CN1429884A - Desulfurization process of gasoline - Google Patents
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- CN1429884A CN1429884A CN 01142833 CN01142833A CN1429884A CN 1429884 A CN1429884 A CN 1429884A CN 01142833 CN01142833 CN 01142833 CN 01142833 A CN01142833 A CN 01142833A CN 1429884 A CN1429884 A CN 1429884A
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Abstract
A process for desulfurizing gasoline includes such steps as reaction between thiol and diolefin in gasoline in fixed-bed reactor to generate S-contained compound with higher boiling point, separating out low-sulfure light fraction from the gasoline in distilling tower, hydrodesulfurizing or selective hydrodesulfurizing in catalytic distilling tower to convert said S-contained compound and other sulfide to hydrogen sulfide, discharging the hydrogen sulfide, residual hydrogen and part of gasoline fraction from the tower top, and discharging the heavy components of gasoline from tower still. Its advantages are less consumption of hydrogen and high output rate of liquid.
Description
Technical field
The present invention relates to a kind of desulfurization process of gasoline, particularly remove the technology of sulfocompound in the catalytically cracked gasoline, when the sulfocompound in the gasoline can be removed, reduce the loss of gasoline octane rating to greatest extent.
Background technology
Along with the continuous enhancing of people's environmental consciousness, the pollution that vehicle exhaust brought more and more becomes the focus that people pay close attention to.Using Exhaust Gas Catalytic Converter for Automobiles is to reduce the optimal path of automobile exhaust pollution thing quantity discharged, but the sulphur content in high performance exhaust catalytic converter the needs high-quality oil fuel, particularly gasoline has remarkable influence to the performance of exhaust catalytic converter.The requirement of 30～150 μ g/g is reduced to the sulphur content in the gasoline in propositions such as the U.S., Europe, Canada for this reason.
Complexity by sulphur content and desulfurization can be divided three classes the gasoline blend component.The first kind comprises reformate, alkylate oil, the very low blend component of isomerization wet goods sulphur content; Second class is light virgin naphtha, although contain a certain amount of sulphur, olefin(e) centent is low, can handle with traditional hydrofining technology; The 3rd class is FCC gasoline, coker gasoline etc., FCC gasoline particularly, sulphur content height (account in the gasoline total sulfur 85～95%) not only, also contain a large amount of alkene, if gasoline is all carried out hydrogenation with traditional hydrogenating desulfurization technology, almost all hydrogenation is saturated for alkene, and hydrogen-consuming volume is big, and loss of octane number is serious.
The sulfocompound in the catalytically cracked gasoline and the distribution of alkene have following characteristics: sulfide mainly concentrates in the last running, and the sulfide in the lighting end (as C5, C6) is based on mercaptan; Olefin(e) centent in the lighting end is higher than the olefin(e) centent in the last running, and high-octane olefin component concentrates in the lighting end.The present invention has utilized these characteristics exactly, and the sulfocompound in the weight gasoline fraction is adopted different treatment processs, when removing sulfide in petrol, reduces alkene (particularly high octane olefins) hydrogenation saturation exponent, reduces loss of octane number.
The gasoline desulfur technology of exploitation mainly contains two classes both at home and abroad at present, and the one, full hydrogen addition technology, in the time of desulfurization, alkene is all saturated; The 2nd, the selective hydrodesulfurization technology, in the time of desulfurization, the alkene fractional saturation.
OCTGAIN and ISAL belong to full hydrogen addition technology.OCTGAIN technology (the NPRAAnnual Meeting of exploitation such as Shih S.S., AM-99-30) divide two sections and in two reactors, carry out, in first reactor, FCC gasoline is carried out hydrofining, remove sulphur wherein, most of alkene is by saturated simultaneously, and therefore octane value also reduces; In second reactor, the product of first reactor is carried out isomerization to recover octane value with a kind of catalyzer that contains molecular sieve.But because of there being cracking reaction that yield of gasoline is descended; Alkene is almost all saturated, and the hydrogen consumption is high.ISAL technology (the NPRA Annual Meeting of exploitation such as Nelson P.M., AM-00-52) use proprietary catalyzer, in the time of sulfocompound in the hydrogenation and removing gasoline, low-octane alkane molecule is reset, the alkane molecular-weight average reduces, though can remedy the saturated loss of octane number that brings of alkene, liquid yield descends simultaneously.
SCANfining technology (the NPRA Annual Meeting of exploitation such as Thomas R. H., AM-00-11) technology adopts selective desulfurization catalyst, compares with traditional Hydrobon catalyst, the alkene saturation exponent descends greatly, has reduced hydrogen consumption and loss of octane number simultaneously.The Prime-G of France IFP exploitation
+(NPRAAnnual Meeting AM-00-61) selects hydrogenation with full cut FCC gasoline earlier to technology, removes diolefine wherein, with protection last running selective desulfurization catalyst; Isolate lighting end from the product of selecting hydrogenation, under the effect of dual catalyst system selective hydrodesulfurization is carried out in last running, alkene saturation exponent and the loss of octane number that causes thus are very little, and the saturated and cracking reaction of aromatic hydrocarbons does not take place, and liquid is received and reached 100%.But the H that its shortcoming is selective hydrodesulfurization to be produced
2S meeting and alkene further react generation mercaptan, and mercaptans content is generally 15～30 μ g/g in the product, need further mercaptan removal.
The disclosed catalytic distillation sulfur removal technology of CN1189183A enters a catalytic distillation tower with whole petroleum naphthas, kerosene, diesel oil, make the light gasoline fraction of high olefin content, low sulfur content also contact Hydrobon catalyst, increase the saturated chance of this part hydrogenation of olefins like this, can cause bigger loss of octane number.US 5,597, and 476 disclosed catalytic distillation sulfur removal technologies comprise two catalytic distillation towers.In first tower, under the effect of catalyzer, make mercaptan and diolefine reaction generation high boiling substance in the light gasoline fraction enter last running, obtain the C of low thioalcohol content from cat head
5Or C
5, C
6Cut is simultaneously remaining diolefin hydrogenate; Last running enters second catalytic distillation tower, adopts common Hydrobon catalyst to carry out hydrogenating desulfurization.Adopt two catalytic distillation tower catalyst loadings loaded down with trivial details, because the voidage of catalytic distillation tower catalyst filling zone is littler than general distillation tower, promptly turndown ratio is little, can not adjust treatment capacity or the desulfurization degree and the loss of octane number amount of two towers neatly.
Summary of the invention
The present invention has overcome the defective of above-mentioned prior art, be that feed gasoline at first enters fixed-bed reactor, make lower boiling sulfocompound such as hydrogen sulfide, mercaptan and diolefine in the gasoline under the effect of catalyzer, react the sulfocompound that generation has higher.Reacted gasoline enters distillation tower, obtain the lower light gasoline fraction of sulphur content from cat head, other cut enters a catalytic distillation tower, and the sulfide that under the Hydrobon catalyst therein or the effect of catalyst for selectively hydrodesulfurizing the reaction of mercaptan in the fixed bed and diolefine is generated and other sulfocompound in the gasoline are converted into hydrogen sulfide; Hydrogen sulfide, unreacting hydrogen are discharged from cat head in company with the part gasoline fraction that enters in the catalytic distillation tower, and hydrogen sulfide and unreacting hydrogen are carried from gasoline as non-condensable gas or through gas and being separated, and other gasoline reform branch is discharged from the tower still.
The catalyzer that is loaded in the fixed-bed reactor can be that nickel or palladium are active ingredient, is carrier with the aluminum oxide.Also can to load active ingredient be two kinds of catalyzer of nickel, palladium or contain nickel, two kinds of active ingredients of palladium on identical carrier.Under the effect of this catalyzer, addition reaction can take place in mercaptan and diolefine, generation has the sulfocompound of higher, at hydrogen atmosphere lower section and the selected monoolefine that is hydrogenated to of the remaining diolefine of thiol reactant, the isomerization reaction of part alkene also may take place, but the hydrogenation of olefins saturation exponent is very low.The material of catalyzer sulfocompounds such as available sulfide hydrogen, dithiocarbonic anhydride, Methyl disulfide before reaction carries out prevulcanized, also can not prevulcanized, but under reaction conditions, with material itself catalyzer is progressively vulcanized.Because the speed of reaction of mercaptan and diolefine addition reaction is the speed of reaction of monoolefine greater than diolefin hydrogenate, therefore be two kinds of catalyzer of nickel, palladium when loading active ingredient, and flow direction of material is for from top to bottom the time, and nickel catalyzator is seated in the top of palladium catalyst; When flow direction of material for from bottom to top the time, palladium catalyst is seated in the top of nickel catalyzator.Can reduce the murder by poisoning that mercaptan produces palladium catalyst so as far as possible.
The operational condition of fixed-bed reactor comprises: 40～250 ℃ of temperature of reaction, reaction pressure 0.2～3MPa (gauge pressure, down together), liquid phase volume air speed 0.5～10h
-1, the volume ratio of hydrogen and gasoline is 0～10.Adding hydrogen can play the certain protection effect to catalyzer, reduces gelationus and generates, and can also make and the selected monoolefine that is hydrogenated to of the remaining diolefine of thiol reactant, improves the stability of gasoline.
Because the sulfocompound in the light gasoline fraction is based on mercaptan, and in fixed-bed reactor, mercaptan and diolefine reaction have generated high boiling sulfide, therefore can obtain low-sulfur content light gasoline fraction from the cat head of common distillation tower.The amount of described light gasoline fraction can change according to total gasoline desulfur rate, when the gasoline desulfur rate is less demanding, the amount of the light gasoline fraction that obtains from the cat head of common distillation tower can be more, as comprise C4～C7 cut in the gasoline, both allowed the part thiophene sulfocompounds to enter light gasoline fraction, to reduce the treatment capacity of catalytic distillation tower, reduce the loss of octane number of hydrogen consumption and gasoline simultaneously; When the gasoline desulfur rate was had relatively high expectations, the amount of the light gasoline fraction that obtains from the cat head of common distillation tower will be hanged down relatively, as included only the C4～C 5 fraction in the gasoline, made thiophene sulfocompounds not enter light gasoline fraction as far as possible.By adjusting the operational condition of distillation tower, as temperature, pressure, the amount that is easy to light gasoline fraction that the cat head from common distillation tower is obtained is regulated; This distillation tower generally can adopt atmospheric operation, can adopt pressurized operation when the amount of light gasoline fraction is relatively low, but that working pressure does not need is very high, as is lower than 0.8MPa.
The gasoline fraction with higher that obtains from described common distillation Tata still enters a catalytic distillation tower, therein under the effect of the Hydrobon catalyst that is loaded, most of sulfocompound is generated hydrogen sulfide by hydrogenation, and together discharge from the return tank top, or come out by stripping through stripping tower as non-condensable gas with unreacting hydrogen.Catalyzer can be divided into a plurality of beds and be seated in the catalytic distillation tower, and what of the amount of the amount of opening for feed top catalyzer and the agent of opening for feed lower catalytic are relevant with what of cat head load, tower still load.Hydrogen can be all from entering below the beds in the tower; Also can be partly below bed, part enters in the tower between the bed.
The Hydrobon catalyst that loads in described catalytic distillation tower can be common Hydrobon catalyst, as carrier is aluminum oxide, active ingredient is a cobalt, the Hydrobon catalyst of molybdenum, it also can be hydrogenation catalyst with selective desulfurization function, a kind of selection Hydrobon catalyst of particularly suitable contains molybdenum and/or tungsten, nickel and/or cobalt, load on and contain spinel, on the complex carrier of activated alumina and cement, wherein the content of molybdenum and/or tungsten accounts for the 0.1-15% of catalyst weight in metal oxide, and the content of nickel and/or cobalt accounts for the 0.1-10% of catalyst weight in metal oxide; In the complex carrier, spinel content is 50-90%, best 55-80%, and aluminum oxide and cement account for respectively and are no more than 45% of vehicle weight; Spinel is preferably magnesium-aluminium spinel, and cement is preferably aluminous cement.
The outer shape of described Hydrobon catalyst or selection Hydrobon catalyst can be column, spherical, trifolium shape, also can be itself to have fractionation and the bifunctional filler shape of katalysis, Chinese patent CN1242410 discloses the double-functional packing shape and has selected hydrogenization catalyst preparation method, is quoted in this patent.
The catalytic distillation tower working pressure is 1.0～2.5MPa, the temperature of beds is 250～400 ℃, unit time catalytic distillation tower liquid phase feeding volume is 0.5～8 with the ratio of catalyst volume, the ratio 50～500 (standard state) of hydrogen and catalytic distillation tower liquid phase feeding volume.
Owing to exist in the catalytic distillation tower and the corresponding to lowly high temperature distribution that goes up of material boiling point, it is the cold zone that sulphur content is lower, olefin(e) centent is higher, boiling point is relatively low cut is in catalytic distillation tower, and the cut that sulphur content is higher, olefin(e) centent is lower, boiling point is higher relatively is in the high-temperature zone of catalytic distillation tower, the carrying out that helps desulphurization reaction, it is saturated simultaneously can to reduce alkene, reduce hydrogen consumption, reduce loss of octane number.
Compared with prior art technology is simple, turndown ratio is big in the present invention, can adjust treatment capacity or the gasoline desulfur rate and the loss of octane number amount of catalytic distillation tower neatly, and the hydrogen consumption is low, liquid yield is high.
Accompanying drawing is a process flow diagram of the present invention
The present invention will be further described below in conjunction with accompanying drawing:
Gasoline enters the first reactor (2) by pipeline (1), hydrogen through piping (22). Alkadienes under the catalyst action that loads therein in the gasoline and thiol reactant generate the sulfur-containing compound with higher. Reacting rear material enters common destilling tower (4) by pipeline (3). Light gasoline fraction enters condenser (6) by cat head through pipeline (5) and is condensed into liquid. Partially liq returns by pipeline (7) and makes phegma in the tower, and part goes out device by pipeline (8). Gasoline distillation tower (4) bottom is equipped with reboiler (9) heat is provided. Tower bottoms enters catalytic distillation tower (11) by pipeline (10), hydrogen through pipeline (12) from entering catalytic distillation tower below the beds. Sulfur-containing compound in the gasoline generates hydrogen sulfide with hydrogen reaction under the effect of catalyst. Hydrogen sulfide, unreacting hydrogen and part gasoline fraction enter condenser (14) by cat head through pipeline (13), material enters return tank (16) by pipeline (15) after the condensation, unreacting hydrogen, hydrogen sulfide go out device as fixed gas through pipeline (18) in return tank, the hydrogen that removes behind the hydrogen sulfide can recycle (not showing among the figure). The condensate liquid part is returned catalytic distillation tower (11) as phegma through pipeline (17), and remainder goes out device through pipeline (19). The catalytic distillation tower bottom is provided with reboiler (20) catalytic distillation tower institute calorific requirement is provided. Heavy distillat in the gasoline is left catalytic distillation tower (11) through pipeline (21) and is gone out device. The gasoline light fraction that is obtained by pipeline (8) can enter the devices such as etherificate, alkylation, also can be mixed to get low sulfur clean gasoline with other gasoline fraction that is obtained by pipeline (19), (21).
Embodiment embodiment 1: raw material is a catalytically cracked gasoline, and its character sees Table 1.
The character of table 1 gasoline stocks
| Alkane content, % (V/V) | ????37.22 | Boiling range distributes ℃ | Initial boiling point | ??38 |
| Olefin(e) centent, % (V/V) | ????48.03 | ??10％ | ??55 | |
| Aromaticity content, % (V/V) | ????14.76 | ??30％ | ??72 | |
| Total sulfur, μ g/g | ????1534 | ??50％ | ??95 | |
| Mercaptan sulfur, μ g/g | ????168 | ??70％ | ??131 | |
| Vapour pressure, KPa | ????54.4 | ??90％ | ??167 | |
| Density, g/cm 3 | ????0.7209 | Do | ??198 |
Fixed-bed reactor are equipped with catalyzer 0.77m in (2)
3, its NiO content is 55%, carrier is an aluminum oxide.Temperature of reaction is 140 ℃, reaction pressure 1.5Mpa.The inlet amount of catalytically cracked gasoline is 1000Kg/h, and the inlet amount of hydrogen is 0.8 mark side/h.
The working pressure of common separation column (4) is 0.3MPa (gauge pressure), 85 ℃ of tower top temperatures.The amount of the light gasoline fraction that obtains from cat head is 490Kg/h, is mainly C4～C6 cut, and all the other are as tower stilling branch.
The working pressure of catalytic distillation tower is 2.5MPa, 230 ℃ of tower top temperatures.The temperature of beds top and the bottom is respectively 290 ℃ and 320 ℃; Catalyzer is that cobalt, molybdenum are Hydrobon catalyst, and its carrier is an aluminum oxide, and the content of molybdenum oxide is 13.3%, and the content of cobalt oxide is 3.5%, and loaded catalyst is 0.6m
3Hydrogen (12) amount that enters catalytic distillation tower is 120 mark sides/h.Catalytic distillation Tata still load is 238.5Kg/h.
The distribution of sulfocompound in each cut sees Table 2:
The distribution of table 2 sulfocompound in each cut
| Raw material | Common distillation tower overhead fraction | The catalytic distillation tower overhead fraction | Catalytic distillation Tata stilling branch | |
| Sulphur content, μ g/g | ????1534 | ????138 | ????71 | ????82 |
| Mercaptan, μ g/g | ????168 | ????4 | ????5 | ????＜1 |
To be mixed obtaining the low-sulfur clean gasoline by the gasoline lighting end that pipeline (8) obtain with other gasoline fraction that is obtained by pipeline (19), (21), its character sees Table 3:
The character of gasoline after table 3 desulfurization
| Alkane content, % (V/V) | ????48.99 | Boiling range distributes ℃ | Initial boiling point | ????38 |
| Olefin(e) centent, % (V/V) | ????36.81 | ??10％ | ????55 | |
| Aromaticity content, % (V/V) | ????14.20 | ??30％ | ????72 | |
| Total sulfur, μ g/g | ????106 | ??50％ | ????95 | |
| Mercaptan sulfur, μ g/g | ????3 | ??70％ | ????123 | |
| Vapour pressure, KPa | ????55.1 | ??90％ | ????164 | |
| Density, g/cm 3 | ????0.7139 | Do | ????197 |
Sulphur content in the raw material FCC gasoline is 1534 μ g/g, and the content of sulfur in gasoline after art breading of the present invention is reduced to 106 μ g/g, and desulfurization degree reaches 93%, and the anti-knock index loss is 1.2.Embodiment 2: raw materials used, treatment capacity, reaction conditions are identical with embodiment 1, and different is is adjusted into 310Kg/h with the cat head load of common distillation tower, and catalytic distillation Tata still load is 365Kg/h.The distribution of resulting sulfocompound in each cut sees Table 4, will be in harmonious proportion by the logistics that pipeline (8), (19) and (21) obtain, and the character of gasoline sees Table 5 after the resulting desulfurization:
The distribution of table 4 sulfocompound in each cut
| Raw material | Common distillation tower overhead fraction | The catalytic distillation tower overhead fraction | Catalytic distillation Tata stilling branch | |
| Sulphur content, μ g/g | ????1534 | ????18 | ????78 | ????96 |
| Mercaptan, μ g/g | ????168 | ????3 | ????5 | ????＜1 |
The character of gasoline after table 5 desulfurization
| Alkane content, % (V/V) | ????51.03 | Boiling range distributes ℃ | Initial boiling point | ????38 |
| Olefin(e) centent, % (V/V) | ????34.68 | ????10％ | ????53 | |
| Aromaticity content, % (V/V) | ????14.29 | ????30％ | ????72 | |
| Total sulfur, μ g/g | ????66 | ????50％ | ????97 | |
| Mercaptan sulfur, μ g/g | ????3 | ????70％ | ????130 | |
| Vapour pressure, Kpa | ????55.6 | ????90％ | ????171 | |
| Density, g/cm 3 | ????0.7133 | Do | ??194 |
Raw material FCC sulfur in gasoline content is 1534 μ g/g, and the sulphur content after art breading of the present invention is reduced to 66 μ g/g, and desulfurization degree reaches 95.7%, and anti-knock index is 1.4.Embodiment 3: raw materials used, treatment capacity, reaction conditions are identical with embodiment 2, different is, and what to load in the catalytic distillation tower is catalyst for selectively hydrodesulfurizing, the carrier of this catalyzer is by 70 parts of magnesium-aluminium spinels, 15 parts of aluminum hydroxide solid elastomer powder and 15 parts of aluminous cements are made, and are downloaded to active ingredient Mo, Co on the catalyzer at last with MoO
3, CoO weight account for whole catalyst weight meter and be respectively 8.3%, 1.6%.The distribution of resulting sulfocompound in each cut sees Table 6, will be in harmonious proportion by the logistics that pipeline (8), (19) and (21) obtain, and the character of gasoline sees Table 7 after the resulting desulfurization:
The distribution of table 6 sulfocompound in each cut
| Raw material | Common distillation tower overhead fraction | The catalytic distillation tower overhead fraction | Catalytic distillation Tata stilling branch | |
| Sulphur content, μ g/g | ????1534 | ????18 | ????105 | ????135 |
| Mercaptan, μ g/g | ????168 | ????3 | ????5 | ????＜1 |
The character of gasoline after table 7 desulfurization
| Alkane content, % (V/V) | ????43.14 | Boiling range distributes ℃ | Initial boiling point | ??38 |
| Olefin(e) centent, % (V/V) | ????42.35 | ??10％ | ??53 | |
| Aromaticity content, % (V/V) | ????14.51 | ??30％ | ??72 | |
| Total sulfur, μ g/g | ????89 | ??50％ | ??97 | |
| Mercaptan sulfur, μ g/g | ????3 | ??70％ | ??130 | |
| Vapour pressure, Kpa | ????55.3 | ??90％ | ??171 | |
| Density, g/cm 3 | ????0.7132 | Do | ??194 |
Raw material FCC sulfur in gasoline content is 1534 μ g/g, and the sulphur content after art breading of the present invention is reduced to 89 μ g/g, and desulfurization degree reaches 94.2%.The anti-knock index loss is 0.9.
Claims (15)
1. technology that removes sulfocompound in the catalytically cracked gasoline is characterized in that:
(a) catalytically cracked gasoline that will contain sulfocompounds such as mercaptan, thiophene-based and diolefine is sent in first reactor;
(b) in described first reactor, lower boiling sulfocompound such as mercaptan generates the higher sulfocompound of boiling point with the diolefine reaction under catalyst action;
(c) material behind described first reactor reaction enters a conventional distillation tower, obtains the gasoline lighting end of low sulfur content from cat head, and other cut enters a catalytic distillation tower by the tower still;
(d) under the Hydrobon catalyst or catalyst for selectively hydrodesulfurizing effect that in described catalytic distillation tower, is loaded, the sulfocompound that the boiling point that step (b) generates is higher and other sulfocompound and hydrogen reaction generate hydrogen sulfide, described hydrogen sulfide and unreacted hydrogen and part gasoline fraction are discharged from cat head, and other gasoline reform branch is discharged from the tower still.
2. according to the described technology of claim 1, wherein first reactor is fixed-bed reactor, and flow direction of material can be from bottom to top, also can be from top to bottom.
3. according to the described technology of claim 1, wherein the activity of such catalysts component in first reactor is nickel and/or palladium.
4. according to claim 1 or 3 described technologies, wherein the catalyzer in first reactor can carry out prevulcanized with the material that contains sulfocompound before reaction.
5. according to the described technology of claim 4, wherein sulfocompound is hydrogen sulfide, dithiocarbonic anhydride or Methyl disulfide.
6. according to claim 1,2 or 3 described technologies, wherein temperature of reaction is 40～250 ℃ in first reactor, and reaction pressure is 0.2～3.0MPa, and liquid hourly space velocity is 0.5～10h
-1
7. according to the described technology of claim 6, wherein temperature of reaction is 40～250 ℃ in first reactor, and reaction pressure is 0.2～3.0MPa, and liquid hourly space velocity is 0.5～10h
-1, the volume ratio of hydrogen and gasoline is 0～10.
8. according to the described technology of claim 1, the light gasoline fraction that obtains from described conventional distillation tower top mainly comprises carbon four, carbon five components.
9. according to the described technology of claim 1, the light gasoline fraction that obtains from described conventional distillation tower top mainly comprises carbon four, carbon five, carbon six components.
10. according to the described technology of claim 1, the light gasoline fraction that obtains from described conventional distillation tower top mainly comprises carbon four, carbon five, carbon six, carbon seven components.
11. according to the described technology of claim 1, the working pressure of described conventional distillation tower is 0～0.8MPa.
12. according to the described technology of claim 1, the working pressure of described catalytic distillation tower is 1.0～2.5MPa, the temperature of beds is 250～400 ℃.
13. according to claim 1 or 12 described technologies, the Hydrobon catalyst in the described catalytic distillation tower is an active ingredient with cobalt, molybdenum, is carrier with the aluminum oxide.
14. according to claim 1 or 12 described technologies, catalyst for selectively hydrodesulfurizing in the described catalytic distillation tower is with molybdenum and/or tungsten, nickel and/or cobalt are active ingredient, load on the complex carrier that contains spinel, activated alumina and cement, wherein the content of molybdenum and/or tungsten accounts for the 0.1-15% of catalyst weight in metal oxide, and the content of nickel and/or cobalt accounts for the 0.1-10% of catalyst weight in metal oxide.
15. according to claim 1 or 12 described technologies, unit time catalytic distillation tower liquid phase feeding volume is 0.5～8 with the ratio of catalyst volume, hydrogen counts 50～500 with the ratio of catalytic distillation tower liquid phase feeding volume with standard state.
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| CN100363742C (en) * | 2004-06-29 | 2008-01-23 | 中国石油化工股份有限公司 | Method for detecting corrosive sulfur content in crude oil or fraction oil |
| CN101307254B (en) * | 2007-05-18 | 2011-06-22 | 中国石油化工股份有限公司 | Process for producing cleaning gasoline from poor-quality gasoline |
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| CN103184071A (en) * | 2011-12-28 | 2013-07-03 | 中国石油天然气股份有限公司 | Gasoline desulfurization method |
| CN103436286A (en) * | 2013-07-18 | 2013-12-11 | 济南开发区星火科学技术研究院 | Catalytic rectification hydrogenation desulfurization process of gasoline heavy distillate |
| CN103881749A (en) * | 2014-03-24 | 2014-06-25 | 南开大学 | Method for removing thiophenic sulfide in fuel oil |
| CN109722270A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of mercaptan and disulfide content in the click-reaction method and its application and reduction light oil of mercaptan and Electron-poor olefin |
| CN110157477A (en) * | 2018-08-09 | 2019-08-23 | 南京大学连云港高新技术研究院 | A kind of high olefin gasolines desulfurization of high-sulfur proposes high-octane method and apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100363742C (en) * | 2004-06-29 | 2008-01-23 | 中国石油化工股份有限公司 | Method for detecting corrosive sulfur content in crude oil or fraction oil |
| CN101307254B (en) * | 2007-05-18 | 2011-06-22 | 中国石油化工股份有限公司 | Process for producing cleaning gasoline from poor-quality gasoline |
| CN103059914A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Method for removing dienes and nitriles from light petroleum product |
| CN103059914B (en) * | 2011-10-21 | 2015-03-18 | 中国石油化工股份有限公司 | Method for removing dienes and nitriles from light petroleum product |
| CN103184071A (en) * | 2011-12-28 | 2013-07-03 | 中国石油天然气股份有限公司 | Gasoline desulfurization method |
| CN103184071B (en) * | 2011-12-28 | 2015-07-22 | 中国石油天然气股份有限公司 | Gasoline desulfurization method |
| CN103436286A (en) * | 2013-07-18 | 2013-12-11 | 济南开发区星火科学技术研究院 | Catalytic rectification hydrogenation desulfurization process of gasoline heavy distillate |
| CN103436286B (en) * | 2013-07-18 | 2015-05-27 | 济南开发区星火科学技术研究院 | Catalytic rectification hydrogenation desulfurization process of gasoline heavy distillate |
| CN103881749A (en) * | 2014-03-24 | 2014-06-25 | 南开大学 | Method for removing thiophenic sulfide in fuel oil |
| CN109722270A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of mercaptan and disulfide content in the click-reaction method and its application and reduction light oil of mercaptan and Electron-poor olefin |
| CN110157477A (en) * | 2018-08-09 | 2019-08-23 | 南京大学连云港高新技术研究院 | A kind of high olefin gasolines desulfurization of high-sulfur proposes high-octane method and apparatus |
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