CN101987970B - Method for removing mercaptan from gasoline - Google Patents
Method for removing mercaptan from gasoline Download PDFInfo
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- CN101987970B CN101987970B CN200910157466.1A CN200910157466A CN101987970B CN 101987970 B CN101987970 B CN 101987970B CN 200910157466 A CN200910157466 A CN 200910157466A CN 101987970 B CN101987970 B CN 101987970B
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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 the method for refining hydrocarbon ils in a kind of situation that does not have hydrogen.More particularly, be a kind of in the situation that not there is not hydrogen, remove the method for mercaptan from gasoline production 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 as sulphur content, vapour pressure, benzene content, aromatic hydrocarbons total content, olefin(e) centent, wherein particularly harsh to the restriction of the sulphur content in gasoline.China plans on December 31st, 2009 motor spirit quality upgrading, to state III standard, to require content of sulfur in gasoline to be not more than 150 μ g/g.Beijing has taken the lead in coming into effect state IV emission standard in 2008, requires content of sulfur in gasoline to be further reduced to below 50 μ g/g.
Catalytically cracked gasoline is the main gasoline component of refinery, accounts for the more than 70% of gasoline harmonic proportion.Catalytic gasoline contains a large amount of alkene and sulfide.The sulfide removing in catalytically cracked gasoline is the key that meets clean gasoline new standard.
Sulfide in gasoline comprises that thio-alcohol, multiple sulfides, heterocycle are sulfide-based as thiophene and homologue and analogue.A thio-alcohol part in gasoline be small molecules mercaptan as methyl mercaptan, ethanethio, propyl group mercaptan etc., these small molecules, lower boiling mercaptan can be removed by the method for alkali extracting.In gasoline, also exist some high boiling points, macromolecular mercaptan as butyl sulfhydryl, pentan-thiol, hexylmercaptan etc.These macromole, high boiling point mercaptan stable in properties, cannot remove by alkali extracting, generally adopts catalytic oxidation technique to convert it into disulphide and be present in product, and do not reduce the total sulfur content of product.
Conventionally adopt the method for hydrogenation can remove macromole mercaptan and the other types sulfide in gasoline, reduce the sulphur content in gasoline.
CN1478866A discloses a kind of method of gasoline desulfur.Gasoline stocks is cut into light gasoline fraction, heavy naphtha by the method; 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 described Hydrobon catalyst and described hydrogenating desulfurization alcohol catalyst are the group vib or the VIII family non-precious metal catalyst that load in unformed aluminum oxide or silica-alumina supports.The method energy production sulphur content is 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.The method comprises that gasoline stocks carries out selective hydrodesulfurization reaction under catalyst for selectively hydrodesulfurizing exists, reaction product contacts with hydrogenating desulfurization alcohol catalyst, after reaction, obtain low-sulphur oil product, 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%.The method can be processed the full distillation gasoline of poor quality of high-sulfur, high alkene content, and flow process is simple, easy to operate, and not only total sulfur content is lower than 50 μ g/g for gained gasoline products, 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 hydrodesulfurization reaction process, H in reactant flow
2s content constantly increases, and can make alkene and hydrogen sulfide reaction in gasoline generate new mercaptan sulfur, and these mercaptan are also mainly C
5above macromole mercaptan.
US6416658B1 proposes a kind of naphtha desulfurization method, petroleum naphtha is carried out to hydrogenating desulfurization simultaneously and is separated into light boiling range petroleum naphtha and heavy boiling range petroleum naphtha, by making light boiling range petroleum naphtha further contact with hydrogen with reflux type, remove the regeneration mercaptan that hydrodesulfurization process generates subsequently in hydrogenating desulfurization fixed bed.
Although adopt countercurrent hydrogenation desulfurization can avoid new mercaptan to generate, because the olefin(e) centent in gasoline is higher, in hydro-sweetening process, still have part olefin saturated, cause product loss of octane number.
Summary of the invention
The object of the invention is on the basis of existing technology, provide a kind of and remove mercaptan from gasoline sulphur under non-hydrogen state, reduce the method for gasoline total sulfur content simultaneously.
A kind of method that removes mercaptan from gasoline 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 loading in reactor, the mercaptan decomposition in raw material is alkene and hydrogen sulfide, and reactor bottom is introduced stripping medium, stripping medium and gasoline counter current contact, the hydrogen sulfide of generation is shifted out to reaction zone in time, 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 method provided by the invention, described raw material comprises that boiling range is the gasoline fraction of 10 DEG C-230 DEG C, for example, in catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline and the pressure gasoline mixture of one or more.Preferably boiling range is the gasoline fraction containing alkene of 40 DEG C-230 DEG C, and olefin(e) centent is at least 5wt%.
In method provided by the invention, operation condition is: temperature of reaction is 150～350 DEG C, preferably 210～260 DEG C, and pressure is 0.2MPa～6MPa, preferred 0.4～2.5MPa, and when feeding liquid, volume space velocity is 2～15h
-1, preferred 4～10h
-1, charging stripping medium and stock oil volume ratio are 5-200 (under standard state), preferably 5～200.
In method provided by the invention, described stripping medium can be under operational condition not the rare gas element reacting with raw material, can ensure that other reactions can not occur gasoline stocks in mercaptan removal as saturated in the hydrogenation of alkene.Typical stripping medium comprises nitrogen, carbonic acid gas, carbon monoxide, methane, hydro carbons or water vapour.Preferred nitrogen is as stripping medium.
In method provided by the invention, described reactor can be various forms, comprises fixed bed, fluidized-bed, ebullated bed etc., and gasoline fraction and stripping medium can contact catalyst surface is reverse in reactor, H that will reaction generation
2s shifts out beds in time, and is taken out of reactor by stripping medium.Preferred reactor types is fixed-bed reactor.
In method provided by the invention, described catalytic desulfurization alcohol catalyst is VIB or the VIII family non-precious metal catalyst loading in amorphous alumina or silica-alumina supports.Preferred catalyzer is Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and the cobalt oxide loading on alumina supporter, taking total catalyst weight as benchmark, in described mercaptan-eliminating catalyst, the content of Tungsten oxide 99.999 and/or molybdenum oxide is 4-10wt%, 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 sulphided state catalyzer, preferably adopts oxidized catalyst.The structure of catalyzer and size can ensure gas-liquid two-phase counter-current operation in reactor.
Brief description of the drawings
Accompanying drawing is the schematic flow sheet of method provided by the invention.
Embodiment
The following examples will be further described method provided by the invention, but therefore not limit the present invention.
Describing with reference to the accompanying drawings method provided by the invention below in detail, is alkene and hydrogen sulfide but therefore the present invention is not subject to limitting catalytic decomposition.Inertia stripping medium is introduced from reactor bottom by pipeline 3, and the hydrogen sulfide that the stripping medium of rising produces reaction in time shifts out beds 2, mercaptan decomposition balance is moved, the mercaptan decomposition in 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 after hydrogen sulfide; Gasoline products after 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, in reactor, gasoline contacts with stripping medium counter flow, and because hydrogen sulfide is removed in the stripping effect of stripping medium, reaction is moved to being conducive to mercaptan decomposition direction, can remove the most of mercaptan in gasoline.For olefine contained gasoline, due to catalytic decomposition mercaptan under the condition not there is not hydrogen, can avoid causing product loss of octane number because of olefins hydrogenation.Method provided by the invention can be produced mercaptan sulfur content lower than 3 μ g/g gasoline products, and gasoline products total sulfur content reduces simultaneously, there is no loss of octane number.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Catalyzer used in embodiment and comparative example is produced by Sinopec catalyzer Chang Ling branch office, and trade names are RSS-1A, and its chief component is, in total catalyst weight, and the NiO that contains 4.5wt%, the WO of 14.5wt%
3al with surplus
2o
3.
Comparative example
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.Taking catalytically cracked gasoline A as raw material, first through caustic wash desulfuration alcohol, the gasoline products character after mercaptan removal is in table 1.From table 1, the product mercaptans content after alkali cleaning is 25 μ g/g, illustrates that the mercaptan in raw material is macromole mercaptan, cannot be by conventional catalytic oxidation desulfurization alcohol art breading.Loading catalyst RSS-1A in fixed-bed reactor, be shaped as trifolium-shaped, diameter is 1.3mm, gasoline fraction after caustic wash desulfuration alcohol and hydrogen pass through fixed-bed reactor under also flowing to, contact and carry out hydro-sweetening reaction with RSS-1A catalyzer, reaction pressure is 1.6Mpa, and temperature is 240 DEG C, hydrogen-oil ratio is 50, and feed volume air speed is 5h
-1.Obtain gasoline products after hydro-sweetening, character is in table 1.
Embodiment 1
The Raschig ring RSS-1A catalyzer that in fixed-bed reactor, filling diameter is 2mm.Taking catalytically cracked gasoline A as raw material, be directly 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 the condition of 200 DEG C, and charging matter volume space velocity is 5h
-1, feeding gas/oil volume ratio is 25 (mark states), and reactor bottom is drawn gasoline products after mercaptan removal, and character is in table 1.
Embodiment 2
In stripping tower, the Raschig ring RSS-1A catalyzer of filling diameter 3mm, taking catalytically cracked gasoline A as raw material, is directly introduced into stripping tower top, N without alkali cleaning
2gas is introduced from stripping tower bottom, and the steam producing with tower reactor reboiler upwards passes through beds.Stripping tower overhead vapours is after condensation, and liquid phase all refluxes, non-condensable gas N
2discharge, the gasoline fraction after mercaptan removal is discharged at the bottom of tower.Stripping tower working pressure is 2.4MPa, and beds medial temperature is 260 DEG C, and feed volume air speed is 8h
-1, charging N
2gas/oil volume ratio is 5 (mark states), and after mercaptan removal, gasoline products character is in table 1.
Table 1
As can be seen from Table 1, embodiment 1 is compared with comparative example, 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 is compared with comparative example, 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.Visible employing method provided by the invention, can remove the mercaptan in gasoline, reduces gasoline products total sulfur content, and octane value does not lose substantially.
Claims (9)
1. removing a method for mercaptan from gasoline sulphur, it is characterized in that raw material introduced by reactor top, from top to bottom flow through reactor, is 150～350 DEG C in temperature of reaction, and pressure is 0.2～6MPa, and when feeding liquid, volume space velocity is 2～15h
-1charging gas-oil ratio is to contact with the mercaptan-eliminating catalyst loading in reactor under 5～200 condition, mercaptan decomposition in raw material is alkene and hydrogen sulfide, reactor bottom is introduced stripping medium, stripping medium and gasoline counter current contact, shift out reaction zone in time by the hydrogen sulfide of generation, and 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; Described mercaptan-eliminating catalyst is VIB and/or the VIII family non-precious metal catalyst loading in aluminum oxide or silica-alumina supports.
2. according to the method for claim 1, its feature is done condition at described operation and is: temperature is 180～260 DEG C, and reaction pressure is 0.4～2.5MPa, and when feeding liquid, volume space velocity is 4～10h
-1, charging gas-oil ratio is under 5～200 standard state.
3. according to the method for claim 1, it is characterized in that in described mercaptan-eliminating catalyst, the metal component loading on carrier contains Tungsten oxide 99.999 and/or molybdenum oxide, and nickel oxide.
4. according to the method for claim 3, it is characterized in that described mercaptan-eliminating catalyst is Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and the cobalt oxide loading on alumina supporter, taking total catalyst weight as benchmark, in described mercaptan-eliminating catalyst, the content of Tungsten oxide 99.999 and/or molybdenum oxide is 4～15wt%, nickel oxide content is 1～5wt%, and cobalt oxide content is 0.01～1wt%.
5. according to the method for claim 1, it is characterized in that described raw material is that boiling range is the petroleum hydrocarbon cut of 10 DEG C～230 DEG C.
6. according to the method for claim 5, it is characterized in that described raw material is that boiling range is 50～230 DEG C, at least contain the petroleum hydrocarbon fraction of 5wt% alkene.
7. according to the method for claim 6, 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 pressure gasoline.
8. according to the method for claim 1, described stripping medium is nitrogen, carbonic acid gas, carbon monoxide, lighter hydrocarbons or water vapor.
9. 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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| 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 |
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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 |
| CN1048916C (en) * | 1995-08-16 | 2000-02-02 | 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 |
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| 赵素芬，等.预硫化催化剂RSS-1A(S)的工业应用.《石化技术》.2008,第15卷(第3期),29-33. * |
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