 2009,2010.The continuous upgrading of gasoline quality standard, makes the gasoline production technology of oil refining enterprise be faced with more and more stern challenge.
At present, in domestic gasoline product, the sulphur of more than 90% carrys out catalytic cracking (FCC) gasoline, and therefore, reducing sulfur content of catalytic cracking gasoline is the key point reducing finished product content of sulfur in gasoline.
The sulphur content reducing catalytically cracked gasoline can adopt catalytically cracked material weighted BMO spaces (front-end hydrogenation), catalytic gasoline hydrogenation desulfurization (back end hydrogenation) two kinds of modes usually.Wherein, catalytically cracked material pre-treatment significantly can reduce the sulphur content of catalytically cracked gasoline, but needs to operate under temperature and pressure all very exacting terms, simultaneously because unit capacity is large, cause hydrogen to consume also larger, these all will improve investment or the running cost of device.However, due to the heaviness of world's crude oil, increasing catalytic cracking unit starts to process the inferior raw material containing normal, vacuum residuum etc., and therefore catalytically cracked material hydrogenation unit amount is also increasing year by year.Meanwhile, along with the innovation of catalytic cracking technology, the application gradually of catalytic cracking desulfurization auxiliary, the sulfur content of catalytic cracking gasoline of China's Some Enterprises can reach 500 below μ g/g, or even 150 below μ g/g.But if the sulphur content of catalytically cracked gasoline will be reduced further, make it to be less than 50 μ g/g (meeting Europe IV emission standard to the restriction of content of sulfur in gasoline), even be less than 10 μ g/g (meeting the restriction of Euro V emissions to content of sulfur in gasoline), then must increase substantially the operating severity of catalytically cracked material hydrogenation unit, very uneconomical economically.
Compare front-end hydrogenation, catalytic gasoline hydrogenation desulfurization is all lower than catalytically cracked material weighted BMO spaces in plant investment, raw tight cost and hydrogen consumption, and its different desulfurization depth can meet the requirement of different size sulphur content.If but it is saturated in a large number and make loss of octane number very large to adopt traditional hydrofinishing process can make to have in catalytically cracked gasoline high-octane olefin component.The effective way solved the problem carries out selective hydrodesulfurization to catalytically cracked gasoline exactly, while hydrogenating desulfurization, namely reduce the degree of saturation of wherein alkene to greatest extent, to reduce loss of octane number as far as possible.
Sulfur Content in Catalytic Cracking Gasoline can be reduced to 50 below μ g/g by the catalytic gasoline selective hydrodesulfurizationmodification second-generation technology (RSDS-II) of Research Institute of Petro-Chemical Engineering's exploitation, and loss of octane number is little.Adopt RSDS-II technology can meet demand to clean gasoline under the existing gasoline standard of China, but under the megatrend of world development, motor spirit specification index can be more and more stricter.Therefore, how existing Technology flow process to be optimized, the clean gasoline (S < 10 μ g/g) for the production of more low sulfur content seems necessary.
Except catalytic gasoline selective hydrodesulfurizationmodification technique, all right hydrogenation of catalytically cracked gasoline is used as the raw material of catalytic reforming process.Specifically, distill out a certain suitable fraction section of catalytically cracked gasoline exactly, then deep hydrodesulfurizationof, denitrogenation saturated whole alkene are carried out to it, obtain without sulphur, low alkene, high-octane gasoline blending component through catalytic reforming process as raw material.
The object of the invention is above-mentioned two kinds of techniques to organically combine, a kind of catalytic gasoline selective hydrodesulfurizationmodification combination technique can producing super low-sulfur oil is provided.Take catalytically cracked gasoline as raw material, after process of the present invention, product sulphur content is less than 10 μ g/g, and loss of octane number is very little.The present invention can be refinery and provides clean gasoline production process more flexibly, provides important technical support for solving domestic catalytic gasoline sulphur content problem.
At present, the RSDS succeeded in developing mainly contains the Scanfining technology of ExxonMobil company of the U.S. and the Prime-G+ technology of French Inst Francais Du Petrole, and domestic RSDS series technique, OCT-M technology etc.
EP0940464 which disclose catalytic gasoline of whole fraction is cut into gently, in, weigh three sections of cuts, last running is sent into the first bed hydrogenating desulfurization, effluent and the lower middle runnings of temperature of the first bed outlet are mixed into the second bed hydrogenating desulfurization.The patent provides a kind of thinking reducing sulfur content of catalytic cracking gasoline.But the method first bed temperature of reaction very high (WABT=360 DEG C), alkene is all saturated, the second bed temperature of reaction WABT=302 DEG C, and olefin saturated rate is 57%.Because the method olefin saturated rate is higher, and do not have octane value recovering means, loss of octane number can be larger.Meanwhile, after being cut by catalytic gasoline of whole fraction described in this patent, lighting end proportion is 50% ~ 80%, a large amount of sulfide, comprises thiophene-type sulfide and to remain in lighting end not through removing, reduce the desulfurization degree of full distillation gasoline product.Gasoline products after this patent process, its sulphur content cannot be less than 10 μ g/g.
US5906730 which discloses FCC gasoline segmentation sulfur removal technology.First paragraph keeps desulfurization degree 60 ~ 90%, processing condition: temperature 200 ~ 350 DEG C, pressure 5 ~ 30kg/cm
2, liquid hourly space velocity 2 ~ 10h
-1, hydrogen to oil volume ratio 89 ~ 534, H
2s concentration controls to be less than 0.1 volume %.Second segment controls desulfurization degree 60 ~ 90%, processing condition: temperature 200 ~ 300 DEG C, pressure 5 ~ 15kg/cm
2, liquid hourly space velocity 2 ~ 10h
-1, hydrogen to oil volume ratio 178 ~ 534, H
2s concentration controls to be less than 0.05 volume %.If second segment desulfurization does not still reach expection object, two sections of desulfurization outlet flow effluent are continued desulfurization, and its processing condition are identical with two sections of desulfurization process conditions.From its implementation result, when production sulphur content is less than 10 μ g/g gasoline, product loss of octane number is larger.
US5290427 this method provides a kind of processing method improving catalytic gasoline quality.Catalytic gasoline is cut into gently by the method, in, weigh three sections of cuts, then respectively from the bottom of reactor, middle part, top enters hydrodesulphurisatioreactors reactors and carries out hydrogenating desulfurization, then hydrodesulphurisatioreactors reactors outlet flow effluent enters two and instead carries out octane value recovering.Due to enter two anti-be olefine contained gasoline cut, octane value recovering process temperature-rise effect can be very large, and process control difficulties increases, and can shorten the work-ing life of catalyzer.The method is mainly applicable to heavier catalytically cracked gasoline cut, if the full distillation gasoline of process initial boiling point about 35 DEG C, then product loss of octane number is comparatively large, or C time loss of octane number is less
5 +yield too low (only about 80 volume %).
Summary of the invention
The present invention provides a kind of method reducing content of sulfur in gasoline on the basis of existing technology, and especially a kind of reduction sulfur content of catalytic cracking gasoline, produces the method for super low-sulfur oil.
Method provided by the invention comprises the following steps:
(1) full distillation gasoline is fractionated into light gasoline fraction, middle gasoline fraction and heavy naphtha, wherein the cut point of light gasoline fraction and middle gasoline fraction is 60 ~ 80 DEG C, and the cut point of middle gasoline fraction and heavy naphtha is 120 ~ 180 DEG C;
(2) light gasoline fraction enters alkali density mercaptan removal unit, refines the mercaptan sulfur removed wherein through alkali cleaning, obtains refining light gasoline fraction;
(3) in the middle of, gasoline fraction enters the first hydrogenation unit, contacts reactions such as carrying out hydrogenating desulfurization, hydrodenitrification and hydrogenation of olefins with Hydrobon catalyst, and generation sulphur, nitrogen content are all less than the refining middle gasoline fraction of 0.5 μ g/g; In the middle of refining, gasoline fraction is through catalytic reforming process, middle gasoline fraction after obtaining the reformation of octane value raising;
(4) heavy naphtha enters the second hydrogenation unit, contacts and carries out selective hydrodesulfurization reaction, obtain hydrogenated heavy gasoline cut with catalyst for selectively hydrodesulfurizing;
(5) in the middle of after the refining light gasoline fraction of step (2) gained and the reformation of step (3) gained, the hydrogenated heavy gasoline cut of gasoline fraction and step (4) gained mixes, and obtains super low-sulfur oil cut.
Preferably described second hydrogenation unit arranges three hydroconversion reaction zones, and the principal reaction of generation respectively is selective hydrogenation and takes off diene, selective hydrodesulfurization and the reaction of selective hydrodesulfurization alcohol.
Advantage of the present invention:
1, the full distillation gasoline product total sulfur content carrying out the later light gasoline fraction of desulfurization process, middle gasoline fraction and heavy naphtha mixing gained according to the present invention is less than 10 μ g/g, and compare full distillation gasoline raw material, octane value RON loss is less than 1.0 units.
2, in the present invention, the middle gasoline fraction of initial boiling point 60 ~ 80 DEG C, final boiling point 120 ~ 180 DEG C is isolated from full distillation gasoline, heavy naphtha olefin(e) centent is higher, aromaticity content is lower, sulfide more easily removes to compare initial boiling point 120 ~ 180 DEG C, to this middle gasoline fraction through hydrogenating desulfurization, hydrodenitrification, olefins hydrogenation, then obtained without sulphur, without alkene, high-octane reformed gasoline by catalytic reforming process.Can make that the sulphur content finally concocting gained gasoline declines to a great extent, olefin(e) centent decrease to some degree, and loss of octane number is very little.
3, in the present invention, the heavy naphtha of initial boiling point 120 ~ 180 DEG C is isolated from full distillation gasoline, olefin(e) centent is very low, aromaticity content is higher, sulfide is the most difficult removes, selective hydrodesulfurization is carried out to this heavy naphtha, while desulfurization, the loss of octane number caused by olefin saturated can be reduced to greatest extent.
Accompanying drawing explanation
Fig. 1 is the main-process stream schematic diagram of reduction content of sulfur in gasoline method provided by the invention.
Fig. 2 is the schematic flow sheet that heavy naphtha carries out selective hydrodesulfurization.
Embodiment
The present invention is so concrete enforcement:
Described full distillation gasoline is selected from one or more in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, the by-product gasoline of preparing ethylene by steam cracking and pressure gasoline, final boiling point ≯ 220 DEG C of above-mentioned gasoline.
(1) full distillation gasoline raw material is cut into light gasoline fraction, middle gasoline fraction and heavy naphtha respectively at 60 ~ 80 DEG C and 120 ~ 180 DEG C.The yield of light gasoline fraction, middle gasoline fraction and heavy naphtha is respectively 20 ~ 40 heavy %, 20 ~ 40 heavy %, 20 ~ 60 heavy % of gasoline stocks.
(2) light gasoline fraction enters alkali density unit, refines the mercaptan sulfur removed wherein through alkali cleaning, obtains refining light gasoline fraction.
(3) in the middle of, gasoline fraction enters the first hydrogenation unit after mixing with hydrogen, contacts with Hydrobon catalyst, temperature of reaction 200 ~ 380 DEG C, and hydrogen dividing potential drop 1.0 ~ 4.0MPa, volume space velocity 0.5 ~ 10.0h
-1, hydrogen to oil volume ratio is under the reaction conditions of 200 ~ 800, carries out desulfurization, denitrogenation, olefin saturation, and obtain sulphur, nitrogen content and be all less than 0.5 μ g/g, olefin(e) centent is less than 1 volume %, meets the gasoline fraction of catalytic reforming feed stock requirement.In the middle of refining, gasoline fraction is through catalytic reforming process, obtains the gasoline fraction that octane value RON is 100.
Described Hydrobon catalyst is the group vib of load on activated alumina and/or silica-alumina supports and/or group VIII non-precious metal catalyst.Be benchmark with oxide basis and with catalyzer, this catalyzer contains the cobalt of the 0.5 heavy % in heavy % ~ 6 and/or nickel, the molybdenum of the 5 heavy % in heavy % ~ 25 and/or tungsten.Described Hydrobon catalyst is also containing co-catalyst component, and co-catalyst component is selected from one or more in Mg, Zn, Fe, Ca.Wherein group VIII metal component is preferably nickel, and group vib metal component is preferably tungsten, can also increase a small amount of cobalt.
(4) in the preferred embodiment of the present invention, in described second hydrogenation unit, heavy naphtha enters the first reaction zone, under the effect of hydrogen, take off diene catalyst exposure with hydrogenation carry out de-two alkene reactions of selectivity, the reaction effluent of the first reaction zone enters second reaction zone, contact with catalyst for selectively hydrodesulfurizing under the effect of hydrogen and carry out selective hydrodesulfurization reaction, the reaction effluent of gained second reaction zone enters the first high-pressure separator after cooling, separation obtains gas I and liquid phase stream I, described liquid phase stream I enters the 3rd reaction zone, hydro-sweetening reaction is carried out with hydro-sweetening catalyst exposure under the effect of hydrogen, the reaction effluent of the 3rd reaction zone enters the second high-pressure separator after cooling, isolate and obtain gas II and liquid phase stream II, described liquid phase stream II enters stabilizer tower, stable bottom stream is hydrogenated heavy gasoline cut, gas phase I and gas phase II uses through depriving hydrogen sulphide Posterior circle.
The reaction conditions of described first reaction zone is: hydrogen dividing potential drop 1.0 ~ 4.0MPa, temperature of reaction 80 ~ 280 DEG C, volume space velocity 2.0 ~ 10.0h
-1, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3;
The reaction conditions of second reaction zone is: hydrogen dividing potential drop 1.0 ~ 4.0MPa, temperature of reaction 200 ~ 400 DEG C, volume space velocity 2.0 ~ 8.0h
-1, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3;
The reaction conditions of the 3rd reaction zone is: hydrogen dividing potential drop 1.0 ~ 4.0MPa, temperature of reaction 150 ~ 300 DEG C, volume space velocity 4.0 ~ 10.0h
-1, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3.
The temperature of reaction of described first reaction zone is lower than the temperature of reaction of second reaction zone 100 ~ 220 DEG C; The temperature of reaction of described 3rd reaction zone is lower than the temperature of reaction of second reaction zone 50 ~ 120 DEG C.Preferably the temperature of reaction of described first reaction zone is 120 ~ 260 DEG C, and the temperature of reaction of second reaction zone is 260 ~ 400 DEG C, and the temperature of reaction of the 3rd reaction zone is 180 ~ 280 DEG C.
In the hydrogen of described 3rd reaction zone, hydrogen sulfide content is 0 ~ 1000 μ L/L.
Described hydrogenation takes off diene catalyzer and contains a kind of alumina supporter and the load cobalt being selected from group VIII on this carrier and/or nickel, the molybdenum of group vib and/or tungsten and alkaline components, be benchmark with oxide basis and with catalyzer, this catalyzer contains the basic metal of the cobalt of the 0.5 heavy % in heavy % ~ 8 and/or nickel, the molybdenum of the 5 heavy % in heavy % ~ 25 and/or tungsten, the heavy % in heavy % ~ 6 of > 1.Preferably, wherein group VIII metal component is cobalt, and group vib metal component is molybdenum, and basic metal is potassium.Described hydrogenation takes off diene catalyzer and has higher hydrogenation activity and selectivity to diolefine, can under the reaction conditions comparatively relaxed, diene hydrogenation in heavy naphtha is removed, thus the problem of the subsequent heat stove boiler tube can effectively avoiding the condensation of etidine hydrocarbon to cause and the too fast rise of reactor pressure decrease, effectively extend the life cycle of follow-up hydrogenation catalyst reactor.
Described catalyst for selectively hydrodesulfurizing is the group vib base metal of load on unformed aluminum oxide and/or silica-alumina supports and/or group VIII non-precious metal catalyst.The carrier of preferred described catalyst for selectively hydrodesulfurizing is aluminum oxide, and active metal component is molybdenum and/or tungsten, nickel and/or cobalt; Be benchmark with oxide basis and with total catalyst weight, described molybdenum and/or the content of tungsten are 5 ~ 30 heavy %, and the content of nickel and/or cobalt is 0.5 ~ 5 heavy %.
In a preferred embodiment in accordance with this invention, described catalyst for selectively hydrodesulfurizing is catalyst for selectively hydrodesulfurizing I and the catalyst for selectively hydrodesulfurizing II of grading loading, wherein, the active metal charge capacity of catalyst for selectively hydrodesulfurizing I is greater than the active metal charge capacity of catalyst for selectively hydrodesulfurizing II.The difference of the preferred active metal charge capacity of described catalyst for selectively hydrodesulfurizing I and the active metal charge capacity of catalyst for selectively hydrodesulfurizing II is less than 5 % by weight.
The hydrogenating desulfurization selectivity of these one or both catalyst for selectively hydrodesulfurizing preferred is very high, can deep removal heavy naphtha medium sulphide content, turn avoid wherein alkene and, by saturated in a large number, the loss of octane number in this hydrodesulfurization process thus can be made very little.
The preparation method of described preferred catalyst for selectively hydrodesulfurizing is as follows.
By hydrated aluminum oxide and auxiliary agent mixing moulding, drying, roasting 2 ~ 6 hours under air again, obtained carrier.Carrier is immersed the aqueous solution containing cobalt and/or nickel compound, molybdenum and/or tungsten compound prepared after 1 ~ 4 hour, dry, at 300 ~ 550 DEG C, namely roasting obtains catalyst prod in 2 ~ 5 hours.
The compound water solution of described cobalt, molybdenum, nickel and tungsten can be prepared according to a conventional method.The compound of cobalt, molybdenum, nickel and tungsten is selected from one or more in their soluble compound respectively.The wherein preferred ammonium molybdate of the compound of molybdenum, the preferred Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of compound of cobalt, cobalt chloride, cobaltous dihydroxycarbonate one or more.The compound of nickel and tungsten is preferably one or more in nickelous nitrate, nickelous chloride, basic nickel carbonate, ammonium tungstate, ammonium metawolframate, ethyl ammonium metawolframate, metatungstic acid nickel respectively.
Preferred vacation-the boehmite of described hydrated aluminum oxide or pseudo-boehmite.
Described hydrogenating desulfurization alcohol catalyst is the VIB base metal of load on unformed aluminum oxide and/or silica-alumina supports and/or VIII non-precious metal catalyst.Preferably described hydrogenating desulfurization alcohol catalyst is identical with catalyst for selectively hydrodesulfurizing.
In one of them preferred embodiment of the present invention, described hydrogenating desulfurization alcohol catalyst is catalyst for selectively hydrodesulfurizing I and/or catalyst for selectively hydrodesulfurizing II.With selective hydrodesulfurization alcohol catalyst, heavy naphtha selective hydrodesulfurization product is carried out to the method for further mercaptan removal, product total sulfur is reduce further while reduction mercaptan sulfur content, both eliminated hydrogenation products air sweetening process, reduce salkali waste discharge, make production process more environmental protection, the desulfurization depth of heavy naphtha can be improved again.
In the hydrogen of described 3rd reaction zone, hydrogen sulfide content is 0 ~ 1000 μ L/L.In hydrodesulfurization process, H in gas phase
2s easily and olefin hydrocarbon molecules recombine generate weight molecule mercaptan sulfur.Therefore hydrogen sulfide content in the 3rd reaction zone restriction hydrogen.Described hydrogen is new hydrogen and/or the recycle hydrogen through depriving hydrogen sulphide process preferably.
Because the temperature of reaction of the first reaction zone and the 3rd reaction zone is all lower than second reaction zone, therefore, the charging of the first reaction zone and the 3rd reaction zone is carried out heat exchange respectively by the reaction effluent with second reaction zone and can be met temperature of reaction.Specifically, the reaction effluent of second reaction zone first carries out heat exchange with the charging of the 3rd reaction zone, then carries out heat exchange with the charging of the first reaction zone.Arrange process furnace between first reaction zone and second reaction zone, the reaction effluent of the first reaction zone enters second reaction zone after process furnace heating.
(5) the product blending of step (2), step (3), step (4) obtains full distillation gasoline product.
Below in conjunction with accompanying drawing, method provided by the present invention is further described.
According to accompanying drawing 1, the technical process of reduction content of sulfur in gasoline method provided by the invention is described in detail as follows:
Full distillation gasoline raw material from pipeline 1 enters separation column 2, obtains light gasoline fraction, middle gasoline fraction and heavy naphtha after fractionation.Light gasoline fraction is drawn through pipeline 3, sends into alkali density unit 4 and carries out alkali cleaning refining desulfurization alcohol, and the refining light gasoline fraction of gained is sent to products pot 14 by pipeline 5 and carried out the mediation of full cut product.Middle gasoline fraction is drawn by pipeline 6, the fixed bed hydrogenation refining reaction system 7 sending into the first hydrogenation unit carries out hydrogenating desulfurization, hydrodenitrification, olefins hydrogenation reaction, the liquid product of reaction is sent into catalytic reforming reaction system 9 through pipeline 8 and is carried out catalytic reforming process, and the product obtained is sent to products pot 14 by pipeline 10 and carried out the blending of full cut product.Heavy naphtha is drawn by pipeline 11, sends into the second hydrogenation unit 12 and carries out selective hydrodesulfurization, and the product obtained is sent to products pot 14 by pipeline 13 and carried out the blending of full cut product.
According to accompanying drawing 2, in method provided by the invention, the technical process of heavy naphtha selective hydrodesulfurization is described in detail as follows:
From pipeline 11 heavy naphtha through feedstock pump 15 boost after mix with the hydrogen from pipeline 48 after enter interchanger 17 through pipeline 16, enter the first hydrogenator 19 with after the material-heat-exchanging from pipeline 26 through pipeline 18, carry out selectivity take off two alkene reactions.First hydrogenator effluent enters after process furnace 21 heating through pipeline 20, enters the second hydrogenator 23, carry out selective hydrodesulfurization reaction through pipeline 22.Second hydrogenator effluent enters interchanger 25 through pipeline 24, sends into interchanger 17 again with after the material-heat-exchanging from pipeline 31 through pipeline 26, with the material-heat-exchanging from pipeline 16, and after enter the first high-pressure separator 28 through pipeline 27.After the first high-pressure separator 28 carries out vapor-liquid separation, the hydrogen rich stream at top is mixed with the hydrogen-rich stream from pipeline 36 by pipeline 29, recycle hydrogen de sulfuration hydrogen tower 41 is entered by pipeline 40, drawn from tower top hydrogen out by pipeline 42, circulating hydrogen compressor 45 is entered through pipeline 44 after mixing with the new hydrogen from pipeline 43, after circulating hydrogen compressor supercharging, one tunnel is through pipeline 46, with the mixing of materials from pipeline 30, one tunnel is through the cold hydrogen of pipeline 47 as the second reactor, and another road mixes with feedstock pump 15 outlet material through pipeline 48.From the stream passes via line 30 that the first high-pressure separator 28 bottom obtains, after mixing with the hydrogen from pipeline 46, send into interchanger 25 by pipeline 31, enter the 3rd hydrogenator 33 with from after the logistics heat exchange of pipeline 24 through pipeline 32, carry out hydro-sweetening reaction.3rd hydrogenator effluent enters the second high-pressure separator 35 through pipeline 34.After the second high-pressure separator 35 carries out vapor-liquid separation, the hydrogen rich stream at top is mixed with the hydrogen-rich stream from pipeline 29 by pipeline 36, enters recycle hydrogen de sulfuration hydrogen tower 41 by pipeline 40.The stream passes via line 37 obtained from the second high-pressure separator 35 bottom enters stabilizer tower 38, and the light hydrocarbon gas of tower top is extracted out by pipeline 39, and bottom product is sent to products pot through pipeline 13 and carried out the blending of full cut product.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
The trade names of the catalyst for selectively hydrodesulfurizing that comparative example is used are RSDS-1.The trade names of the middle gasoline fraction Hydrobon catalyst that embodiment is used are RS-1.The trade names that embodiment selectivity used takes off diene catalyzer are RGO-2.Above-mentioned catalyzer is Sinopec catalyzer branch office and produces.
Embodiment catalyst for selectively hydrodesulfurizing used is catalyzer C1 and catalyzer C2.
Embodiment selective hydrodesulfurization alcohol catalyst used is catalyzer C1 and/or catalyzer C2.
The carrier of catalyzer C1 is aluminum oxide, and active metal consists of: the heavy % of molybdenum oxide 11.6, the heavy % of cobalt oxide 3.5.The carrier of catalyzer C2 is aluminum oxide, and active metal consists of: the heavy % of molybdenum oxide 8.0, the heavy % of cobalt oxide 2.5.
Comparative example
With a kind of catalytically cracked gasoline for stock oil A, its character is as shown in table 1.With 68 DEG C for cut point stock oil A is cut into light, weigh two sections of cuts, gained lighting end and last running account for 30.0 heavy % and the 70.0 weight % of raw material respectively.Lighting end is through soda finishing mercaptan removal, and last running enters fixed-bed reactor and contacts with catalyzer RSDS-1 and carry out hydrodesulfurization reaction after mixing with hydrogen.After mercaptan removal, after lighting end and hydrogenation, last running is in harmonious proportion and obtains full distillation gasoline product.The character of hydrogenation process conditions and full distillation gasoline product lists in table 2.As can be seen from Table 2, after being in harmonious proportion, product RON loss is 4.0 units, total sulfur content is 20 μ g/g, mercaptan sulfur content is 12 μ g/g, needing to carry out air sweetening process to it again can make its gasoline meeting mercaptan sulfur < 10 μ g/g dispatch from the factory requirement, but after air sweetening, product total sulfur still cannot be less than 10 μ g/g.
Embodiment 1
The present embodiment adopts the stock oil A identical with comparative example 1, for cut point, stock oil A is cut into three sections of cuts with 60 DEG C and 120 DEG C, gained light gasoline fraction, middle gasoline fraction and heavy naphtha account for 30.0 heavy %, 30.0 heavy % and the 40.0 heavy % of raw material respectively.Light gasoline fraction is through alkali cleaning refining desulfurization alcohol sulphur.Enter fixed-bed reactor after middle gasoline fraction mixes with hydrogen and carry out hydrofining reaction, then send catalytic reforming process.Enter successively after heavy naphtha mixes with hydrogen three hydrotreating reactors carry out selective hydrogenation take off diene, selective hydrodesulfurization and selective hydrodesulfurization alcohol reaction.The product blending of above-mentioned three sections of gasoline fractions, obtains full distillation gasoline product.
The hydrogenation conditions of middle gasoline fraction and heavy naphtha hydrotreatment the reaction conditions of three hydrotreating reactors of process in table 3.The character of full cut product is in table 4.The sulphur content of product is 6.7 μ g/g as can be seen from Table 4, and olefin(e) centent is 22.5 volume %, and RON only loses 0.5, and product yield reaches 99.8 heavy %.
Embodiment 2
With a kind of catalytically cracked gasoline for stock oil B, its stock oil character is as shown in table 1.For cut point, stock oil B is cut into three sections of cuts with 65 DEG C and 140 DEG C, gained light gasoline fraction, middle gasoline fraction and heavy naphtha account for 33.0 heavy %, 33.0 heavy % and the 34.0 heavy % of raw material respectively.Light gasoline fraction is through alkali cleaning refining desulfurization alcohol sulphur.Enter fixed-bed reactor after middle gasoline fraction mixes with hydrogen and carry out hydrofining reaction, then send catalytic reforming process.Enter successively after heavy naphtha mixes with hydrogen three hydrotreating reactors carry out selective hydrogenation take off diene, selective hydrodesulfurization and selective hydrodesulfurization alcohol reaction.The product blending of above-mentioned three sections of gasoline fractions, obtains full distillation gasoline product.
The hydrogenation conditions of middle gasoline fraction and heavy naphtha hydrotreatment the reaction conditions of three hydrotreating reactors of process in table 3.The character of full cut product is in table 4.The sulphur content of product is 9.2 μ g/g as can be seen from Table 4, and olefin(e) centent is 30.2 volume %, and RON only loses 0.8, and product yield reaches 100.0 heavy %.
Embodiment 3
With a kind of catalytically cracked gasoline for stock oil C, its stock oil character is as shown in table 1.For cut point, stock oil C is cut into three sections of cuts with 80 DEG C and 160 DEG C, gained light gasoline fraction, middle gasoline fraction and heavy naphtha account for 40.0 heavy %, 40.0 heavy % and the 20.0 heavy % of raw material respectively.Light gasoline fraction is through alkali cleaning refining desulfurization alcohol sulphur.Enter fixed-bed reactor after middle gasoline fraction mixes with hydrogen and carry out hydrofining reaction, then send catalytic reforming process.Enter successively after heavy naphtha mixes with hydrogen three hydrotreating reactors carry out selective hydrogenation take off diene, selective hydrodesulfurization and selective hydrodesulfurization alcohol reaction.The product blending of above-mentioned three sections of gasoline fractions, obtains full distillation gasoline product.
The hydrogenation conditions of middle gasoline fraction and heavy naphtha hydrotreatment the reaction conditions of three hydrotreating reactors of process in table 3.The character of full cut product is in table 4.The sulphur content of product is 4.8 μ g/g as can be seen from Table 4, and olefin(e) centent is 19.0 volume %, and RON only loses 0.2, and product yield reaches 99.7 heavy %.
Table 1
| Material name | A | B | C |
| Density (20 DEG C), g/cm 3 | 0.7320 | 0.7300 | 0.7250 |
| Sulphur content, μ g/g | 772 | 1100 | 380 |
| Alkene, volume % | 28.7 | 42.0 | 25.0 |
| Boiling range (ASTM D86), DEG C | |||
| Initial boiling point | 35 | 32 | 33 |
| 10％ | 51 | 52 | 44 |
| 50％ | 89 | 94 | 85 |
| 90％ | 180 | 175 | 168 |
| Final boiling point | 202 | 191 | 193 |
| RON | 93.6 | 94.5 | 93.4 |
Table 2
| Comparative example | |
| Stock oil | A |
| Catalyzer | RSDS-1 |
| Hydrogenation process conditions: | |
| Hydrogen dividing potential drop, MPa | 1.6 |
| Temperature of reaction, DEG C | 310 |
| Liquid hourly space velocity, h-1 | 4.0 |
| Hydrogen to oil volume ratio | 400 |
| Full cut product property: | |
| Density (20 DEG C), g/cm 3 | 0.7315 |
| Sulphur content, μ g/g | 20 |
| Mercaptan sulfur content, μ g/g | 12 |
| Alkene, volume % | 15.8 |
| Desulfurization degree, heavy % | 97.4 |
| Olefin saturated rate, volume % | 44.9 |
| RON | 89.6 |
| RON loses | 4.0 |
| Product yield, heavy % | 99.8 |
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Stock oil | A | B | C |
| Reaction conditions | |||
| Middle runnings hydrofining reactor: | |||
| Catalyzer | RS-1 | RS-1 | RS-1 |
| Hydrogen dividing potential drop, MPa | 3.2 | 3.2 | 2.5 |
| Temperature of reaction, DEG C | 300 | 310 | 290 |
| Liquid hourly space velocity, h -1 | 3.5 | 3.0 | 3.5 |
| Hydrogen to oil volume ratio | 300 | 400 | 300 |
| Last running first hydrotreating reactor: | |||
| Catalyzer | RGO-2 | RGO-2 | RGO-2 |
| Hydrogen dividing potential drop, MPa | 1.6 | 1.6 | 1.6 |
| Temperature of reaction, DEG C | 190 | 200 | 180 |
| Liquid hourly space velocity, h -1 | 8.0 | 6.0 | 6.0 |
| Hydrogen to oil volume ratio | 400 | 400 | 500 |
| Last running second hydrotreating reactor: | |||
| Catalyzer | C1+C2 | C1+C2 | C1+C2 |
| Hydrogen dividing potential drop, MPa | 1.6 | 1.6 | 1.6 |
| Temperature of reaction, DEG C | 310 | 315 | 300 |
| Liquid hourly space velocity, h -1 | 4.0 | 4.0 | 4.0 |
| Hydrogen to oil volume ratio | 400 | 400 | 400 |
| Last running the 3rd hydrotreating reactor: | |||
| Catalyzer | C1 | C1+C2 | C2 |
| Hydrogen dividing potential drop, MPa | 240 | 260 | 250 |
| Temperature of reaction, DEG C | 1.6 | 1.6 | 1.6 |
| Liquid hourly space velocity, h -1 | 8.0 | 8.0 | 8.0 |
| Hydrogen to oil volume ratio | 500 | 500 | 500 |
Table 4
| Product property | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density (20 DEG C), g/cm 3 | 0.7260 | 0.7250 | 0.7200 |
| Sulphur content, μ g/g | 6.7 | 9.2 | 4.8 |
| Mercaptan sulfur content, μ g/g | ＜3 | 5 | ＜3 |
| Alkene, volume % | 22.5 | 30.2 | 19.0 |
| Desulfurization degree, heavy % | 99.1 | 99.2 | 98.7 |
| Olefin saturated rate, volume % | 21.6 | 28.1 | 24.0 |
| RON | 93.1 | 93.7 | 93.2 |
| RON loses | 0.5 | 0.8 | 0.2 |
| Product yield, heavy % | 99.8 | 100.0 | 99.7 |
Claims (19)
1. reduce a method for content of sulfur in gasoline, comprising:
(1) full distillation gasoline is fractionated into light gasoline fraction, middle gasoline fraction and heavy naphtha, wherein the cut point of light gasoline fraction and middle gasoline fraction is 60 ~ 80 DEG C, and the cut point of middle gasoline fraction and heavy naphtha is 120 ~ 180 DEG C;
(2) light gasoline fraction enters alkali density mercaptan removal unit, refines the mercaptan sulfur removed wherein through alkali cleaning, obtains refining light gasoline fraction;
(3) in the middle of, gasoline fraction enters the first hydrogenation unit, contacts carry out hydrogenating desulfurization, hydrodenitrification and olefin hydrogenation with Hydrobon catalyst, and generation sulphur, nitrogen content are all less than the refining middle gasoline fraction of 0.5 μ g/g; In the middle of refining, gasoline fraction is through catalytic reforming process, middle gasoline fraction after obtaining the reformation of octane value raising;
(4) heavy naphtha enters the second hydrogenation unit, contacts and carries out selective hydrodesulfurization reaction, obtain hydrogenated heavy gasoline cut with catalyst for selectively hydrodesulfurizing; Described second hydrogenation unit arranges three hydroconversion reaction zones, and the reaction of generation is followed successively by selective hydrogenation and takes off diene, selective hydrodesulfurization and the reaction of selective hydrodesulfurization alcohol;
(5) in the middle of after the refining light gasoline fraction of step (2) gained and the reformation of step (3) gained, the hydrogenated heavy gasoline cut of gasoline fraction and step (4) gained mixes, obtain super low-sulfur oil cut, described super low-sulfur oil cut is full distillation gasoline product, and the total sulfur content of described super low-sulfur oil cut is less than 10 μ g/g.
2. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of described first hydrogenation unit is: temperature of reaction 200 ~ 380 DEG C, hydrogen dividing potential drop 1.0 ~ 4.0MPa, volume space velocity 0.5 ~ 10.0h
-1, hydrogen to oil volume ratio is 200 ~ 800Nm
3/ m
3.
3. in accordance with the method for claim 1, it is characterized in that, Hydrobon catalyst described in first hydrogenation unit is the non-precious metal catalyst of load on activated alumina and/or silica-alumina supports, with oxide basis, and be benchmark with catalyzer, this Hydrobon catalyst contains the cobalt of the 0.5 heavy % in heavy % ~ 6 and/or nickel, the molybdenum of the 5 heavy % in heavy % ~ 25 and/or tungsten.
4. in accordance with the method for claim 3, it is characterized in that, described Hydrobon catalyst is also containing co-catalyst component, and co-catalyst component is selected from one or more in Mg, Zn, Fe, Ca.
5. in accordance with the method for claim 3, it is characterized in that, the active metal component of described Hydrobon catalyst is nickel, tungsten and cobalt.
6. in accordance with the method for claim 1, it is characterized in that, in described second hydrogenation unit, heavy naphtha enters the first reaction zone, under the effect of hydrogen, take off diene catalyzer with hydrogenation carry out de-two alkene reactions of selectivity, the reaction effluent of the first reaction zone enters second reaction zone, contact with catalyst for selectively hydrodesulfurizing under the effect of hydrogen and carry out selective hydrodesulfurization reaction, the reaction effluent of gained second reaction zone enters the first high-pressure separator after cooling, separation obtains gas I and liquid phase stream I, described liquid phase stream I enters the 3rd reaction zone, hydro-sweetening reaction is carried out with hydro-sweetening catalyst exposure under the effect of hydrogen, the reaction effluent of the 3rd reaction zone enters the second high-pressure separator after cooling, isolate and obtain gas II and liquid phase stream II, described liquid phase stream II enters stabilizer tower, stable bottom stream is hydrogenated heavy gasoline cut, the temperature of reaction of described first reaction zone is lower than the temperature of reaction of second reaction zone 100 ~ 220 DEG C, the temperature of reaction of described 3rd reaction zone is lower than the temperature of reaction of second reaction zone 50 ~ 120 DEG C.
7. in accordance with the method for claim 6, it is characterized in that, the reaction conditions of described first reaction zone is: hydrogen dividing potential drop 1.0 ~ 4.0MPa, temperature of reaction 80 ~ 280 DEG C, volume space velocity 2.0 ~ 10.0h
-1, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3;
The reaction conditions of second reaction zone is: hydrogen dividing potential drop 1.0 ~ 4.0MPa, temperature of reaction 200 ~ 400 DEG C, volume space velocity 2.0 ~ 8.0h
-1, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3;
The reaction conditions of the 3rd reaction zone is: hydrogen dividing potential drop 1.0 ~ 4.0MPa, temperature of reaction 150 ~ 300 DEG C, volume space velocity 4.0 ~ 10.0h
-1, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3.
8. in accordance with the method for claim 6, it is characterized in that, the temperature of reaction of described first reaction zone is 120 ~ 260 DEG C, and the temperature of reaction of second reaction zone is 260 ~ 400 DEG C, and the temperature of reaction of the 3rd reaction zone is 180 ~ 280 DEG C.
9. in accordance with the method for claim 6, it is characterized in that, hydrogenation takes off diene catalyzer and contains a kind of alumina supporter and the load cobalt being selected from group VIII on this carrier and/or nickel, the molybdenum of group vib and/or tungsten and alkaline components, be benchmark with oxide basis and with catalyzer, this catalyzer contains the cobalt of the 0.5 heavy % in heavy % ~ 8 and/or nickel, the molybdenum of the 5 heavy % in heavy % ~ 25 and/or tungsten, is greater than the basic metal that 1 heavy % is less than or equal to 6 heavy %.
10. in accordance with the method for claim 9, it is characterized in that, wherein group VIII metal component is cobalt, and group vib metal component is molybdenum, and basic metal is potassium.
11., according to the method described in claim 1 or 6, is characterized in that, described catalyst for selectively hydrodesulfurizing is the group vib base metal of load on unformed aluminum oxide and/or silica-alumina supports and/or group VIII non-precious metal catalyst.
12. in accordance with the method for claim 11, it is characterized in that, the carrier of described catalyst for selectively hydrodesulfurizing is aluminum oxide, and active metal component is molybdenum and/or tungsten, nickel and/or cobalt; Be benchmark with oxide basis and with total catalyst weight, described molybdenum and/or the content of tungsten are 5 ~ 30 heavy %, and the content of nickel and/or cobalt is 0.5 ~ 5 heavy %.
13. according to the method described in claim 1 or 6 or 12, it is characterized in that, described catalyst for selectively hydrodesulfurizing is catalyst for selectively hydrodesulfurizing I and the catalyst for selectively hydrodesulfurizing II of grading loading, wherein, the active metal charge capacity of catalyst for selectively hydrodesulfurizing I is greater than the active metal charge capacity of catalyst for selectively hydrodesulfurizing II.
14. in accordance with the method for claim 13, it is characterized in that, the difference of the active metal charge capacity of described catalyst for selectively hydrodesulfurizing I and the active metal charge capacity of catalyst for selectively hydrodesulfurizing II is less than 5 % by weight.
15. in accordance with the method for claim 6, it is characterized in that, described hydrogenating desulfurization alcohol catalyst is the VIB base metal of load on unformed aluminum oxide and/or silica-alumina supports and/or VIII non-precious metal catalyst.
16. in accordance with the method for claim 6, it is characterized in that, described hydrogenating desulfurization alcohol catalyst is identical with catalyst for selectively hydrodesulfurizing.
17. in accordance with the method for claim 13, it is characterized in that, described hydrogenating desulfurization alcohol catalyst is catalyst for selectively hydrodesulfurizing I and/or catalyst for selectively hydrodesulfurizing II.
18. in accordance with the method for claim 6, it is characterized in that, in the hydrogen of described 3rd reaction zone, hydrogen sulfide content is 0 ~ 1000 μ L/L.
19. in accordance with the method for claim 1, it is characterized in that, described full distillation gasoline is selected from one or more in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, the by-product gasoline of preparing ethylene by steam cracking and pressure gasoline, final boiling point ≯ 220 DEG C of above-mentioned gasoline.
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| US9683183B2 (en) | 2015-02-04 | 2017-06-20 | China University of Petroleum—Beijing | Method for deep desulfurization of gasoline |
| WO2016123860A1 (en) * | 2015-02-04 | 2016-08-11 | 中国石油大学(北京) | Gasoline deep desulfurization method |
| CN104673379B (en) * | 2015-02-04 | 2016-08-24 | 中国石油大学(北京) | A kind of deep desulfurization of gasoline method |
| CN105462611A (en) * | 2016-01-13 | 2016-04-06 | 山东联星能源集团有限公司 | Non-selective hydrogen desulfurization method for preparing ultra-low sulphur clean gasoline |
| CN106753524B (en) * | 2016-11-21 | 2020-11-20 | 山东昌邑石化有限公司 | Gasoline hydrogenation process |
| CN116515526B (en) * | 2022-01-20 | 2024-06-28 | 中国石油化工股份有限公司 | Hydrogenation-active metal desulfurization combined process for catalytically cracked gasoline |
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| CN1912063A (en) * | 2005-08-09 | 2007-02-14 | 中国石油化工股份有限公司 | Method of producing catalytic reforming raw material |
| CN1912062A (en) * | 2005-08-09 | 2007-02-14 | 中国石油化工股份有限公司 | Hydrogenation method for producing catalytic reforming raw material |
| CN101275084A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Method for reducing sulfur content of catalytically cracked gasoline |
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| CN1912062A (en) * | 2005-08-09 | 2007-02-14 | 中国石油化工股份有限公司 | Hydrogenation method for producing catalytic reforming raw material |
| CN101275084A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Method for reducing sulfur content of catalytically cracked gasoline |
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