CN103695035B - A kind of combined method of producing super low-sulfur oil - Google Patents
A kind of combined method of producing super low-sulfur oil Download PDFInfo
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Abstract
A kind of combined method of producing super low-sulfur oil, gasoline stocks is fractionated into lighting end gasoline and last running gasoline, lighting end gasoline enters alkali density unit, last running gasoline to contact with catalyst for selectively hydrodesulfurizing at the first hydrogenator and reacts, after middle gas stripping column air lift, enter the second hydrogenator contact with waste residue oil hydrogenation catalyst and react, after refining lighting end gasoline mixes with hydrogenation last running gasoline, obtain super low-sulfur oil cut.The present invention can process the catalytically cracked gasoline of high olefin content, and gained full distillation gasoline product 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 less than 1.5 units.
Description
Technical field
The present invention relates to a kind of method reducing content of sulfur in gasoline, for not depositing the combined method removing sulphur in the case of hydrogen and refine hydrocarbon ils two processes in presence of hydrogen.
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 V emission standard in 2009, required that content of sulfur in gasoline is less than 10 μ g/g, also planned to carry out more strict Europe VI standard at about 2014.Sulfur content in gasoline is respectively provided not higher than 30 μ g/g, 15 μ g/g in second and third stage gasoline standard of California, USA.China will come into effect in the end of the year 2009 the state III gasoline standard (GB 17930-2006) that sulphur content is not more than 150 μ g/g, and state IV gasoline standard (GB17930-2011) will be come into effect the end of the year 2013, require that content of sulfur in gasoline is not more than 50 μ g/g, following state V gasoline standard then may limit content of sulfur in gasoline and be not more than 10 μ g/g.
In China's gasoline product, the sulphur of more than 90% is from catalytically cracked gasoline (FCC gasoline), and therefore, the sulphur content reducing FCC gasoline reduces the key point of finished product content of sulfur in gasoline.
The sulphur content reducing FCC gasoline can adopt hydrotreating of FCC feedstock, catalytic gasoline hydrogenation process two kinds of technical schemes usually.Hydrotreating of FCC feedstock device needs to operate under temperature and pressure all very exacting terms, and treatment capacity is large, and hydrogen consumption is large, plant investment and running cost higher.If only the hydrotreatment of applied catalysis cracking stock can make the FCC gasoline sulphur content of Some Enterprises reach 500 below μ g/g or 150 below μ g/g.But if the sulphur content of FCC gasoline will be reduced further, would making it to meet Europe IV, Europe V emission standard to the restriction of content of sulfur in gasoline, with regard to still needing, hydrogenating desulfurization being carried out to FCC gasoline.
When adopting traditional catalyzer and technique to carry out hydrogenating desulfurization to FCC gasoline, can due to alkene significantly hydrotreated lube base oil and make the loss of octane number of gasoline very large.RSDS is the technology reducing loss of octane number catalytic gasoline hydrogenation desulfurization while by reducing olefins hydrogenation as far as possible, by the technology of domestic and international extensive exploitation, application.
About the method for catalytic gasoline selective hydrodesulfurizationmodification is a lot of in prior art, but majority is all difficult to realize product sulphur content is 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.
EP0940464 proposes a kind of processing method of catalytically cracked gasoline desulfurization.Catalytically cracked gasoline cuts into gently by the method, in, weigh three kinds of different cuts.Last running is in the first bed hydrogenating desulfurization, and its reaction product and middle runnings, after the first bed exit mixes, enter the second bed and carry out hydrogenating desulfurization.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 process cannot be less than 10 μ g/g.
US5906730 proposes a kind of method of FCC gasoline segmentation desulfurization.First paragraph keeps desulfurization degree 60 ~ 90%, and processing condition are: 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%, and processing condition are: 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.Embodiment shows, adopts the catalytically cracked gasoline cut of the method hydrotreatment boiling range 80 ~ 220 DEG C, sulphur content 220 μ g/g, volume fraction of olefins 32%, and when product sulphur content is 8 μ g/g, octane value RON loses 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 proposes a kind of method of producing low-sulphur oil, gasoline stocks is 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 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 proposes a kind of method of gasoline desulfur, 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 isolated after gas phase through high-pressure separator, remaining liquid phase after mixing with new hydrogen again with hydro-sweetening catalyst exposure, effluent enters high-pressure separator successively, stabilizer tower obtains qualified product; After recycle compressor boosting, return hydrotreating reactor from the isolated hydrogen rich stream of high-pressure separator to recycle.The main purpose of the method is the gasoline that production mercaptan sulfur is less than 10 μ g/g, and product total sulfur content can not be made to be less than 10 μ g/g.
CN101619234A discloses a kind of method of producing low sulfur gasoline by using light weight gasoline.This technique adopts 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 and hydro-sweetening catalyst exposure again, obtains clean gasoline product after reaction.Catalyst for selectively hydrodesulfurizing wherein used take aluminum oxide as carrier, with molybdenum and cobalt for active ingredient, simultaneously containing auxiliary agent potassium and phosphorus.Hydrogenating desulfurization alcohol catalyst used with copper and zinc for main ingredient.The method can production sulphur content is less than 10 μ g/g, mercaptan sulfur content is less than 5.0 μ g/g gasoline, and octane value RON loses lower than 2.0 units.Its shortcoming is, the method is only applicable to carry out hydrogenating desulfurization, sweetening reaction to sulphur content 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 combined method of producing sulphur content and being less than the super low-sulfur oil of 10 μ g/g.
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 DEG C ~ 70 DEG C;
(2) lighting end gasoline enters alkali density unit, refines the mercaptan sulfur removed wherein through alkali cleaning, obtains refining lighting end gasoline;
(3) last running gasoline is together with hydrogen, enter the first hydrogenator to contact with catalyst for selectively hydrodesulfurizing and react, the reaction effluent of the first hydrogenator enters middle gas stripping column and carries out air lift, middle gas stripping column gained liquid phase stream enters the second hydrogenator together with hydrogen, contact with waste residue oil hydrogenation catalyst and react, the temperature of reaction of the second hydrogenator is lower than the temperature of reaction of the first hydrogenator
The reaction effluent of (4) second hydrogenators carries out cooling, being 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 DEG C.Containing major part alkene and smaller portions sulfide and be all non-thiophene-type sulfide in lighting end gasoline, containing major part sulfide and smaller portions alkene in last running gasoline, 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 density unit, refines the mercaptan sulfur removed wherein through alkali cleaning, obtains refining lighting end gasoline.
In step (3), the last running gasoline of step (1) gained carries out two-part selective hydrodesulfurization after mixing with hydrogen.First enter the first hydrogenator after last running gasoline mixes with hydrogen, contact with catalyst for selectively hydrodesulfurizing, at hydrogen dividing potential drop 1.0 ~ 4.0MPa, temperature of reaction 200 ~ 400 DEG C, volume space velocity 2 ~ 8h
-1, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3reaction conditions under carry out selective hydrodesulfurization reaction.
First hydrogenator effluent enters middle gas stripping column, isolates gaseous stream and liquid phase stream under gas stripping, and gaseous stream is the hydrogen-rich gas containing hydrogen sulfide, and it uses through depriving hydrogen sulphide Posterior circle; Recycle hydrogen after liquid phase stream and depriving hydrogen sulphide is mixed into the second reactor, contacts, at hydrogen dividing potential drop 1.0 ~ 4.0MPa, temperature of reaction 200 ~ 400 DEG C, volume space velocity 2 ~ 8h with waste residue oil hydrogenation catalyst
-1, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3reaction conditions under, remove the reproducibility mercaptan that first paragraph hydrogenation produces while removing remaining non-mercaptan sulfur compound.The stripping medium of described middle gas stripping column is hydrogen, preferred fresh hydrogen, and the operational condition of middle gas stripping column is: pressure 1.0 ~ 4.0MPa.The temperature of reaction of described second hydrogenator is lower than the temperature of reaction of the first hydrogenator 5 ~ 50 DEG C.
In addition, the present invention can by regulating the processing condition of light, last running cut point and/or two hydrogenators, thus realize producing low super sulfur oil and controlling the minimum target of loss of octane number.
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 DEG C of above-mentioned gasoline, is preferably catalytically cracked gasoline.
Catalyst for selectively hydrodesulfurizing in described first hydrogenator is the group vib base metal of a kind of load on aluminum oxide and/or silica-alumina supports and/or group VIII non-precious metal catalyst.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, be benchmark with oxide basis and with total catalyst weight, this catalyst for selectively hydrodesulfurizing contains molybdenum and/or the tungsten of the 5.0 heavy % in heavy % ~ 20, the nickel of the 2.0 heavy % in heavy % ~ 10.0 and/or cobalt.
The preparation method of this catalyst for selectively hydrodesulfurizing preferred is as follows: by hydrated aluminum oxide and auxiliary agent mixing moulding, drying, roasting 2 ~ 6 hours under air again, obtain 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 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 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.
Waste residue oil hydrogenation catalyst in described second hydrogenator is the residual oil hydrocatalyst after coming from the use of residual hydrogenation process, after waste residue oil hydrogenation catalyst is packed into the second hydrogenator, does not need regeneration also need not carry out prevulcanized.
Residual oil hydrocatalyst needs a certain proportion of mesopore to macropore and higher pore volume, can arrive the active surface of catalyzer with the macromole meeting residual oil medium-high viscosity, can hold a large amount of metals and coke again simultaneously.In reaction process, cover the active centre of catalyzer gradually due to metal and coke deposition on a catalyst and its duct is narrowed, causing the loss of catalyst reaction activity.When the activity of residual oil hydrocatalyst drop to residual hydrogenation product can not meet refinery require time, just will be drawn off.The inactivation of residual oil hydrocatalyst mainly metal deposition causes, and be irreversible, the mode not by regeneration makes catalyzer reuse.Therefore, the residual oil hydrocatalyst drawn off can only carry out waste treatment usually.
But because gasoline hydrodesulfurizationmethod is generally carry out under the condition of gas-phase reaction, the catalyzer duct narrowed still can meet the needs of gasoline hydrodesulfurizationmethod reaction.Further, waste residue oil hydrogenation catalyst still remains certain hydrogenation activity, and compared with live catalyst, residual activity is approximately 10 ~ 40% of live catalyst.Waste residue oil hydrogenation catalyst is usually containing heavy metal Ni, V, Fe and coke, and pore volume and the specific surface area of catalyzer significantly reduce, and the metal that catalyzer deposits all exists, as V with sulfide state
3s
4, Ni
3s
2deng.And deposition V on a catalyst
3s
4not only make catalyst pore 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 relative to olefins hydrogenation activity when processing vapor oil distillate.Analyzing reason is because hydrodesulfurization reaction in gasoline process and olefins hydrogenation reaction carry out on two kinds of different active centre, carbon deposit on waste residue oil hydrogenation catalyst covers 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, utilizes the hydrodesulfurization activity of waste residue oil hydrogenation catalyst in the second hydrogenator, and the higher desulfuration selectivity 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, with waste residue oil hydrogenation catalyst for benchmark, the total metal content that described waste residue oil hydrogenation catalyst deposits 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 be load group vib base metal on the alumina support and/or group VIII non-precious metal catalyst.Residual oil hydrocatalyst of the present invention, wherein group vib base metal is preferably molybdenum, and group VIII base metal is preferably cobalt, is benchmark with oxide basis and with total catalyst weight, the molybdenum containing 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 gained full distillation gasoline product 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 less than 1.5 units.
2, by the gas stripping column between utilization two reactors, not sulfide hydrogen can be made to enter in the reaction feed of the second reactor, its mix with the circulating hydrogen after depriving hydrogen sulphide process carry out selective hydrodesulfurization again after the product that obtains not easily generate reproducibility mercaptan sulfur, so more easily realize the target that total sulfur content is less than 10 μ g/g.
3, in the second hydrogenator, waste residue oil hydrogenation catalyst is used, it not only can be utilized the hydrodesulfurization activity of gasoline fraction and desulfuration selectivity, and the second stage employ of residuum hydrodesulfurization catalyzer can be realized, save enterprise cost, and there is environment protection significance.
4, the total sulfur content of the second hydrogenator outlet streams and mercaptan sulfur content have been less than 10 μ g/g all, without the need to carrying out further air sweetening process to it, decreasing waste lye discharge, making production process more environmental protection.
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 combined 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, and send into alkali density unit 4 and carry out alkali cleaning refining desulfurization alcohol, the refining lighting end gasoline of gained sends to products pot by pipeline 5.Last running gasoline is drawn by pipeline 6, interchanger 9 is entered through pipeline 8 after mixing with the hydrogen from pipeline 34 after feedstock pump 7 boosts, process furnace 11 temperature raising is entered through pipeline 10 with after the material-heat-exchanging from pipeline 23, and after enter the first hydrogenator 13 through pipeline 12, carry out selective hydrodesulfurization reaction.The effluent of the first hydrogenator 13 enters middle stripping tower 15 through pipeline 14, under the gas stripping of the fresh hydrogen from pipeline 16, remove the impurity such as the hydrogen sulfide in liquid phase, the gaseous stream containing hydrogen sulfide sends into recycle hydrogen de sulfuration hydrogen tower 31 through pipeline 17; Not hydrogen sulfide containing liquid phase stream then enters interchanger 19 by pipeline 18, after carrying out heat exchange, sends into the second hydrogenator 21 through pipeline 20 with the second hydrogenator 21 effluent from pipeline 22.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.After high-pressure separator 25 carries out vapor-liquid separation, the hydrogen rich stream at top enters recycle hydrogen de sulfuration hydrogen tower 31 by pipeline 30, circulating hydrogen compressor 33 is entered by pipeline 32 from tower top hydrogen out, after circulating hydrogen compressor supercharging, one tunnel mixes with feedstock pump 7 outlet material through pipeline 34, and a road is mixed into the second hydrogenator 21 through pipeline 35 and the logistics from pipeline 20.The stream passes via line 26 obtained from high-pressure separator 25 bottom enters stabilizer tower 27, and the light hydrocarbon gas of tower top is extracted out by pipeline 28, and bottom product sends 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.
The catalyst for selectively hydrodesulfurizing that in embodiment 1, first hydrogenator is used is catalyzer C, the useless agent of the second hydrogenator waste residue oil hydrogenation catalyst used to be trade names be 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 operated nearly 10000 hours in a fixed bed residual hydrogenation equipment, and its main character lists in table 1.
The carrier of catalyzer C is aluminum oxide, and active metal consists of: the heavy % of molybdenum oxide 13.0, the heavy % of cobalt oxide 3.8.
Comparative example 1
With a kind of catalytically cracked gasoline F1 for stock oil, its character is as shown in table 2.With 68 DEG C for cut point stock oil F1 is cut into light, weigh two sections of cuts, gained lighting end and last running account for 35.0 heavy % and the 65.0 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 selective 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 3.As can be seen from Table 3, even if temperature of reaction is up to 330 DEG C, the sulphur content (25 μ g/g) of full cut product still cannot be less than 10 μ g/g, and RON loss is up to 7.5 units.And the mercaptan sulfur content of full cut product is 16 μ g/g, needing to carry out air sweetening process to it more just 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
Embodiment 1 adopts the stock oil F1 identical with comparative example 1, still with 68 DEG C for cut point stock oil F1 is cut into light, weigh two sections of cuts, gained lighting end and last running account for 35.0 heavy % and the 65.0 weight % of raw material respectively.Lighting end is through alkali cleaning refining desulfurization alcohol sulphur.First last running enter the first hydrogenator and contact with catalyzer C and carry out selective hydrodesulfurization after mixing with hydrogen, and after after middle gas stripping column air lift removes hydrogen sulfide, be mixed into the second hydrogenator with hydrogen, under the effect of useless RMS-1, continue desulfurization obtain refining last running gasoline.Lighting end after refining and last running are mixed to get full distillation gasoline product.The reaction conditions of the first hydrogenator and the second hydrogenator and the character of full cut product are in table 3.The sulphur content of full cut product is 6.8 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 that 31.0 volume %, RON loss is only 1.4.
Comparative example 2
With a kind of catalytically cracked gasoline F2 for stock oil, its character is as shown in table 2.With 65 DEG C for cut point stock oil F2 is cut into light, weigh two sections of cuts, gained lighting end and last running account for 33.0 heavy % and the 67.0 weight % of raw material respectively.Lighting end is through soda finishing mercaptan removal, and last running enters fixed-bed reactor and contacts with catalyzer C and carry out selective 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 4.As can be seen from Table 4, temperature of reaction is 320 DEG C can make the sulphur content of full cut product be 9.0 μ g/g, and now the olefin(e) centent of product is that 18.0 volume %, RON lose 3.0 units.
Embodiment 2
With a kind of catalytically cracked gasoline F2 for stock oil, its character is as shown in table 2.Still with 65 DEG C for cut point stock oil F2 is cut into light, weigh two sections of cuts, gained lighting end and last running account for 33.0 heavy % and the 67.0 weight % of raw material respectively.Lighting end is through alkali cleaning refining desulfurization alcohol sulphur.First last running enter the first hydrogenator and contact with catalyzer C and carry out selective hydrodesulfurization after mixing with hydrogen, and after after middle gas stripping column air lift removes hydrogen sulfide, be mixed into the second hydrogenator with hydrogen, under the effect of useless RMS-1, continue desulfurization obtain refining last running gasoline.Lighting end after refining and last running are mixed to get full distillation gasoline product.The reaction conditions of the first hydrogenator and the second hydrogenator and the character of full cut product are in table 4.As can be seen from Table 4, first, second hydrogenator is only needed to adopt the temperature of reaction of 295 DEG C, 290 DEG C that the sulphur content of full cut product just can be made to be reduced to 8.5 μ g/g respectively, now mercaptan sulfur content is 3 μ g/g, and olefin(e) centent is 24.5 volume %, RON loss is 1.1 units.
Embodiment 3
With a kind of catalytically cracked gasoline F3 for stock oil, its character is as shown in table 2.With 60 DEG C for cut point stock oil F3 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 alkali cleaning refining desulfurization alcohol sulphur.First last running enter the first hydrogenator and contact with catalyzer C and carry out selective hydrodesulfurization after mixing with hydrogen, and after after middle gas stripping column air lift removes hydrogen sulfide, be mixed into the second hydrogenator with hydrogen, under the effect of useless RMS-1, continue desulfurization obtain refining last running gasoline.Lighting end after refining and last running are mixed to get full distillation gasoline product.The reaction conditions of the first hydrogenator and the second hydrogenator and the character of full cut product are in table 5.The sulphur content of full cut product is 3.8 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 that 21.5 volume %, RON loss is only 0.8.
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 DEG C), 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), DEG C | |||
| Initial boiling point | 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. produce a combined method for 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 DEG C ~ 70 DEG C;
(2) lighting end gasoline enters alkali density unit, refines the mercaptan sulfur removed wherein through alkali cleaning, obtains refining lighting end gasoline;
(3) last running gasoline is together with hydrogen, enter the first hydrogenator to contact with catalyst for selectively hydrodesulfurizing and react, the reaction effluent of the first hydrogenator enters middle gas stripping column and carries out air lift, middle gas stripping column gained liquid phase stream enters the second hydrogenator together with hydrogen, contact with waste residue oil hydrogenation catalyst and react, the temperature of reaction of the second hydrogenator is lower than the temperature of reaction of the first hydrogenator, with waste residue oil hydrogenation catalyst for benchmark, the total metal content that described waste residue oil hydrogenation catalyst deposits is 1 ~ 50 heavy %, the coke of deposition is 5 ~ 30 heavy %,
The reaction effluent of (4) second hydrogenators carries out cooling, being 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, temperature of reaction 200 ~ 400 DEG C, 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, the stripping 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, the temperature of reaction of the second hydrogenator is lower than the temperature of reaction of the first hydrogenator 5 ~ 50 DEG C.
5. according to the method described in claim 1 or 4, it is characterized in that, catalyst for selectively hydrodesulfurizing is the group vib base metal of a kind of load on aluminum oxide and/or silica-alumina supports and/or group VIII non-precious metal catalyst.
6. according to the method described in claim 1 or 4, 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, be benchmark with oxide basis and with total catalyst weight, this catalyst for selectively hydrodesulfurizing contains molybdenum and/or the tungsten of the 5.0 heavy % in heavy % ~ 20, the nickel of the 2.0 heavy % in heavy % ~ 10.0 and/or cobalt.
7. in accordance with the method for claim 1, it is characterized in that, described waste residue oil hydrogenation catalyst is the residual oil hydrocatalyst after coming from the use of residual hydrogenation process, after waste residue oil hydrogenation catalyst is packed into the second hydrogenator, does not need regeneration also need not carry out prevulcanized.
8. according to the method described in claim 1 or 7, 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.
9. in accordance with the method for claim 7, it is characterized in that, described residual oil hydrocatalyst be load group vib base metal on the alumina support and/or group VIII non-precious metal catalyst, wherein group vib base metal is preferably molybdenum, group VIII base metal is preferably cobalt, be benchmark with oxide basis and with total catalyst weight, the molybdenum containing 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 DEG C of above-mentioned gasoline.
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