CN103710045A - Method for producing ultralow-sulfur gasoline - Google Patents
Method for producing ultralow-sulfur gasoline Download PDFInfo
- Publication number
- CN103710045A CN103710045A CN201210371143.4A CN201210371143A CN103710045A CN 103710045 A CN103710045 A CN 103710045A CN 201210371143 A CN201210371143 A CN 201210371143A CN 103710045 A CN103710045 A CN 103710045A
- Authority
- CN
- China
- Prior art keywords
- gasoline
- heavy
- catalyst
- hydrogenator
- last running
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method for producing ultralow-sulfur gasoline comprises the following steps: a gasoline raw material is fractionated to form light-fraction gasoline and heavy-fraction gasoline, the light-fraction gasoline enters an alkaline extraction unit, a contact reaction of the heavy-fraction gasoline and a selective hydrodesulfurization catalyst in a first hydrogenation reactor to remove sulfides in the heavy-fraction gasoline, accounting for 90-95wt% of the total sulfur of the heavy-fraction gasoline, the obtained reaction effluent of the first hydrogenation reactor enters a second hydrogenation reactor, and contacts and reacts with a waste oil hydrogenation catalyst, and the obtained refined light-fraction gasoline is mixed with the obtained hydrogenated heavy-fraction gasoline to obtain an ultralow-sulfur gasoline fraction. High-olefin-content catalytic cracking gasoline can be processed through the method, and the total sulfur content of the obtained full-range gasoline product is less than 10mug/g; and compared with the full-range gasoline raw material, the product has a small octane number, and has an RON (research octane number) loss of 1.0 or less.
Description
Technical field
The present invention relates to a kind of method that reduces content of sulfur in gasoline, for not existing, in the situation of hydrogen, remove sulphur and the combined method of refining two processes of hydrocarbon ils under hydrogen exists.
Background technology
Along with the enhancing of human environment protection consciousness, in vehicle exhaust, objectionable impurities more and more causes people's attention to the pollution of atmospheric environment, and countries in the world have all proposed increasingly strict restriction, especially sulphur content to the composition of motor spirit.European Union has come into effect Europe V emission standard in 2009, require content of sulfur in gasoline to be less than 10 μ g/g, also plans to carry out more strict Europe VI standard about 2014.In second and third stage gasoline standard of California, USA, separate provision sulfur content in gasoline is not higher than 30 μ g/g, 15 μ g/g.China will come into effect the state III gasoline standard (GB17930-2006) that sulphur content is not more than 150 μ g/g in the end of the year 2009, and will come into effect the end of the year 2013 state's IV gasoline standard (GB17930-2011), require content of sulfur in gasoline to be not more than 50 μ g/g, following state V gasoline standard may limit content of sulfur in gasoline and be not more than 10 μ g/g.
Sulphur in China's gasoline product more than 90% is from catalytically cracked gasoline (FCC gasoline), and therefore, the sulphur content that reduces FCC gasoline is to reduce the key point of finished product content of sulfur in gasoline.
The sulphur content that reduces FCC gasoline can adopt hydrotreating of FCC feedstock, catalytic gasoline hydrogenation to process two kinds of technical schemes conventionally.Hydrotreating of FCC feedstock device need to all operate under exacting terms at temperature and pressure very much, and treatment capacity is large, and hydrogen consumption is large, and plant investment and running cost are higher.If only the hydrotreatment of applied catalysis cracking stock can make the FCC content of sulfur in gasoline of Some Enterprises reach below 500 μ g/g or below 150 μ g/g.But if further reduce the sulphur content of FCC gasoline, make it to meet Europe IV, the restriction of Europe V emission standard to content of sulfur in gasoline, with regard to still needing, FCC gasoline is carried out to hydrogenating desulfurization.
When adopting traditional catalyzer and technique to carry out hydrogenating desulfurization to FCC gasoline, due to alkene, significantly the saturated loss of octane number of gasoline that makes of hydrogenation is very large in meeting.RSDS is in catalytic gasoline hydrogenation desulfurization, by reducing as far as possible olefins hydrogenation, to reduce the technology of loss of octane number, by the technology of domestic and international extensive exploitation, application.
In prior art, the method for relevant catalytic gasoline selective hydrodesulfurizationmodification is a lot, be less than 10 μ g/g, or the loss of octane value is larger when product sulphur content is less than 10 μ g/g but majority is all difficult to realize product sulphur content.
EP0940464 has proposed a kind of processing method of catalytically cracked gasoline desulfurization.The method by catalytically cracked gasoline cut into gently, in, weigh three kinds of different cuts.Last running is in the first bed hydrogenating desulfurization, and its reaction product, enters the second bed and carries out hydrogenating desulfurization with middle runnings after mix in the first bed exit.But the method hydrogenation process olefin saturated rate is too high, and loss of octane number is excessive, and the gasoline products sulphur content after this patent is processed cannot be less than 10 μ g/g.
US5906730 has proposed a kind of method of FCC gasoline segmentation desulfurization.First paragraph keeps desulfurization degree 60～90%, and processing condition are: 200～350 ℃ of temperature, pressure 5～30kg/cm
2, liquid hourly space velocity 2～10h
-1, hydrogen to oil volume ratio 89～534, H
2s concentration is controlled and is less than 0.1 volume %.Second segment is controlled desulfurization degree 60 ~ 90%, and processing condition are: 200～300 ℃ of temperature, pressure 5～15kg/cm
2, liquid hourly space velocity 2～10h
-1, hydrogen to oil volume ratio 178～534, H
2s concentration is controlled and is less than 0.05 volume %.If second segment desulfurization does not still reach expection object, two sections of desulfurization outlet effluents are continued to desulfurization, its processing condition are identical with two sections of sulfur removal technology conditions.Embodiment shows, adopts the catalytically cracked gasoline cut of 80～220 ℃ of the method hydrotreatment boiling ranges, sulphur content 220 μ g/g, volume fraction of olefins 32%, when product sulphur content is 8 μ g/g, and octane value RON loss 2.6.If adopt the catalytically cracked gasoline of the method processing high-sulfur, high olefin content, loss of octane number will be very large.
CN1465668A has proposed a kind of method of producing low-sulphur oil, by gasoline stocks be cut into gently, last running, lighting end is through soda finishing mercaptan removal, last running contacts with Hydrobon catalyst together with hydrogen, carry out selective hydrodesulfurization reaction, gasoline fraction after hydrogenation carries out hydrogenation or non-hydro-sweetening, and light, last running after desulfurization are mixed to get to gasoline products.The method energy production sulphur content is lower than the gasoline of 200 μ g/g, and anti-knock index ((RON+MON)/2) loss is less than 2 units.The desulfurization depth of the method is inadequate, cannot obtain the gasoline that sulphur content is less than 10 μ g/g.
CN1478866A has proposed a kind of method of gasoline desulfur, and gasoline stocks is cut into light gasoline fraction, heavy naphtha; Heavy naphtha contacts with Hydrobon catalyst together with hydrogen, carry out selective hydrodesulfurization reaction, reaction effluent is after high-pressure separator is isolated gas phase, remaining liquid phase contacts with hydrogenating desulfurization alcohol catalyst after mixing with new hydrogen again, and effluent enters high-pressure separator successively, stabilizer tower obtains qualified product; From the isolated hydrogen rich stream of high-pressure separator, returning to hydrotreating reactor after recycle compressor boosts recycles.The main purpose of the method is to produce the gasoline that mercaptan sulfur is less than 10 μ g/g, can not make product total sulfur content be less than 10 μ g/g.
CN101619234A discloses a kind of method of producing low sulfur gasoline by using light weight gasoline.This process using two-stage hydrogenation technology: first paragraph adopts a kind of catalyst for selectively hydrodesulfurizing to carry out selective hydrodesulfurization to gasoline stocks, reaction product enters second segment reactor again and contacts with hydrogenating desulfurization alcohol catalyst, obtains clean gasoline product after reaction.Wherein catalyst for selectively hydrodesulfurizing used be take aluminum oxide as carrier, take molybdenum and cobalt as active ingredient, contains auxiliary agent potassium and phosphorus simultaneously.It is main ingredient that hydrogenating desulfurization alcohol catalyst used be take copper and zinc.The method can production sulphur content be less than the gasoline that 10 μ g/g, mercaptan sulfur content are less than 5.0 μ g/g, and octane value RON loses lower than 2.0Ge unit.Its shortcoming is, the method is only applicable to sulphur content to carry out hydrogenating desulfurization, sweetening reaction lower than the gasoline of 700 μ g/g.
Summary of the invention
On the basis of existing technology, the invention provides a kind of method that sulphur content is less than the super low-sulfur oil of 10 μ g/g of producing.
Technical scheme provided by the invention comprises the following steps:
(1) gasoline stocks is fractionated into lighting end gasoline and last running gasoline, and wherein the cut point of lighting end gasoline and last running gasoline is 50 ℃～70 ℃;
(2) lighting end gasoline enters alkali extracting unit, through alkali cleaning, refines and removes mercaptan sulfur wherein, obtains refining lighting end gasoline;
(3) last running gasoline is together with hydrogen, entering the first hydrogenator contacts and reacts with catalyst for selectively hydrodesulfurizing, the total sulfur of take in last running gasoline is benchmark, remove the sulfide of the 90 heavy % in heavy %～95 in last running gasoline, the reaction effluent of the first hydrogenator enters the second hydrogenator, contact and react with waste residue oil hydrogenation catalyst
The reaction effluent of (4) second hydrogenators carries out cooling, separated, and isolated liquid phase stream enters stabilizer tower, and stable bottom stream is hydrogenation last running gasoline,
(5) the refining lighting end gasoline of step (2) gained mixes with the hydrogenation last running gasoline of step (4) gained, obtains super low-sulfur oil cut.
In step (1), gasoline stocks is cut into lighting end gasoline and last running gasoline at 50～70 ℃.In lighting end gasoline, contain major part alkene and smaller portions sulfide and be all non-thiophene-type sulfide, in last running gasoline, contain major part sulfide and smaller portions alkene, wherein the yield of lighting end gasoline and last running gasoline is respectively the 25 heavy % in heavy %～35 and the heavy % in 65 heavy %～75 of gasoline stocks.
The lighting end gasoline of step (1) gained enters alkali extracting unit, through alkali cleaning, refines and removes mercaptan sulfur wherein, obtains refining lighting end gasoline.
In step (3), after mixing with hydrogen, the last running gasoline of step (1) gained carries out two-part selective hydrodesulfurization.First last running gasoline enter the first hydrogenator after mixing with hydrogen, contact, at hydrogen dividing potential drop 1.0～4.0MPa, 200～400 ℃ of temperature of reaction, volume space velocity 2～8h with catalyst for selectively hydrodesulfurizing
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3reaction conditions under carry out selective hydrodesulfurization reaction.The total sulfur of take in last running gasoline is benchmark, in the first hydrogenator of step (3), removes the sulfide of the 90 heavy % in heavy %～95 in last running gasoline.When carrying out two-part selective hydrodesulfurization, the olefin saturated degree during for other value is low than first paragraph desulfurization degree to control first paragraph desulfurization degree and be 90～95% caused olefin saturated degree, thereby causes final loss of octane number also lower.
The first reactor gained reactant flow contacts with waste residue oil hydrogenation catalyst at the second hydrogenator, at hydrogen dividing potential drop 1.0～4.0MPa, 200～400 ℃ of temperature of reaction, volume space velocity 2～8h
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3reaction conditions under, when removing remaining non-mercaptan sulfur compound, remove the reproducibility mercaptan that first paragraph hydrogenation produces.
One preferred embodiment in, in the middle of the first hydrogenator effluent enters, gas stripping column carries out air lift, the air lift medium of middle gas stripping column is hydrogen, preferred fresh hydrogen, the operational condition of middle gas stripping column is: pressure 1.0～4.0MPa.The first hydrogenator effluent is isolated gaseous stream and liquid phase stream under gas stripping, and gaseous stream is the hydrogen-rich gas that contains hydrogen sulfide, and it recycles after depriving hydrogen sulphide; Recycle hydrogen after liquid phase stream and depriving hydrogen sulphide is mixed into described the second hydrogenator.
In addition, the present invention can be light by regulating, the processing condition of last running cut point and/or two hydrogenators, thereby realize the target of producing low super sulfur oil and controlling loss of octane number minimum.
Described gasoline stocks is selected from one or more in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline, and final boiling point ≯ 220 ℃ of above-mentioned gasoline, are preferably catalytically cracked gasoline.
Catalyst for selectively hydrodesulfurizing in described the first hydrogenator is a kind of group vib base metal and/or group VIII non-precious metal catalyst loading in aluminum oxide and/or silica-alumina supports.In preferred described selective desulfurization catalyst, group vib base metal is selected from molybdenum and/or tungsten, group VIII base metal is selected from cobalt and/or nickel, in oxide compound and take total catalyst weight as benchmark, molybdenum and/or tungsten that this catalyst for selectively hydrodesulfurizing contains the 5.0 heavy % in heavy %～20, nickel and/or the cobalt of the 2.0 heavy % in heavy %～10.0.
The preparation method of preferred this catalyst for selectively hydrodesulfurizing is as follows: by hydrated aluminum oxide with auxiliary agent mixing moulding, be dried, roasting 2～6 hours under air again, make carrier.The aqueous solution containing cobalt and/or nickel compound, molybdenum and/or tungsten compound that carrier immersion is prepared is after 1～4 hour, and dry, at 300～550 ℃, roasting obtains catalyst prod for 1～3 hour.
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 respectively one or more in their soluble compound.The preferred ammonium molybdate of the compound of molybdenum wherein, 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 be preferably respectively in nickelous nitrate, nickelous chloride, basic nickel carbonate, ammonium tungstate, ammonium metawolframate, ethyl ammonium metawolframate, metatungstic acid nickel in one or more.
Preferred vacation-the boehmite of described hydrated aluminum oxide or pseudo-boehmite.
Waste residue oil hydrogenation catalyst in described the second hydrogenator is the residual oil hydrocatalyst coming from after residual hydrogenation process is used, and waste residue oil hydrogenation catalyst is packed into after the second hydrogenator, does not need regeneration also needn't carry out prevulcanized.
Residual oil hydrocatalyst need to have a certain proportion of mesopore to macropore and higher pore volume, can arrive the active surface of catalyzer to meet the macromole of residual oil medium-high viscosity, can hold a large amount of metals and coke again simultaneously.In reaction process, due to deposition on catalyzer of metal and coke and the Bing Shiqi duct, active centre that has covered gradually catalyzer narrow down, cause the loss of catalyst reaction activity.When the activity of residual oil hydrocatalyst drops to residual hydrogenation product and can not meet refinery and require, just will be drawn off.The inactivation of residual oil hydrocatalyst is mainly that metal deposition causes, and is irreversible, can not catalyzer be reused by the mode of regeneration.Therefore the residual oil hydrocatalyst, drawing off can only carry out waste treatment conventionally.
But because gasoline hydrodesulfurizationmethod is generally to carry out under the condition of gas-phase reaction, the catalyzer duct narrowing down still can meet the needs of gasoline hydrodesulfurizationmethod reaction.And waste residue oil hydrogenation catalyst still remains certain hydrogenation activity, to compare with live catalyst, residual activity is approximately 10～40% of live catalyst.Waste residue oil hydrogenation catalyst contains heavy metal Ni, V, Fe and coke conventionally, and pore volume and the specific surface area of catalyzer significantly reduce, and the metal depositing on catalyzer all exists with sulfide state, as V
3s
4, Ni
3s
2deng.And be deposited on the V on catalyzer
3s
4not only make catalyst pores structure change, and itself also have certain high active of hydrogenation catalysis.The present inventor found through experiments waste residue oil hydrogenation catalyst can show the higher desulphurizing activated selectivity with respect to olefins hydrogenation activity when processing vapor oil distillate.Analyze reason and be because hydrodesulfurization reaction in gasoline process and olefins hydrogenation reaction are to carry out on two kinds of different active centre, carbon deposit on waste residue oil hydrogenation catalyst has covered hydrogenation of olefins active centre more, hydrodesulfurization activity center but relatively more retains, and therefore makes catalyzer show higher desulfuration selectivity.Method provided by the invention is utilized the hydrodesulfurization activity of waste residue oil hydrogenation catalyst in the second hydrogenator, and the higher desulfuration selectivity of utilizing it to have due to coking deactivation.The pore volume of described waste residue oil hydrogenation catalyst catalyzer is 0.1～0.5mL/g, and specific surface area is 10～100m
2/ g, take waste residue oil hydrogenation catalyst as benchmark, and the total metal content depositing on described waste residue oil hydrogenation catalyst is 1～50 heavy %, and the coke of deposition is 5～30 heavy %, and the metal of deposition comprises vanadium, nickel and/or iron.
Described residual oil hydrocatalyst for loading on group vib base metal and/or the group VIII non-precious metal catalyst on alumina supporter.Residual oil hydrocatalyst of the present invention, wherein group vib base metal is preferably molybdenum, and group VIII base metal is preferably cobalt, in oxide compound and take total catalyst weight as benchmark, the molybdenum that contains the 8.0 heavy % in heavy %～30, the cobalt of the 1.0 heavy % in heavy %～10.0.
Advantage of the present invention:
1, the present invention can process the catalytically cracked gasoline of China's high olefin content, and the full distillation gasoline product of gained total sulfur content is less than 10 μ g/g, and compares full distillation gasoline raw material, and loss of octane number is little, and RON loss is not more than 1.0Ge unit.
2, controlling first paragraph desulfurization degree is that 90～95% olefin saturated degree of carrying out the caused olefin saturated degree of two-part selective hydrodesulfurization when controlling first paragraph desulfurization degree for other value are low, thereby the loss of octane number causing is also lower.
3, by using the gas stripping column between two reactors, can make to enter in the reaction feed of the second reactor not sulfide hydrogen, it mixes with circulating hydrogen after depriving hydrogen sulphide is processed the product that carries out obtaining after selective hydrodesulfurization again and is difficult for generation reproducibility mercaptan sulfur, so more easily realize the target that total sulfur content is less than 10 μ g/g.
4, in the second hydrogenator, use waste residue oil hydrogenation catalyst, not only can utilize it to the hydrodesulfurization activity of gasoline fraction and desulfuration selectivity, and can realize the second stage employ of residuum hydrodesulfurization catalyzer, save enterprise cost, and there is environment protection significance.
5, total sulfur content and the mercaptan sulfur content of the second hydrogenator outlet logistics have all been less than 10 μ g/g, without it being carried out to further air sweetening process, have reduced waste lye discharge, make more environmental protection of production process.
Accompanying drawing explanation
Accompanying drawing is the schematic flow sheet of production super low-sulfur oil method provided by the invention.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further described.
The method of production super low-sulfur oil provided by the invention is described in detail as follows: the full distillation gasoline raw material from pipeline 1 enters separation column 2, obtains lighting end gasoline and last running gasoline after fractionation.Light gasoline fraction is drawn through pipeline 3, sends into alkali extracting unit 4 and carries out alkali cleaning refining desulfurization alcohol, and the refining lighting end gasoline of gained is sent to products pot by pipeline 5.Last running gasoline is drawn by pipeline 6, after feedstock pump 7 boosts, mix by pipeline 8 and enter interchanger 9 with hydrogen from pipeline 34, by pipeline 10, enter process furnace 11 temperature raisings with the material-heat-exchanging from pipeline 23, and enter the first hydrogenator 13 by pipeline 12, carry out selective hydrodesulfurization reaction.The effluent of the first hydrogenator 13 is stripping tower 15 in the middle of pipeline 14 enters, under the gas stripping of the fresh hydrogen from pipeline 16, remove the impurity such as hydrogen sulfide in liquid phase, the gaseous stream that contains hydrogen sulfide is sent into recycle hydrogen de sulfuration hydrogen tower 31 through pipeline 17; Not hydrogen sulfide containing liquid phase stream enters interchanger 19 by pipeline 18, carries out after heat exchange with the second hydrogenator 21 effluents from pipeline 22, through pipeline 20, sends into the second hydrogenator 21.The effluent of the second hydrogenator is sent through pipeline 22, enters high-pressure separator 25 successively after interchanger 19, pipeline 23, interchanger 9 heat exchange by pipeline 24.In high-pressure separator 25, carry out after vapor-liquid separation, the hydrogen rich stream at top enters recycle hydrogen de sulfuration hydrogen tower 31 by pipeline 30, from tower top hydrogen out, by pipeline 32, enter circulating hydrogen compressor 33, after circulating hydrogen compressor supercharging, mix with feedstock pump 7 outlet materials through pipeline 34 on one tunnel, and a road is mixed into the second hydrogenator 21 through pipeline 35 and the logistics from pipeline 20.The logistics obtaining from high-pressure separator 25 bottoms enters stabilizer tower 27 through pipeline 26, and the light hydrocarbon gas of tower top is extracted out by pipeline 28, and bottom product is sent to products pot through pipeline 29.
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 1 is used are RSDS-1, for Sinopec catalyzer branch office produces.
In embodiment 1, the first hydrogenator catalyst for selectively hydrodesulfurizing used is catalyzer C, and the second hydrogenator waste residue oil hydrogenation catalyst used is that trade names are the useless agent of the catalyzer of RMS-1.Trade names are that the residual oil hydrocatalyst of RMS-1 is produced by Sinopec catalyzer branch office.Useless RMS-1 used has turned round nearly 10000 hours in a fixed bed residual hydrogenation equipment, and its main character is listed in table 1.
The carrier of catalyzer C is aluminum oxide, and active metal composition is: the heavy % of molybdenum oxide 13.0, the heavy % of cobalt oxide 3.8.
Comparative example 1
It is stock oil that this comparative example be take a kind of catalytically cracked gasoline F1, and its character is as shown in table 2.Take 68 ℃ as cut point by stock oil F1 be cut into light, weigh two sections of cuts, gained lighting end and last running account for respectively 35.0 heavy % and the 65.0 heavy % of raw material.Lighting end is through soda finishing mercaptan removal, and last running enters fixed-bed reactor after mixing with hydrogen and contacts and carry out selective hydrodesulfurization reaction with catalyzer RSDS-1.After mercaptan removal, after lighting end and hydrogenation, last running is in harmonious proportion and obtains full distillation gasoline product.The character of hydrogenation technique condition and full distillation gasoline product is listed in table 3.As can be seen from Table 3, though temperature of reaction up to 330 ℃, the total sulfur content (25 μ g/g) of full cut product still cannot be less than 10 μ g/g, and RON loss is up to 7.5Ge unit.And the mercaptan sulfur content of full cut product is 16 μ g/g, need to be again it be carried out to air sweetening processing and just can make the requirement of dispatching from the factory of its gasoline that meets mercaptan sulfur < 10 μ g/g, but after air sweetening, product total sulfur still cannot be less than 10 μ g/g.
Embodiment 1
Embodiment 1 adopts the stock oil F1 identical with comparative example 1, still take 68 ℃ as cut point by stock oil F1 be cut into light, weigh two sections of cuts, gained lighting end and last running account for respectively 35.0 heavy % and the 65.0 weight % of raw material.Lighting end is through alkali cleaning refining desulfurization alcohol sulphur.Last running adopts two different operation operating modes to carry out selective hydrodesulfurization.
First operation operating mode is: first last running enter the first hydrogenator and carry out selective hydrodesulfurization with catalyst for selectively hydrodesulfurizing (catalyzer C) and react after mixing with hydrogen.The total sulfur of take in last running gasoline is benchmark, in the first hydrogenator, removes the sulfide of 94.8 heavy % in last running gasoline.And be mixed into the second hydrogenator with hydrogen after removing hydrogen sulfide by middle gas stripping column air lift, under the effect of useless RMS-1, continue desulfurization and obtain refining last running gasoline.Lighting end and last running after refining are mixed to get full distillation gasoline product.
The character of the reaction conditions of the first hydrogenator and the second hydrogenator and full cut product is in Table 3.The sulphur content of full cut product is 8.2 μ g/g as can be seen from Table 3, and mercaptan sulfur content is less than 3 μ g/g, and olefin(e) centent is 33.5 volume %, and RON loss is only 0.9.
Second operation operating mode is: first last running enter the first hydrogenator after mixing with hydrogen and contact and carry out selective hydrodesulfurization reaction with catalyzer C.The total sulfur of take in last running gasoline is benchmark, in the first hydrogenator, removes the sulfide of 90.6 heavy % in last running gasoline.And be mixed into the second hydrogenator with hydrogen after removing hydrogen sulfide by middle gas stripping column air lift, under the effect of useless RMS-1, continue desulfurization and obtain refining last running gasoline.Lighting end and last running after refining are mixed to get full distillation gasoline product.
The character of the reaction conditions of the first hydrogenator and the second hydrogenator and full cut product is in Table 3.The sulphur content of full cut product is 6.0 μ g/g as can be seen from Table 3, and mercaptan sulfur content is less than 3 μ g/g, and olefin(e) centent is 32.0 volume %, and RON loss is only 1.0.
Comparative example 2
Comparative example 2 adopts the two-part selective hydrodesulfurization of the middle gas stripping column of band to reduce the sulphur content of gasoline.It is stock oil that comparative example 2 be take a kind of catalytically cracked gasoline F2, and its character is as shown in table 2.Take 65 ℃ as cut point by stock oil F2 be cut into light, weigh two sections of cuts, gained lighting end and last running account for respectively 33.0 heavy % and the 67.0 heavy % of raw material.Lighting end is through alkali cleaning refining desulfurization alcohol sulphur.Last running adopts two different operation operating modes to carry out selective hydrodesulfurization.
First operation operating mode is: first last running enter the first hydrogenator after mixing with hydrogen and contact and carry out selective hydrodesulfurization reaction with catalyzer C.The total sulfur of take in last running gasoline is benchmark, in the first hydrogenator, removes the sulfide of 97.0 heavy % in last running gasoline.And be mixed into the second hydrogenator with hydrogen after removing hydrogen sulfide by middle gas stripping column air lift, under the effect of useless RMS-1, continue desulfurization and obtain refining last running gasoline.Lighting end and last running after refining are mixed to get full distillation gasoline product.The character of the reaction conditions of the first hydrogenator and the second hydrogenator and full cut product is in Table 4.The sulphur content of full cut product is 9.0 μ g/g as can be seen from Table 4, and mercaptan sulfur content is 5 μ g/g, and olefin(e) centent is 18.5 volume %, and RON loss is 2.3.
Second operation operating mode is: first last running enter the first hydrogenator after mixing with hydrogen and contact and carry out selective hydrodesulfurization reaction with catalyzer C.The total sulfur of take in last running gasoline is benchmark, in the first hydrogenator, removes the sulfide of 85.2 heavy % in last running gasoline.And be mixed into the second hydrogenator with hydrogen after removing hydrogen sulfide by middle gas stripping column air lift, under the effect of useless RMS-1, continue desulfurization and obtain refining last running gasoline.Lighting end and last running after refining are mixed to get full distillation gasoline product.The character of the reaction conditions of the first hydrogenator and the second hydrogenator and full cut product is in Table 4.The sulphur content of full cut product is 9.8 μ g/g as can be seen from Table 4, and mercaptan sulfur content is 6 μ g/g, and olefin(e) centent is 20.0 volume %, and RON loss is 2.3.
Embodiment 2
Embodiment 2 adopts the stock oil F2 identical with comparative example 2, still take 65 ℃ as cut point by stock oil F2 be cut into light, weigh two sections of cuts, gained lighting end and last running account for respectively 33.0 heavy % and the 67.0 weight % of raw material.Lighting end is through alkali cleaning refining desulfurization alcohol sulphur.First last running enter the first hydrogenator after mixing with hydrogen and contact and carry out selective hydrodesulfurization reaction with catalyzer C.The total sulfur of take in last running gasoline is benchmark, in the first hydrogenator, removes the sulfide of 92.6 heavy % in last running gasoline.And be mixed into the second hydrogenator with hydrogen after removing hydrogen sulfide by middle gas stripping column air lift, under the effect of useless RMS-1, continue desulfurization and obtain refining last running gasoline.Lighting end and last running after refining are mixed to get full distillation gasoline product.
The character of the reaction conditions of the first hydrogenator and the second hydrogenator and full cut product is in Table 4.The sulphur content of full cut product is 8.0 μ g/g as can be seen from Table 4, and mercaptan sulfur content is 3 μ g/g, and olefin(e) centent is 26.0 volume %, and RON loss is 0.9.
Comparative example 3
Comparative example 3 adopts the sulphur content that reduces gasoline without two step series connection selective hydrodesulfurizations of middle gas stripping column.It is stock oil that comparative example 3 be take a kind of catalytically cracked gasoline F3, and its character is as shown in table 2.Take 60 ℃ as cut point by stock oil F3 be cut into light, weigh two sections of cuts, gained lighting end and last running account for respectively 30.0 heavy % and the 70.0 heavy % of raw material.Lighting end is through alkali cleaning refining desulfurization alcohol sulphur.First last running enter the first hydrogenator after mixing with hydrogen and contact and carry out selective hydrodesulfurization reaction with catalyzer C.The total sulfur of take in last running gasoline is benchmark, in the first hydrogenator, removes the sulfide of 94.0 heavy % in last running gasoline, then enters continuously the second hydrogenator, continues desulfurization and obtain refining last running gasoline under the effect of useless RMS-1.Lighting end and last running after refining are mixed to get full distillation gasoline product.The character of the reaction conditions of the first hydrogenator and the second hydrogenator and full cut product is in Table 5.When the sulphur content of full cut product is 9.9 μ g/g as can be seen from Table 5, mercaptan sulfur content is 7 μ g/g, and olefin(e) centent is 16.0 volume %, and RON loss is 2.4.
Embodiment 3
Embodiment 3 adopts the stock oil F3 identical with comparative example 3, still take 60 ℃ as cut point by stock oil F3 be cut into light, weigh two sections of cuts, gained lighting end and last running account for respectively 30.0 heavy % and the 70.0 weight % of raw material.Lighting end is through alkali cleaning refining desulfurization alcohol sulphur.First last running enter the first hydrogenator after mixing with hydrogen and contact and carry out selective hydrodesulfurization reaction with catalyzer C.The total sulfur of take in last running gasoline is benchmark, in the first hydrogenator, remove the sulfide of 94.0 heavy % in last running gasoline, and be mixed into the second hydrogenator with hydrogen after removing hydrogen sulfide by middle gas stripping column air lift, under the effect of useless RMS-1, continue desulfurization and obtain refining last running gasoline.Lighting end and last running after refining are mixed to get full distillation gasoline product.The character of the reaction conditions of the first hydrogenator and the second hydrogenator and full cut product is in Table 5.The sulphur content of full cut product is 6.8 μ g/g as can be seen from Table 5, and mercaptan sulfur content is less than 3 μ g/g, and olefin(e) centent is 21.5 volume %, and RON loss is only 0.7.
Table 1
| Catalyzer | Useless RMS-1 |
| Specific surface area, m 2/g | 74 |
| Pore volume, mL/g | 0.15 |
| Foreign matter content, heavy % | |
| S | 9.6 |
| C | 12.2 |
| N | 0.21 |
| Ni+V | 11.5 |
| Ni+V+Fe+Ca+Na | 13.1 |
Table 2
| Material name | F1 | F2 | F3 |
| Density (20 ℃), g/cm 3 | 0.7320 | 0.7300 | 0.7250 |
| Sulphur content, μ g/g | 942 | 550 | 380 |
| Alkene, volume % | 38.8 | 30.0 | 25.0 |
| Boiling range (ASTM D86), ℃ | |||
| |
28 | 32 | 33 |
| 10% | 44 | 43 | 44 |
| 50% | 94 | 89 | 85 |
| 90% | 175 | 169 | 168 |
| Final boiling point | 198 | 191 | 193 |
| RON | 92.7 | 94.0 | 93.4 |
Table 3
Table 4
Table 5
Claims (10)
1. a method of producing super low-sulfur oil, comprising:
(1) gasoline stocks is fractionated into lighting end gasoline and last running gasoline, and wherein the cut point of lighting end gasoline and last running gasoline is 50 ℃～70 ℃;
(2) lighting end gasoline enters alkali extracting unit, through alkali cleaning, refines and removes mercaptan sulfur wherein, obtains refining lighting end gasoline;
(3) last running gasoline is together with hydrogen, entering the first hydrogenator contacts and reacts with catalyst for selectively hydrodesulfurizing, the total sulfur of take in last running gasoline is benchmark, remove the sulfide of the 90 heavy % in heavy %～95 in last running gasoline, the reaction effluent of the first hydrogenator enters the second hydrogenator, contact and react with waste residue oil hydrogenation catalyst
The reaction effluent of (4) second hydrogenators carries out cooling, separated, and isolated liquid phase stream enters stabilizer tower, and stable bottom stream is hydrogenation last running gasoline,
(5) the refining lighting end gasoline of step (2) gained mixes with the hydrogenation last running gasoline of step (4) gained, obtains super low-sulfur oil cut.
2. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the first hydrogenator and the second hydrogenator is: hydrogen dividing potential drop 1.0～4.0MPa, 200～400 ℃ of temperature of reaction, volume space velocity 2～8h
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3.
3. in accordance with the method for claim 1, it is characterized in that, in the middle of the first hydrogenator effluent enters, gas stripping column carries out air lift, and the air lift medium of middle gas stripping column is hydrogen, and the operational condition of middle gas stripping column is: pressure 1.0～4.0MPa.
4. in accordance with the method for claim 1, it is characterized in that, catalyst for selectively hydrodesulfurizing is a kind of group vib base metal and/or group VIII non-precious metal catalyst loading in aluminum oxide and/or silica-alumina supports.
5. in accordance with the method for claim 1, it is characterized in that, in described selective desulfurization catalyst, group vib base metal is selected from molybdenum and/or tungsten, group VIII base metal is selected from cobalt and/or nickel, in oxide compound and take total catalyst weight as benchmark, molybdenum and/or tungsten that this catalyst for selectively hydrodesulfurizing contains the 5.0 heavy % in heavy %～20, nickel and/or the cobalt of the 2.0 heavy % in heavy %～10.0.
6. in accordance with the method for claim 1, it is characterized in that, described waste residue oil hydrogenation catalyst is the residual oil hydrocatalyst coming from after residual hydrogenation process is used, and waste residue oil hydrogenation catalyst is packed into after the second hydrogenator, does not need regeneration also needn't carry out prevulcanized.
7. according to the method described in claim 1 or 6, it is characterized in that, the pore volume of waste residue oil hydrogenation catalyst catalyzer is 0.1～0.5mL/g, and specific surface area is 10～100m
2/ g.
8. according to the method described in claim 1 or 6, it is characterized in that, take waste residue oil hydrogenation catalyst as benchmark, the total metal content depositing on described waste residue oil hydrogenation catalyst is 1～50 heavy %, and the coke of deposition is 5～30 heavy %.
9. in accordance with the method for claim 6, it is characterized in that, described residual oil hydrocatalyst for loading on group vib base metal and/or the group VIII non-precious metal catalyst on alumina supporter, wherein group vib base metal is preferably molybdenum, group VIII base metal is preferably cobalt, in oxide compound and take total catalyst weight as benchmark, the molybdenum that contains the 8.0 heavy % in heavy %～30, the cobalt of the 1.0 heavy % in heavy %～10.0.
10. in accordance with the method for claim 1, described gasoline stocks is selected from one or more in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline, final boiling point ≯ 220 ℃ of above-mentioned gasoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210371143.4A CN103710045B (en) | 2012-09-28 | 2012-09-28 | A kind of method of producing super low-sulfur oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210371143.4A CN103710045B (en) | 2012-09-28 | 2012-09-28 | A kind of method of producing super low-sulfur oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103710045A true CN103710045A (en) | 2014-04-09 |
| CN103710045B CN103710045B (en) | 2016-01-20 |
Family
ID=50403411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210371143.4A Active CN103710045B (en) | 2012-09-28 | 2012-09-28 | A kind of method of producing super low-sulfur oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103710045B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354225A (en) * | 2000-11-17 | 2002-06-19 | 中国石油化工股份有限公司 | Method for raising induction period of gasoline |
| CN102604672A (en) * | 2011-01-20 | 2012-07-25 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
-
2012
- 2012-09-28 CN CN201210371143.4A patent/CN103710045B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354225A (en) * | 2000-11-17 | 2002-06-19 | 中国石油化工股份有限公司 | Method for raising induction period of gasoline |
| CN102604672A (en) * | 2011-01-20 | 2012-07-25 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103710045B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101787307B (en) | Gasoline hydrodesulfurization method | |
| CN103074107B (en) | A kind of method of producing the full distillation gasoline product of super low sulfur | |
| CN101368111B (en) | Hydrogenation modification method for catalytically cracked gasoline | |
| CN101275084B (en) | Method for reducing sulfur content of catalytically cracked gasoline | |
| CN103074106B (en) | A kind of method reducing content of sulfur in gasoline | |
| CN103305269B (en) | Method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar | |
| CN102757818A (en) | Sulfur-free gasoline production method | |
| CN101993725B (en) | Method for producing low-sulfur gasoline | |
| CN106147844A (en) | A kind of method of hydrotreating producing super low-sulfur oil | |
| CN103059946B (en) | Low-energy consumption catalytic gasoline hydrodesulfurizationmethod method | |
| CN101161791B (en) | Method for producing clean gasoline | |
| CN103059964B (en) | Method for producing ultra-low sulfur gasoline | |
| CN101314734B (en) | Selective hydrogenation desulfurization method for gasoline | |
| CN103059956B (en) | Deep hydrodesulfurization method for catalytic gasoline | |
| CN103396832A (en) | Modification method for full-range catalytic cracking gasoline | |
| CN103059965B (en) | Catalytic gasoline deep hydrodesulfurizationmethod method | |
| CN103710045B (en) | A kind of method of producing super low-sulfur oil | |
| CN103695035B (en) | A kind of combined method of producing super low-sulfur oil | |
| CN102757817B (en) | Gasoline processing method | |
| CN109722308B (en) | Method for producing low-sulfur low-olefin gasoline | |
| CN103059958B (en) | Catalytic cracking and catalytic gasoline hydrogenation combined process | |
| CN103695034B (en) | A kind of method of processing high olefin gasoline stocks production super low-sulfur oil | |
| CN102399588A (en) | Method for reducing sulfur content in sulfur-containing light oil | |
| CN103805269B (en) | A kind of catalytic gasoline deep hydrodesulfurizationmethod method | |
| CN103450935A (en) | Method for producing ultra-low sulfur gasoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |