CN103074107B - A kind of method of producing the full distillation gasoline product of super low sulfur - Google Patents
A kind of method of producing the full distillation gasoline product of super low sulfur Download PDFInfo
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Abstract
A kind of method of producing the full distillation gasoline product of super low sulfur, 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, enter two hydrotreatment reaction zones successively, carry out selective hydrogenation respectively and take off diene and selective hydrodesulfurization reaction, the hydrogenated heavy gasoline cut obtained is after air sweetening sulphur, obtain low-sulfur heavy naphtha.Light gasoline fraction will be refined mix with gasoline fraction middle after reformation and low-sulfur heavy naphtha, obtain the full distillation gasoline product 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, production 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.
At present, the RSDS succeeded in developing mainly contains the Scanfining technology of ExxonMobil company of the U.S. and the Prime-G of French Inst Francais Du Petrole
+technology, 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 of producing the full distillation gasoline product of super low sulfur 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.
Technical scheme 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, enter two hydrotreatment reaction zones successively, carry out selective hydrogenation respectively and take off diene and selective hydrodesulfurization reaction, the hydrogenated heavy gasoline cut obtained, after air sweetening sulphur, obtains low-sulfur heavy naphtha;
(5) in the middle of after the refining light gasoline fraction of step (2) gained and the reformation of step (3) gained, the low-sulfur heavy naphtha of gasoline fraction and step (4) gained mixes, and obtains the full distillation gasoline product of super low sulfur.
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
Accompanying drawing 1 is the main-process stream schematic diagram of the method for the full distillation gasoline product of production super low sulfur provided by the invention.
Accompanying drawing 2 is schematic flow sheets that heavy naphtha carries out selective hydrodesulfurization.
Embodiment
The present invention is so concrete enforcement:
(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 full distillation gasoline raw material.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.
(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 ~ 10h
-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.This gasoline fraction is carried out catalytic reforming process, obtains the gasoline fraction that octane value RON is 100.
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.Described Hydrobon catalyst is also containing co-catalyst component, and co-catalyst component is selected from one or more in Mg, Zn, Fe, Ca.The active metal component of preferred described Hydrobon catalyst is nickel, tungsten and 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 high-pressure separator after cooling, separation obtains liquid phase stream and enters stabilizer tower, stablize bottom stream after air sweetening sulphur, obtain low-sulfur heavy naphtha, 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 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.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.
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.Preferably, 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 8 ~ 35 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.
(5) in the middle of after the refining light gasoline fraction of step (2) gained and the reformation of step (3) gained, the low-sulfur heavy naphtha of gasoline fraction and step (4) gained mixes, and obtains the full distillation gasoline product of super low sulfur.
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: the 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 15 by pipeline 5 and carried out the mediation of full cut product.Middle gasoline fraction is drawn by pipeline 6, send into fixed bed hydrogenation refining reaction system 7 and carry 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 15 by pipeline 10 and carried out the blending of full cut product.Heavy naphtha is drawn by pipeline 11, and send into fixed bed hydrogenation desulphurization reaction system 12 and carry out selective hydrodesulfurization, the product obtained sends to air sweetening by pipeline 13, then is drawn by pipeline 14, sends to products pot 15 and carries 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 16 boost after mix with the hydrogen from pipeline 38 after enter interchanger 18 through pipeline 17, enter the first hydrogenator 20 with after the material-heat-exchanging from pipeline 25 through pipeline 19, carry out selectivity take off two alkene reactions.First hydrogenator effluent enters after process furnace 22 heating through pipeline 21, enters the second hydrogenator 24, carry out selective hydrodesulfurization reaction through pipeline 23.Second hydrogenator effluent enters interchanger 18 through pipeline 25, enters high-pressure separator 27 again with after the material-heat-exchanging from pipeline 17 through pipeline 26.After high-pressure separator 27 carries out vapor-liquid separation, the hydrogen rich stream at top enters recycle hydrogen de sulfuration hydrogen tower 32 by pipeline 28, drawn from tower top hydrogen out by pipeline 33, circulating hydrogen compressor 36 is entered through pipeline 35 after mixing with the new hydrogen from pipeline 34, after circulating hydrogen compressor supercharging, one tunnel is through the cold hydrogen of pipeline 37 as the second reactor, and another road mixes with feedstock pump 16 outlet material through pipeline 38.The stream passes via line 29 obtained bottom high-pressure separator 27 enters stabilizer tower 30, and the light hydrocarbon gas of tower top is extracted out by pipeline 31, and bottom product sends to air sweetening through pipeline 13, sends to products pot afterwards carry out the blending of full cut product by pipeline 14.
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-1A.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.The carrier of catalyzer C1 is aluminum oxide, and active metal consists of: the heavy % of molybdenum oxide 15.6, 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 11.0, 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, and total sulfur content is 20 μ g/g, and mercaptan sulfur content is 12 μ g/g, the gasoline meeting mercaptan sulfur < 10 μ g/g after air sweetening dispatches from the factory requirement, but product total sulfur 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 135 DEG C, gained light gasoline fraction, middle gasoline fraction and heavy naphtha account for 30.0 heavy %, 35.0 heavy % and the 35.0 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 two hydrotreating reactors after heavy naphtha mixes with hydrogen successively to carry out selective hydrogenation and take off diene, selective hydrodesulfurization reaction, then through air sweetening.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 two hydrotreating reactors of process in table 3.The character of full cut product is in table 4.The sulphur content of product is 8.2 μ g/g as can be seen from Table 4, and olefin(e) centent is 21.5 volume %, and RON only loses 0.7, and product yield reaches 100.0 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 150 DEG C, gained light gasoline fraction, middle gasoline fraction and heavy naphtha account for 33.0 heavy %, 37.0 heavy % and the 30.0 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 two hydrotreating reactors after heavy naphtha mixes with hydrogen successively to carry out selective hydrogenation and take off diene, selective hydrodesulfurization reaction, then through air sweetening.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 two hydrotreating reactors of process in table 3.The character of full cut product is in table 4.The sulphur content of product is 9.8 μ g/g as can be seen from Table 4, and olefin(e) centent is 29.0 volume %, and RON only loses 0.9, and product yield reaches 100.2 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 two hydrotreating reactors after heavy naphtha mixes with hydrogen successively to carry out selective hydrogenation and take off diene, selective hydrodesulfurization reaction, then through air sweetening.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 two hydrotreating reactors of process in table 3.The character of full cut product is in table 4.The sulphur content of product is 6.5 μ g/g as can be seen from Table 4, and olefin(e) centent is 19.0 volume %, and RON only loses 0.4, and product yield reaches 99.9 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, % | 97.4 |
| RON | 89.6 |
| RON loses | 4.0 |
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Stock oil | A | B | C |
| Reaction conditions | |||
| Middle runnings hydrofining reactor: | |||
| Catalyzer | RS-1A | RS-1A | RS-1A |
| Hydrogen dividing potential drop, MPa | 3.2 | 3.2 | 2.5 |
| Temperature of reaction, DEG C | 310 | 315 | 290 |
| Liquid hourly space velocity, h -1 | 3.5 | 3.0 | 3.5 |
| Hydrogen to oil volume ratio | 400 | 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 | 3.5 | 3.5 | 4.0 |
| 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 | 8.2 | 9.8 | 6.5 |
| Mercaptan sulfur content, μ g/g | 5 | 5 | 4 |
| Alkene, volume % | 21.5 | 29.0 | 19.0 |
| Desulfurization degree, heavy % | 98.9 | 99.1 | 98.3 |
| Olefin saturated rate, volume % | 24.6 | 30.9 | 24.0 |
| RON | 92.9 | 93.6 | 93.0 |
| RON loses | 0.7 | 0.9 | 0.4 |
| Product yield, heavy % | 100.0 | 100.2 | 99.9 |
Claims (15)
1. produce a method for the full distillation gasoline product of super low sulfur, 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, enter two hydrotreatment reaction zones successively, carry out selective hydrogenation respectively and take off diene and selective hydrodesulfurization reaction, the hydrogenated heavy gasoline cut obtained, after air sweetening sulphur, obtains low-sulfur heavy naphtha;
(5) in the middle of after the refining light gasoline fraction of step (2) gained and the reformation of step (3) gained, the low-sulfur heavy naphtha of gasoline fraction and step (4) gained mixes, obtain the full distillation gasoline product of super low sulfur, the total sulfur content of the full distillation gasoline product of described super low sulfur 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 high-pressure separator after cooling, separation obtains liquid phase stream and enters stabilizer tower, stablize bottom stream after air sweetening sulphur, obtain low-sulfur heavy naphtha, the temperature of reaction of described first reaction zone is lower than the temperature of reaction of second reaction zone 100 ~ 220 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.
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.
9. according to the method described in claim 1 or 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. in accordance with the method for claim 6, it 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 8 ~ 35 heavy %, and the content of nickel and/or cobalt is 0.5 ~ 5 heavy %.
13. according to the method described in claim 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 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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| CN103409162B (en) * | 2013-07-17 | 2015-12-09 | 辽宁石油化工大学 | Pretreatment process before a kind of hydrogenation of coker gasoline |
| US9683183B2 (en) | 2015-02-04 | 2017-06-20 | China University of Petroleum—Beijing | Method for deep desulfurization of gasoline |
| CN104673379B (en) * | 2015-02-04 | 2016-08-24 | 中国石油大学(北京) | A kind of deep desulfurization of gasoline method |
| CN104673378B (en) * | 2015-02-04 | 2016-08-17 | 中国石油大学(北京) | A kind of production method of sulfur-free gasoline |
| CN105542853A (en) * | 2016-01-13 | 2016-05-04 | 山东联星能源集团有限公司 | Selective hydrodesulfurization process for preparing ultra-low sulfur clean gasoline |
| 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 |
| CN107488464B (en) | 2017-04-27 | 2019-04-30 | 中国石油大学(北京) | A kind of production method and production system of ultra-clean high-knock rating gasoline |
| CN114426885B (en) * | 2020-09-25 | 2023-09-05 | 中国石油化工股份有限公司 | Method and device for processing residual oil |
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