CN101987970A - Method for removing mercaptan from gasoline - Google Patents

Abstract

Translated fromChinese

一种脱除汽油中硫醇的方法，原料由反应器上部引入，由上而下流过反应器，在一定的操作条件下和反应器中装填的脱硫醇催化剂接触，原料中的硫醇分解为烯烃和硫化氢气体，反应器底部引入汽提介质，汽提介质与汽油逆流接触，将生成的硫化氢气体及时移出反应区，含有硫化氢的汽提介质由反应器上部排出，反应器底部引出脱除了硫醇的汽油产品，所述的汽提介质为惰性气体和/或蒸汽。采用本发明提供的方法能生产硫醇硫含量低于3μg/g汽油产品，同时汽油产品总硫含量降低，没有辛烷值损失。

A method for removing mercaptans in gasoline. The raw material is introduced from the upper part of the reactor, flows through the reactor from top to bottom, and contacts with the sweetening catalyst packed in the reactor under certain operating conditions. The mercaptans in the raw materials are decomposed into Olefin and hydrogen sulfide gas, the stripping medium is introduced into the bottom of the reactor, and the stripping medium is in countercurrent contact with gasoline, and the generated hydrogen sulfide gas is removed from the reaction area in time, the stripping medium containing hydrogen sulfide is discharged from the upper part of the reactor, and the bottom of the reactor is drawn For the gasoline product from which mercaptan has been removed, the stripping medium is inert gas and/or steam. The method provided by the invention can produce gasoline products with mercaptan sulfur content lower than 3 μg/g, meanwhile, the total sulfur content of gasoline products is reduced without octane number loss.

Description

A kind of method that removes sulfur in gasoline alcohol

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 flow₂S content constantly increases, and can make alkene and hydrogen sulfide reaction in the gasoline generate new mercaptan sulfur, and these mercaptan mainly also are C₅Above 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 generation₂S 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 bypipeline 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 throughpipeline 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 surplus₂O₃

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 cleaning₂Gas 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 cleaning₂Gas 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 N₂Discharge, 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 N₂Gas/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)

Translated fromChinese

1.一种脱除汽油中硫醇硫的方法，其特征在于原料由反应器上部引入，由上而下流过反应器，在一定的操作条件下和反应器中装填的脱硫醇催化剂接触，原料中的硫醇分解为烯烃和硫化氢气体，反应器底部引入汽提介质，汽提介质与汽油逆流接触，将生成的硫化氢气体及时移出反应区，含有硫化氢的汽提介质由反应器上部排出，反应器底部引出脱除了硫醇的汽油产品，所述的汽提介质为惰性气体和/或蒸汽。1. A method for removing mercaptan sulfur in gasoline is characterized in that the raw material is introduced from the top of the reactor, flows through the reactor from top to bottom, and contacts with the sweetening catalyst packed in the reactor under certain operating conditions, and the raw material The mercaptan in the reaction zone is decomposed into olefins and hydrogen sulfide gas. The stripping medium is introduced into the bottom of the reactor, and the stripping medium is in countercurrent contact with gasoline, and the generated hydrogen sulfide gas is removed from the reaction zone in time. The stripping medium containing hydrogen sulfide is discharged from the upper part of the reactor. The gasoline product from which mercaptans have been removed is drawn from the bottom of the reactor, and the stripping medium is inert gas and/or steam.2.按照权利要求1的方法，其特征在于所述的反应操作条件为：反应温度为150～350℃，压力为0.2～6MPa，进料液时体积空速为2～15h^-1，进料气油体积比为5～200(标准状态下)。2. The method according to claim 1, characterized in that the operating conditions of the reaction are as follows: the reaction temperature is 150-350°C, the pressure is 0.2-6MPa, the volumetric space velocity of the feed liquid is 2-15h^-1 , the feed liquid The gas-oil volume ratio is 5-200 (under standard conditions).3.按照权利要求2的方法，其特征在所述的反应操作做条件为：温度为180～260℃，反应压力为0.4～2.5MPa。进料液时体积空速为4～10h^-1，进料气油体积比为5～200(标准状态下)。3. according to the method for claim 2, it is characterized in that described reaction operation does condition as: temperature is 180～260 ℃, and reaction pressure is 0.4～2.5MPa. The volumetric space velocity of the feed liquid is 4-10h^-1 , and the feed gas-oil volume ratio is 5-200 (under standard conditions).4.按照权利要求1的方法，其特征在于所述的脱硫醇催化剂为负载在氧化铝或硅铝载体上的VIB和/或VIII族非贵金属催化剂。4. according to the method for claim 1, it is characterized in that described sweetening catalyst is the VIB and/or group VIII non-noble metal catalyst supported on alumina or silica-alumina carrier.5.按照权利要求4的方法，其特征在于所述的脱硫醇催化剂中，负载在载体上的金属组分含有氧化钨和/或氧化钼，和氧化镍。5. The method according to claim 4, characterized in that in the sweetening catalyst, the metal component loaded on the carrier contains tungsten oxide and/or molybdenum oxide, and nickel oxide.6.按照权利要求5的方法，其特征在于所述的脱硫醇催化剂为负载在氧化铝载体上的氧化钨和/或氧化钼、氧化镍和氧化钴，以催化剂总重量为基准，所述的脱硫醇催化剂中氧化钨和/或氧化钼的含量为4～15wt％，氧化镍含量为1～5wt％，氧化钴含量为0.01～1wt％。6. according to the method for claim 5, it is characterized in that described sweetening catalyst is tungsten oxide and/or molybdenum oxide, nickel oxide and cobalt oxide that are loaded on the alumina support, take catalyst gross weight as benchmark, described The content of tungsten oxide and/or molybdenum oxide in the sweetening catalyst is 4-15 wt%, the content of nickel oxide is 1-5 wt%, and the content of cobalt oxide is 0.01-1 wt%.7.按照权利要求1的方法，其特征在于所述的原料为馏程为10℃～230℃的石油烃馏分。7. according to the method for claim 1, it is characterized in that described raw material is the petroleum hydrocarbon fraction that distillation range is 10 ℃～230 ℃.8.按照权利要求7的方法，其特征在于所述的原料为馏程为50～230℃，至少含有5wt％烯烃的石油烃馏份。8. according to the method for claim 7, it is characterized in that described raw material is the petroleum hydrocarbon fraction that distillation range is 50～230 ℃, contains at least 5wt% olefin.9.按照权利要求8的方法，其特征在于所述的原料为催化裂化汽油、催化裂解汽油、焦化汽油、裂解汽油和热裂化汽油中的一种或几种的混合物。9. according to the method for claim 8, it is characterized in that described raw material is the mixture of one or more in catalytic cracking gasoline, catalytic cracking gasoline, coker gasoline, pyrolysis gasoline and thermal cracking gasoline.10.按照权利要求1的方法，所述的汽提介质为氮气、二氧化碳、一氧化碳、轻烃或水蒸汽。10. according to the method for claim 1, described stripping medium is nitrogen, carbon dioxide, carbon monoxide, light hydrocarbon or steam.11.按照权利要求1的方法，所述的反应器为固定床反应器、流化床反应器、蒸馏塔反应器或沸腾床反应器。11. The method according to claim 1, wherein said reactor is a fixed bed reactor, a fluidized bed reactor, a distillation column reactor or an ebullated bed reactor.

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