CN101987970A - Method for removing mercaptan from gasoline - Google Patents
Method for removing mercaptan from gasoline Download PDFInfo
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- CN101987970A CN101987970A CN2009101574661A CN200910157466A CN101987970A CN 101987970 A CN101987970 A CN 101987970A CN 2009101574661 A CN2009101574661 A CN 2009101574661A CN 200910157466 A CN200910157466 A CN 200910157466A CN 101987970 A CN101987970 A CN 101987970A
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Abstract
The invention discloses a method for removing mercaptan from gasoline. The method comprises that: raw materials are introduced from the top of a reactor, flow through the reactor from top to bottom, and are in contact with a mercaptan-removing catalyst filled in the reactor under certain operation condition; the mercaptan in the raw materials is decomposed into olefin and hydrogen sulfide gas; a steam stripping medium is introduced into the bottom of the reactor and is in countercurrent contact with the gasoline so as to remove the produced hydrogen sulfide gas from the reaction zone timely; the steam stripping medium containing the hydrogen sulfide gas is discharged from the top of the reactor; and a gasoline product from which the mercaptan is removed is led out of the bottom of the reactor, wherein the steam stripping medium is an inert gas and/or steam. By using the method, one gram of gasoline product produced by the method contains less than 3 micrograms of mercaptan sulfur, the total sulfur content of the gasoline product is reduced, and octane number loss is avoided.
Description
Technical field
The present invention relates to a kind of method made from extra care hydrocarbon ils under the situation of hydrogen that do not exist.More particularly, be a kind of under the situation that does not have hydrogen, remove the method that sulfur in gasoline alcohol is produced low-sulphur oil.
Background technology
Along with the increasingly stringent of environmental regulation, countries in the world have proposed stricter restriction to the composition of motor spirit such as sulphur content, vapour pressure, benzene content, aromatic hydrocarbons total content, olefin(e) centent, and are wherein particularly harsh to the restriction of the sulphur content in the gasoline.China plans on December 31st, 2009 the motor spirit quality upgrading to require content of sulfur in gasoline to be not more than 150 μ g/g to state III standard.Beijing has taken the lead in coming into effect state IV emission standard in 2008, requires content of sulfur in gasoline further to be reduced to below the 50 μ g/g.
Catalytically cracked gasoline is the main gasoline component of refinery, accounts for more than 70% of gasoline harmonic proportion.Catalytic gasoline contains a large amount of alkene and sulfide.The sulfide that removes in the catalytically cracked gasoline is the key that satisfies the clean gasoline new standard.
Sulfide in the gasoline comprises that thio-alcohol, multiple sulfides, heterocycle are sulfide-based as thiophene and homologue and analogue.Thio-alcohol part in the gasoline is small molecules mercaptan such as methyl mercaptan, ethanethio, propyl group mercaptan etc., and these small molecules, lower boiling mercaptan can be removed by the extractive method of alkali.Also there are some high boiling points, macromolecular mercaptan such as butyl sulfhydryl, pentan-thiol, hexylmercaptan etc. in the gasoline.These macromole, high boiling point mercaptan stable in properties can't remove by the alkali extracting, generally adopt catalyzed oxidation technology to convert it into disulphide and are present in the product, and do not reduce the total sulfur content of product.
Usually the method for employing hydrogenation can remove macromole mercaptan and the other types sulfide in the gasoline, reduces the sulphur content in the gasoline.
CN1478866A discloses a kind of method of gasoline desulfur.This method is cut into light gasoline fraction, heavy naphtha with gasoline stocks; Heavy naphtha contacts with Hydrobon catalyst together with hydrogen, carry out the selective hydrodesulfurization reaction, after reaction effluent is isolated gas phase through high-pressure separator, remaining liquid phase with contact with the hydrogenating desulfurization alcohol catalyst again after new hydrogen mixes, described Hydrobon catalyst and described hydrogenating desulfurization alcohol catalyst are group vib or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports.This method can the production sulphur content be lower than 200 μ g/g, and mercaptan sulfur is lower than the gasoline of 10 μ g/g, and hydro-sweetening process octane value does not lose substantially.
CN101089130A discloses a kind of method of producing low-sulphur oil.This method comprises that gasoline stocks carries out the selective hydrodesulfurization reaction in the presence of catalyst for selectively hydrodesulfurizing, reaction product contacts with the hydrogenating desulfurization alcohol catalyst, obtain the low-sulphur oil product after the reaction, the content of described hydrogenating desulfurization alcohol catalyst mesolite is 50.0wt%-90.0wt%, and the total content of transition metal oxide and lanthanide rare metal oxide is 11.0wt%-31.0wt%.This method can be handled the inferior full distillation gasoline of high-sulfur, high alkene content, and flow process is simple, and is easy to operate, and gained gasoline products not only total sulfur content is lower than 50 μ g/g, and mercaptan sulfur content is lower than 10 μ g/g, and its product loss of octane number is lower than 2 units.
But in the hydrodesulfurization reaction process, H in the reactant flow
2S content constantly increases, and can make alkene and hydrogen sulfide reaction in the gasoline generate new mercaptan sulfur, and these mercaptan mainly also are C
5Above macromole mercaptan.
US6416658B1 proposes a kind of naphtha desulfurization method, petroleum naphtha is carried out hydrogenating desulfurization simultaneously and is separated into the light boiling range petroleum naphtha and the heavy boiling range petroleum naphtha, by the light boiling range petroleum naphtha is further contacted with hydrogen with reflux type, remove the regeneration mercaptan that hydrodesulfurization process generates subsequently.
Though adopt the countercurrent hydrogenation desulfurization can avoid new mercaptan to generate, because olefin content in gasoline is higher, it is saturated still to have part alkene in the hydro-sweetening process, causes the product loss of octane number.
Summary of the invention
The objective of the invention is on the basis of existing technology, provide a kind of under the non-hydrogen state, remove sulfur in gasoline alcohol sulphur, reduce the method for gasoline total sulfur content simultaneously.
A kind of method that removes sulfur in gasoline alcohol sulphur provided by the invention, raw material is introduced by reactor top, from top to bottom flow through reactor, contact with the mercaptan-eliminating catalyst that loads in the reactor, the mercaptan decomposition in the raw material is alkene and hydrogen sulfide, and reactor bottom is introduced the stripping medium, stripping medium and gasoline counter current contact, the hydrogen sulfide that generates is in time shifted out reaction zone, and the stripping medium that contains hydrogen sulfide is discharged by reactor top, and reactor bottom is drawn the gasoline fraction that has removed mercaptan.
In the method provided by the invention, described raw material comprises that boiling range is 10 ℃-230 ℃ a gasoline fraction, for example one or more mixture in catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline and the pressure gasoline.Preferred boiling range is 40 ℃-230 ℃ the gasoline fraction that contains alkene, and olefin(e) centent is at least 5wt%.
In the method provided by the invention, operation condition is: temperature of reaction is 150～350 ℃, preferred 210～260 ℃, and pressure is 0.2MPa～6MPa, preferred 0.4～2.5MPa, and volume space velocity is 2～15h during feeding liquid
-1, preferred 4～10h
-1, charging stripping medium and stock oil volume ratio are 5-200 (under the standard state), preferred 5～200.
In the method provided by the invention, described stripping medium can be under the operational condition not the rare gas element that reacts with raw material, and it is saturated as the hydrogenation of alkene to guarantee that other reactions can not take place in mercaptan removal gasoline stocks.Typical stripping medium comprises nitrogen, carbonic acid gas, carbon monoxide, methane, hydro carbons or water vapour.Preferred nitrogen is as the stripping medium.
In the method provided by the invention, described reactor can be a various forms, comprises fixed bed, fluidized-bed, ebullated bed etc., and gasoline fraction and stripping medium can contact in that catalyst surface is reverse in the reactor, H that will the reaction generation
2S in time shifts out beds, and is taken out of reactor by the stripping medium.Preferred reactor types is fixed-bed reactor.
In the method provided by the invention, described catalytic desulfurization alcohol catalyst is VIB or the VIII family non-precious metal catalyst that loads on amorphous alumina or the silica-alumina supports.Preferred catalyzer is Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and the cobalt oxide that loads on the alumina supporter, with the total catalyst weight is benchmark, the content of Tungsten oxide 99.999 and/or molybdenum oxide is 4-10wt% in the described mercaptan-eliminating catalyst, nickel oxide content is 1～5wt%, cobalt oxide content is 0.01～1wt%, and the total atom number of nickel and cobalt is 0.3～0.9 with the ratio of Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and cobalt oxide total atom number.More preferably, wherein nickel oxide content is 2～4wt%, and cobalt oxide content is 0.02～0.5wt%; The content of Tungsten oxide 99.999 and/or molybdenum oxide is 4.5～9wt%, and the total atom number of nickel and cobalt is 0.4～0.7 with the ratio of Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and cobalt oxide total atom number.Described mercaptan-eliminating catalyst can adopt oxidized catalyst, also can adopt the sulphided state catalyzer, preferably adopts oxidized catalyst.The structure of catalyzer and size can guarantee gas-liquid two-phase counter-current operation in the reactor.
Description of drawings
Accompanying drawing is the schematic flow sheet of method provided by the invention.
Embodiment
The following examples will give further instruction to method provided by the invention, but therefore not limit the present invention.
Describing method provided by the invention below with reference to the accompanying drawings in detail, is alkene and hydrogen sulfide but therefore the present invention is not subjected to limitting catalytic decomposition.Inertia stripping medium is introduced from reactor bottom by pipeline 3, and the stripping medium of rising in time will react the hydrogen sulfide that produces and shift out beds 2, the mercaptan decomposition balance be moved, the mercaptan decomposition in the gasoline fraction to the direction of hydrogen sulfide and alkene.The hydrogen sulfide that stripping medium and reaction produce is discharged from reactor head through pipeline 4, removes recycle behind the hydrogen sulfide; Gasoline products behind the mercaptan removal is drawn through pipeline 6 from reactor 1 bottom.
The beneficial effect of method provided by the invention is:
Adopt method provided by the invention, gasoline contacts with the stripping medium counter flow in the reactor, because hydrogen sulfide is removed in the stripping effect of stripping medium, reaction is moved to helping the mercaptan decomposition direction, can remove the most of mercaptan in the gasoline.For olefine contained gasoline since under the condition that does not have hydrogen catalytic decomposition mercaptan, can avoid causing the product loss of octane number because of hydrogenation of olefins is saturated.Method provided by the invention can be produced mercaptan sulfur content and is lower than 3 μ g/g gasoline products, and the gasoline products total sulfur content reduces simultaneously, does not have loss of octane number.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Catalyzer used in embodiment and the Comparative Examples is produced by Sinopec catalyzer Chang Ling branch office, and trade names are RSS-1A, and it mainly consists of, and in total catalyst weight, contains the NiO of 4.5wt%, the WO of 14.5wt%
3Al with surplus
2O
3
Comparative Examples
Catalytically cracked gasoline A character is as shown in table 1, and wherein olefin(e) centent is 27.3%, and total sulfur content is 60 μ g/g, and mercaptans content is 26 μ g/g.With catalytically cracked gasoline A is raw material, and earlier through caustic wash desulfuration alcohol, the gasoline products character behind the mercaptan removal sees Table 1.From table 1, the product mercaptans content after the alkali cleaning is 25 μ g/g, illustrates that the mercaptan in the raw material is macromole mercaptan, can't use conventional catalytic oxidation desulfurization alcohol art breading.Loading catalyst RSS-1A in the fixed-bed reactor, be shaped as trifolium-shaped, diameter is 1.3mm, gasoline fraction behind the caustic wash desulfuration alcohol and hydrogen pass through fixed-bed reactor under also flowing to, contact with the RSS-1A catalyzer and to carry out the hydro-sweetening reaction, reaction pressure is 1.6Mpa, and temperature is 240 ℃, hydrogen-oil ratio is 50, and the feed volume air speed is 5h
-1Obtain gasoline products behind the hydro-sweetening, character sees Table 1.
Embodiment 1
The filling diameter is the Raschig ring RSS-1A catalyzer of 2mm in the fixed-bed reactor.With catalytically cracked gasoline A is raw material, directly is introduced into fixed-bed reactor top, N without alkali cleaning
2Gas is introduced from reactor bottom, and gas-liquid two-phase is counter current contact on catalyzer, is 1.4Mpa at pressure, and temperature is to react under 200 ℃ the condition, and the long-pending air speed of charging plastid is 5h
-1, feeding gas/oil volume ratio is 25 (mark attitudes), and reactor bottom is drawn gasoline products behind the mercaptan removal, and character sees Table 1.
Embodiment 2
The Raschig ring RSS-1A catalyzer of filling diameter 3mm is a raw material with catalytically cracked gasoline A in the stripping tower, directly is introduced into stripping tower top, N without alkali cleaning
2Gas is introduced from the stripping tower bottom, and the steam that produces with tower still reboiler upwards passes through beds.The stripping tower overhead vapours is after condensation, and liquid phase all refluxes, non-condensable gas N
2Discharge, the gasoline fraction behind the mercaptan removal is discharged at the bottom of tower.The stripping tower working pressure is 2.4MPa, and the beds medial temperature is 260 ℃, and the feed volume air speed is 8h
-1, charging N
2Gas/oil volume ratio is 5 (mark attitudes), and gasoline products character sees Table 1 behind the mercaptan removal.
Table 1
As can be seen from Table 1, embodiment 1 compares with Comparative Examples, and the mercaptans content of gasoline products drops to 2.8 μ g/g from 9 μ g/g, and total sulfur content drops to 37 μ g/g by 42 μ g/g.Embodiment 2 compares with Comparative Examples, and the mercaptans content of gasoline products drops to 2.2 μ g/g from 9 μ g/g, and sulphur content is fallen by 42 μ g/g and dropped to 36 μ g/g.As seen adopt method provided by the invention, can remove the mercaptan in the gasoline, reduce the gasoline products total sulfur content, octane value does not lose substantially.
Claims (11)
1. method that removes sulfur in gasoline alcohol sulphur, it is characterized in that raw material introduced by reactor top, from top to bottom flow through reactor, under certain operational condition, contact with the mercaptan-eliminating catalyst that loads in the reactor, mercaptan decomposition in the raw material is alkene and hydrogen sulfide, reactor bottom is introduced the stripping medium, stripping medium and gasoline counter current contact, the hydrogen sulfide that generates is in time shifted out reaction zone, the stripping medium that contains hydrogen sulfide is discharged by reactor top, reactor bottom is drawn the gasoline products that has removed mercaptan, and described stripping medium is rare gas element and/or steam.
2. according to the method for claim 1, it is characterized in that described operation condition is: temperature of reaction is 150～350 ℃, and pressure is 0.2～6MPa, and volume space velocity is 2～15h during feeding liquid
-1, feeding gas oil volume ratio is 5～200 (under the standard state).
3. according to the method for claim 2, its feature is done condition at described operation and is: temperature is 180～260 ℃, and reaction pressure is 0.4～2.5MPa.Volume space velocity is 4～10h during feeding liquid
-1, feeding gas oil volume ratio is 5～200 (under the standard state).
4. according to the method for claim 1, it is characterized in that described mercaptan-eliminating catalyst is VIB and/or the VIII family non-precious metal catalyst that loads on aluminum oxide or the silica-alumina supports.
5. according to the method for claim 4, it is characterized in that in the described mercaptan-eliminating catalyst that the metal component that loads on the carrier contains Tungsten oxide 99.999 and/or molybdenum oxide, and nickel oxide.
6. according to the method for claim 5, it is characterized in that described mercaptan-eliminating catalyst is Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and the cobalt oxide that loads on the alumina supporter, with the total catalyst weight is benchmark, the content of Tungsten oxide 99.999 and/or molybdenum oxide is 4～15wt% in the described mercaptan-eliminating catalyst, nickel oxide content is 1～5wt%, and cobalt oxide content is 0.01～1wt%.
7. according to the method for claim 1, it is characterized in that described raw material is that boiling range is 10 ℃～230 ℃ a petroleum hydrocarbon cut.
8. according to the method for claim 7, it is characterized in that described raw material is that boiling range is 50～230 ℃, contains the petroleum hydrocarbon fraction of 5wt% alkene at least.
9. according to the method for claim 8, it is characterized in that described raw material is one or more the mixture in catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, pyrolysis gasoline and the pressure gasoline.
10. according to the method for claim 1, described stripping medium is nitrogen, carbonic acid gas, carbon monoxide, lighter hydrocarbons or water vapor.
11. according to the method for claim 1, described reactor is fixed-bed reactor, fluidized-bed reactor, distillation column reactor or ebullated bed reactor.
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| CN200910157466.1A CN101987970B (en) | 2009-07-30 | 2009-07-30 | Method for removing mercaptan from gasoline |
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| CN200910157466.1A CN101987970B (en) | 2009-07-30 | 2009-07-30 | Method for removing mercaptan from gasoline |
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| CN101987970A true CN101987970A (en) | 2011-03-23 |
| CN101987970B CN101987970B (en) | 2014-08-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773440A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Pretreatment method for desulphurization adsorbents and desulphurization method for sulfur-containing hydrocarbon raw materials |
| CN107660268A (en) * | 2015-05-12 | 2018-02-02 | 国际壳牌研究有限公司 | Method including analyzing streaming flow |
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| US5062947A (en) * | 1988-04-28 | 1991-11-05 | Shell Oil Company | Sulfiding of hydrogel derived catalysts |
| US5482617A (en) * | 1993-03-08 | 1996-01-09 | Mobil Oil Corporation | Desulfurization of hydrocarbon streams |
| CN1134312A (en) * | 1995-08-16 | 1996-10-30 | 南京化学工业(集团)公司催化剂厂 | Organic sulfur hydrolysis catalyst and preparation thereof |
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2009
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Patent Citations (4)
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| US5062947A (en) * | 1988-04-28 | 1991-11-05 | Shell Oil Company | Sulfiding of hydrogel derived catalysts |
| US5482617A (en) * | 1993-03-08 | 1996-01-09 | Mobil Oil Corporation | Desulfurization of hydrocarbon streams |
| CN1134312A (en) * | 1995-08-16 | 1996-10-30 | 南京化学工业(集团)公司催化剂厂 | Organic sulfur hydrolysis catalyst and preparation thereof |
| JP2004095445A (en) * | 2002-09-02 | 2004-03-25 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery and nonaqueous electrolyte used for the same |
Non-Patent Citations (1)
| Title |
|---|
| 赵素芬，等: "预硫化催化剂RSS-1A(S)的工业应用", 《石化技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773440A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Pretreatment method for desulphurization adsorbents and desulphurization method for sulfur-containing hydrocarbon raw materials |
| CN103773440B (en) * | 2012-10-24 | 2016-01-13 | 中国石油化工股份有限公司 | The sulfur method of the pretreatment process of desulfuration adsorbent and the hydrocarbon feed of sulfur-bearing |
| CN107660268A (en) * | 2015-05-12 | 2018-02-02 | 国际壳牌研究有限公司 | Method including analyzing streaming flow |
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| CN101987970B (en) | 2014-08-20 |
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