CN108018083B

CN108018083B - Method for deep desulfurization of gasoline and equipment for deep desulfurization of gasoline

Info

Publication number: CN108018083B
Application number: CN201610971963.5A
Authority: CN
Inventors: 潘光成; 赵杰; 赵丽萍; 习远兵; 唐文成; 褚阳; 常春艳; 李涛; 吴明清; 陶志平; 李明丰; 田龙胜; 胡志海
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-28
Filing date: 2016-10-28
Publication date: 2020-09-18
Anticipated expiration: 2036-10-28
Also published as: CN108018083A

Abstract

The invention relates to the field of refining of hydrocarbon materials, and discloses a method for deep desulfurization of gasoline and equipment for deep desulfurization of gasoline, wherein the method comprises the following steps: (1) fractionating a gasoline feedstock to obtain a light fraction and a heavy fraction; (2) in the presence of an oxidation deodorization catalyst, contacting the light fraction with an oxidant to obtain an oxidation-deodorized light fraction; (3) contacting the oxidized and deodorized light fraction with an extraction solvent to obtain a sulfur-containing solvent and a solvent-extracted light fraction, and then separating the sulfur-containing solvent from sulfides contained in the sulfur-containing solvent; (4) contacting the heavy fraction with a hydrodesulfurization catalyst to perform a selective hydrodesulfurization reaction to obtain a hydrogenated heavy fraction; (5) and (3) mixing the hydrogenated heavy fraction in the step (4) with the solvent-extracted light fraction in the step (3) to obtain a gasoline product. The method provided by the invention can obtain a gasoline product with lower sulfur on the premise of avoiding larger loss of octane number.

Description

Method for deep desulfurization of gasoline and equipment for deep desulfurization of gasoline

Technical Field

The invention relates to the field of refining of hydrocarbon materials, in particular to a gasoline deep desulfurization method and equipment for gasoline deep desulfurization, and more particularly relates to a deep desulfurization process for sulfur-containing gasoline by combining a hydrogenation mode and a non-hydrogenation mode.

Background

As is well known, the emission of toxic and harmful substances in automobile exhaust seriously affects the air quality, and therefore, increasingly strict standards are defined in all countries in the world for the quality of oil products as engine fuels. China has implemented No. IV emission standard nationwide from 1 month and 1 day in 2013, and has implemented No. V emission standard in big cities such as Beijing, Shanghai, and the like. Emission standards IV and V respectively stipulate that the sulfur content of the motor gasoline is not more than 50 mu g/g and 10 mu g/g.

The sulfur in gasoline mainly comes from catalytic cracking gasoline, and the sulfur content of the catalytic cracking gasoline is further increased along with the development of oil processing raw materials to the heavy state. Therefore, reducing the sulfur content of catalytically cracked gasoline is the key to reducing the sulfur content of finished gasoline.

The sulfur in gasoline mainly comprises thiols, thioethers, dithioethers and thiophenes (including thiophene and thiophene derivatives). The maximum limit of the mercaptan sulfur content and the total sulfur content of a gasoline standard as a fuel is specified. When the sulfur content of mercaptan exceeds the standard or the total sulfur content exceeds the standard, the gasoline must be subjected to mercaptan removal or desulfurization refining.

As the catalytic cracking gasoline used as the blending component of the gasoline pool for the automobile is rich in olefin, the octane number loss is easily caused by the saturation of the olefin by adopting the conventional hydrogenation mode. In order to avoid the great loss of octane number in the processing process, the catalytic cracking gasoline is usually desulfurized and refined by adopting a sectional treatment mode.

US3957625 reports a process for the desulfurization of gasoline. The method is characterized in that gasoline is cut into a light part and a heavy part, and the sulfur content in the gasoline is reduced by carrying out selective hydrogenation treatment on heavy gasoline fraction. And US6610197 reports a process for the desulfurization of gasoline by cutting the gasoline into a light fraction and a heavy fraction, subjecting the light fraction to non-hydrotreating, and subjecting the heavy fraction to hydrotreating, thereby reducing the sulfur content in the gasoline.

US6623627 reports a process for the production of low sulphur gasoline by cutting gasoline into three fractions of low, medium and high boiling point, in which the low boiling point fraction containing mercaptans is contacted with alkali liquor to selectively remove mercaptans, the medium boiling point fraction containing thiophenes is desulfurized by extraction, the extraction liquid containing thiophenes of the medium boiling point fraction and the high boiling point fraction are subjected to a desulfurization reaction in a hydrodesulfurization zone, and then the light, medium and heavy fractions after the respective treatments are mixed to obtain a gasoline product with reduced sulphur content. The contact of the low boiling point fraction and the alkali liquor is carried out by adopting an alkali liquor extraction mode, the alkali liquor is oxidized and regenerated after mercaptan is extracted, and disulfide generated in the oxidation process is separated by a sedimentation mode and then recycled. However, this prior art does not disclose a process for the solvent extraction of the medium-boiling fractions containing thiophene.

CN102851069A reports a method for desulphurizing gasoline, which comprises cutting gasoline into heavy fraction with relatively high boiling range and light fraction with relatively low boiling range; under the condition of selective hydrodesulfurization, contacting the heavy fraction and hydrogen with a hydrodesulfurization catalyst to perform selective hydrodesulfurization to obtain desulfurized heavy fraction; contacting the light fraction with alkali liquor to desulfurize the light fraction, contacting the obtained alkali liquor and oxidant which absorb sulfide with oxidation catalyst and a part of the desulfurized heavy fraction, and simultaneously performing alkali liquor regeneration and alkali liquor desulfurization to oxidize the sulfide salt in the alkali liquor into disulfide, simultaneously extracting the disulfide in the alkali liquor into the desulfurized heavy fraction, then performing phase separation, and discharging tail gas; returning at least a portion of said disulfide-absorbed heavy fraction obtained to said selective hydrodesulfurization; and mixing the desulfurized heavy fraction with the desulfurized light fraction to obtain a product.

CN103555359A discloses a deep desulfurization method for catalytically cracked gasoline, which also removes sulfides in gasoline fractions by means of solvent extraction. The solvent extraction part adopts a liquid-liquid extraction desulfurization mode.

CN103740405A discloses an alkali washing-extraction-hydrogenation combined process for producing low-sulfur gasoline, which comprises the steps of cutting gasoline into light and heavy fractions, refining the light fraction with alkali, then carrying out extraction desulfurization, mixing the extracted sulfur-containing components with the heavy fraction for selective hydrogenation, and mixing the light fraction after extraction desulfurization and the heavy fraction after selective hydrogenation into a low-sulfur gasoline product. The alkali refining is carried out by adopting a simple alkali washing mode, and the alkali consumption is inevitably serious. The extraction desulfurization mode also adopts a liquid-liquid extraction mode.

In the above disclosed desulfurization method or process, the alkali treatment is aimed at removing mercaptans of relatively small molecular mass, such as mercaptans having a carbon number of not more than 4, from the gasoline fraction, and the solvent extraction is aimed at removing sulfides other than mercaptans, mainly thiophene compounds, from the gasoline fraction. When the mass fraction of the gasoline fraction subjected to the alkali treatment and the solvent treatment is increased and the mass fraction of the gasoline fraction subjected to the hydrotreatment is correspondingly decreased, the octane number loss caused by the hydrotreatment is undoubtedly relatively reduced. However, the conventional liquid-liquid solvent extraction generally has low desulfurization efficiency, absorbs more non-sulfide hydrocarbons, and needs to be washed and separated subsequently, and the separated sulfur-containing material also carries more impurities, which is not favorable for being sent into a hydrogenation device for treatment, and particularly, the recovered solvent is not completely regenerated, so that the sulfide extraction capacity is reduced when the solvent is recycled.

In order to obtain a gasoline product with lower sulfur and avoid a large loss of octane number, it is necessary to provide a new process which overcomes the aforementioned drawbacks of the prior art.

Disclosure of Invention

The object of the present invention is to overcome the drawbacks of the prior art and to provide a new process for the deep desulfurization of gasolines and a plant for use in this process, which allow to obtain a gasoline product with lower sulfur, while avoiding a greater loss of octane number.

The inventor of the invention finds that the removal efficiency of the extractive distillation phase on sulfide is higher than that of the conventional liquid-liquid extraction, and the absorption of the extraction solvent on olefin is less than that of the conventional liquid-liquid extraction in the extractive distillation process, so that on one hand, the extraction solvent is beneficial to more retaining olefin and reducing octane number loss caused by the olefin along with the sulfide extraction in the subsequent (merged into heavy fraction) hydrogenation treatment, on the other hand, the less olefin is dissolved in the extraction solvent, the harmful influence of oxidative polymerization and the like on the recycling of the solvent can be reduced, and the frequent regeneration of the extraction solvent due to the accumulation of harmful impurities can be avoided. It is found that small molecular weight mercaptan is difficult to be completely extracted by the extraction solvent, but after the low boiling point mercaptan is converted into high boiling point thioether disulfide, although the low boiling point mercaptan is still difficult to be removed by the conventional liquid-liquid extraction method, under the condition of extractive distillation, the high boiling point disulfide is easily separated from the gasoline fraction by the temperature difference between the upper part and the lower part of the distillation tower and is discharged together with the extraction solvent absorbing the thiophene sulfur to be removed. The inventors of the present invention have provided the following method for deep desulfurization of gasoline according to the present invention based on the aforementioned studies.

In order to achieve the above object, in a first aspect, the present invention provides a method for deep desulfurization of gasoline, comprising:

(1) fractionating a gasoline raw material at a cutting point temperature of 70-140 ℃ to obtain a light fraction and a heavy fraction;

(2) in the presence of an oxidation deodorization catalyst, contacting the light fraction with an oxidant to perform oxidation deodorization reaction to obtain an oxidation-deodorized light fraction;

(3) contacting the oxidized and deodorized light fraction with an extraction solvent to perform solvent extraction through distillation to obtain a sulfur-containing solvent and a solvent-extracted light fraction, and then separating the sulfur-containing solvent from sulfides contained in the sulfur-containing solvent through reduced pressure distillation to obtain a solvent-extracted sulfur-containing material and a recovered solvent from which the sulfides are removed;

(4) contacting the heavy fraction with a hydrodesulfurization catalyst to perform selective hydrodesulfurization reaction to obtain hydrogenated heavy fraction;

(5) and (3) mixing the hydrogenated heavy fraction in the step (4) with the solvent-extracted light fraction in the step (3) to obtain a gasoline product.

In a second aspect, the present invention provides an apparatus for deep desulfurization of gasoline, comprising:

a fractionation system through which the gasoline feedstock is fractionated to obtain a light fraction and a heavy fraction;

an oxidation deodorization system, which is used for carrying out oxidation deodorization reaction on the light fraction to obtain oxidized and deodorized light fraction;

the solvent extraction system comprises a solvent extraction distillation unit and a solvent recovery unit, wherein the solvent extraction distillation unit is used for carrying out solvent extraction on the oxidized and deodorized light fraction from the oxidation deodorization system to obtain a sulfur-containing solvent and the solvent-extracted light fraction; the solvent recovery unit is used for separating the sulfur-containing solvent from the sulfide contained in the sulfur-containing solvent to obtain a sulfur-containing material subjected to solvent extraction and a recovered solvent from which the sulfide is removed;

the selective hydrogenation system is used for introducing the heavy fraction from the fractionation system into the selective hydrogenation system through a pipeline to perform selective hydrodesulfurization reaction so as to obtain hydrogenated heavy fraction;

the hydrogenated heavy fraction is mixed with the solvent extracted light fraction and is led out as a gasoline product through a pipeline.

In order to obtain a gasoline product with lower sulfur and avoid great loss of octane number, the method flexibly applies non-hydrogenation modes such as oxidation deodorization, solvent extraction and the like while adopting a hydrogenation mode, so that the method provided by the invention can obtain the gasoline product with lower sulfur on the premise of avoiding great loss of the octane number.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a schematic structural diagram of a gasoline deep desulfurization apparatus according to a preferred embodiment of the present invention.

Description of the reference numerals

1. Gasoline raw material 2, fractionation system

3. Heavy fraction 4, light fraction

5. Oxidation deodorization system 6, light fraction after oxidation deodorization

7. Solvent extraction system 8, sulfur-containing material after solvent extraction

9. Light fraction 10 after solvent extraction and heavy fraction after hydrogenation

11. Etherification system 12, light ends after etherification

13. Selective hydrogenation system

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In a first aspect, the invention provides a method for deep desulfurization of gasoline, comprising the following steps:

The light fraction is a fraction with a relatively light distillation range, and the heavy fraction is a fraction with a relatively heavy distillation range. The light fraction of the invention concentrates most of the mercaptans and olefins in the gasoline feedstock, and the heavy fraction concentrates most of the other relatively high boiling sulfides, primarily thiophenes, in the gasoline feedstock.

The invention makes the light fraction after fractionation contact with oxidant in the presence of oxidation deodorization catalyst to carry out oxidation deodorization reaction to obtain the light fraction after oxidation deodorization, and mercaptan in the light fraction is oxidized into disulfide with relatively high boiling point.

It is known that mercaptans which are rich in the light fraction can be removed by means of lye extraction and that the sulphur content of the light fraction is reduced. However, lye extraction usually requires the use of large amounts of caustic lye, which results in the production of caustic sludge that is difficult to handle, while a back extraction operation is usually required to remove the disulfides converted from the mercaptides from the lye, which will produce a sulfur-containing material that requires additional handling. In order to overcome the technical defects brought by the alkali liquor extraction, the invention adopts an oxidation deodorization mode to treat the light fraction so as to convert mercaptan in the light fraction into disulfide. Due to the relatively high boiling point of the disulfide, it is easily removed in a subsequent solvent extractive distillation.

The following provides the oxidation deodorization step in a preferred case of the present invention:

according to the present invention, the light fraction is brought into contact with an oxidizing agent under the action of an oxidation deodorization catalyst for oxidation deodorization reaction, and the oxidation deodorization catalyst is an oxidation deodorization catalyst capable of oxidizing mercaptan into disulfide, and includes a metal phthalocyanine type catalyst, a metal salt (e.g., copper chloride salt) type catalyst, a metal oxide (e.g., iron oxide, manganese oxide, lead oxide, copper oxide, zinc oxide, etc.) catalyst, a copper molecular sieve or copper ion exchange resin catalyst, a perovskite type oxidation deodorization catalyst, various molecular sieve catalysts having an oxidizing function, an organic compound type catalyst having an oxidizing property, a heteropolyacid type oxidation deodorization catalyst, and the like. Preferably a metal phthalocyanine type catalyst, more preferably a supported metal phthalocyanine catalyst. The oxidant is oxygen, air, ozone, peroxide, or the like reactant capable of oxidizing the mercaptan to the disulfide, and more preferably, the oxidant is oxygen and/or air. The injection amount of the air is usually 1.0-10 times of the theoretical oxygen demand of the mercaptan removal reaction, and preferably 1.5-4 times.

Preferably, the conditions of the oxidative deodorization reaction include: the reaction temperature is 0-300 ℃, and preferably room temperature-200 ℃; the reaction pressure is 0.01MPa to 7.0MPa, preferably 0.1MPa to 2.0 MPa; the liquid hourly space velocity is 0.05-10 h^-1Preferably 0.5h^-1～5.0h^-1。

An activating agent can be added in the oxidation deodorization reaction, and the activating agent is an oxidation deodorization auxiliary agent capable of improving the efficiency of the oxidation deodorization reaction. The activating agent is an onium compound containing nitrogen, phosphorus, oxygen, sulfur, arsenic and antimony, more preferably a quaternary ammonium compound, and most preferably a quaternary ammonium base. Usually, the activator is dissolved in a solvent to participate in the oxidative deodorization reaction in the form of an activator solution. The solvent is one or more of water, alcohol and liquid hydrocarbon, and the alcohol is C_1-6Monohydric alcohol of (1), C_1-6The polyhydric alcohol of (3) is preferably methanol, ethanol or isopropanol.

Preferably, the supported metal phthalocyanine catalyst comprises a carrier and metal phthalocyanine supported on the carrier, wherein the carrier is a porous material, and the supported amount of the metal phthalocyanine is 0.05-10 wt%, preferably 0.1-5 wt%. The loading is based on the total amount of supported metal phthalocyanine catalyst.

Preferably, the metal phthalocyanine is selected from at least one of magnesium phthalocyanine, titanium phthalocyanine, hafnium phthalocyanine, vanadium phthalocyanine, tantalum phthalocyanine, molybdenum phthalocyanine, manganese phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, platinum phthalocyanine, palladium phthalocyanine, copper phthalocyanine, silver phthalocyanine, zinc phthalocyanine, and tin phthalocyanine; more preferably, the metal phthalocyanine is a cobalt phthalocyanine and/or a vanadium phthalocyanine. The phthalocyanine ring constituting the metal phthalocyanine may be monocyclic, bicyclic or polycyclic, and particularly, the phthalocyanine ring may have a substituent group bonded thereto, and the substituent group may be at least one selected from the group consisting of a sulfo group, a carboxyl group, an amide group, an acid halide group, a quaternary ammonium compound, an onium compound, a halogen, and the like. The cobalt phthalocyanine is preferably a cobalt phthalocyanine sulfonate comprising cobalt phthalocyanine sulfonic acid, i.e. sulfonated cobalt phthalocyanine, and a cobalt phthalocyanine sulfonate comprising a mixture of one or more of a mono-sulfonic acid of cobalt phthalocyanine (mono-sulfonated cobalt phthalocyanine), a bis-sulfonic acid of cobalt phthalocyanine (bis-sulfonated cobalt phthalocyanine), a tri-sulfonic acid of cobalt phthalocyanine (tri-sulfonated cobalt phthalocyanine) and a tetra-sulfonic acid of cobalt phthalocyanine (tetra-sulfonated cobalt phthalocyanine), and/or a cobalt phthalocyanine carboxylate comprising cobalt phthalocyanine carboxylic acid, a cobalt phthalocyanine carboxylate, preferably a bicyclic cobalt phthalocyanine having a carboxylic acid group as a substituent.

The porous material as the carrier of the supported metal phthalocyanine catalyst is preferably selected from at least one of materials containing aluminum, silicon, alkaline earth metal, transition metal, rare earth metal and carbonaceous material, for example, one or more selected from alumina, silica, aluminosilicate, calcium oxide, magnesium oxide, titanium oxide, natural and artificial clay, natural and artificial zeolite, carbonaceous material derived from mineral material (such as coal and petroleum), plant material (such as wood chips, fruit shells and kernels) and synthetic resin, and the carrier of the supported metal phthalocyanine catalyst is preferably activated carbon. More preferably, it isThe specific surface area of the porous material as the carrier is 10 to 1500m²Preferably 100 to 1200 m/g²/g。

The preparation of the supported metal phthalocyanine catalyst according to the present invention is well known to those skilled in the art and can be carried out, for example, in a manner known in the literature by impregnating a solution of the metal phthalocyanine into the porous support and drying it.

According to the invention, it is preferred that the light ends after oxidative deodorization are substantially free of oxygen or air.

The solvent extraction in a preferred case in connection with the present invention is provided below:

and the solvent extraction is used for transferring sulfide mainly containing thiophene in the oxidized and deodorized light fraction into the extraction solvent to form a sulfur-containing solvent.

Preferably, the solvent extraction is carried out in an extractive distillation tower, the oxidized and deodorized light fraction enters the extractive distillation tower from the middle part of the extractive distillation tower, the extraction solvent enters the extractive distillation tower from the upper part of the extractive distillation tower, and under the selective action of the solvent, thiophene and thioether compounds with relatively high boiling points in the oxidized and deodorized light fraction enter the bottom of the extractive distillation tower along with the extraction solvent. And part of the low-sulfur light fraction distilled from the top of the extractive distillation tower is refluxed and circulated at the top of the tower, and part of the low-sulfur light fraction is discharged outside to be the light fraction extracted by the solvent. And a part of the sulfur-rich solvent at the bottom of the extractive distillation tower circulates at the bottom of the tower, and a part of the sulfur-rich solvent is discharged to a solvent recovery unit for treatment.

The weight ratio of the extraction solvent to the oxidized and deodorized light fraction is (0.5-20): 1, more preferably (1-5): 1. the inventor finds that in the liquid-liquid extraction mode, the sulfur-containing solvent absorbs sulfur in the light fraction and also absorbs other components much more than the sulfur, so that the problems of a solvent recovery system in a distillation mode are brought, such as increased energy consumption, more residual components in the recovered solvent, and rapid reduction of solvent extraction capacity caused by returning to the solvent extraction system. In the solvent extraction distillation desulfurization mode, the extraction solvent absorbs fewer components of the material to be treated, and the extraction capacity of the recovered solvent can be effectively recovered.

Preferably, the solvent extraction is carried out in an extractive distillation column, the conditions in the extractive distillation column comprising: the pressure at the top of the column is 100kPa to 500kPa, preferably 110kPa to 300 kPa; the temperature of the tower top is 65-180 ℃; the temperature of the tower bottom is 80-260 ℃, and preferably 140-200 ℃.

Preferably, the sulfur content in the light fraction obtained after solvent extraction is not more than 10 mu g/g.

Preferably, the extraction solvent contains a main extraction solvent, and the boiling point of the main extraction solvent is 175-320 ℃, and more preferably 175-250 ℃.

Preferably, the primary extraction solvent is selected from sulfolane, 3-methylsulfolane, 2, 4-dimethylsulfolane, 3-ethylsulfolane, methylethylsulfone, dimethylsulfone, diethylsulfone, dipropylsulfone, dibutylsulfone, dimethylsulfoxide, furfural, furfuryl alcohol, α -pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, at least one of N-propyl-2-pyrrolidone, N-formyl morpholine, dimethylformamide, triethylene glycol, tetraethylene glycol, pentaethylene glycol, triethylene glycol methyl ether, tetraethylene glycol methyl ether, ethylene carbonate, propylene carbonate, acetonitrile, nitrobenzene, polyethylene glycol having a relative molecular mass of 200 to 400, and polyethylene glycol methyl ether having a relative molecular mass of 200 to 400; more preferably, the main extraction solvent is selected from at least one of sulfolane, N-formyl morpholine, N-methyl-2-pyrrolidone, tetraethylene glycol and pentaethylene glycol.

In the solvent extraction distillation tower, both gas phase and liquid phase exist, the liquid phase is a single liquid phase, namely, in the liquid phase interval, the solvent of the liquid phase and the light fraction of the liquid phase are in a dissolved state, so that the sulfide in the light fraction is favorably transferred into the extraction solvent, and once a multi-liquid phase state is formed, the extraction of the sulfide is not favorably realized. In order to improve the sulfide absorption capacity of the extraction solvent and help the liquid phase region of the extractive distillation column to maintain a single liquid phase, it is preferable that the extraction solvent further contains an auxiliary agent, wherein the auxiliary agent is at least one of alcohols, ketones, organic acids and organic nitrides, and/or water, which is miscible with the main extraction solvent and has a boiling point or a dry point not higher than that of the main extraction solvent, and the organic nitrides are at least one of amines, ureas and alcamines.

Preferably, the auxiliary agent is at least one of alcohols with the boiling point or the dry point not higher than that of the main extraction solvent and with the carbon number not more than 6, ketones with the carbon number not more than 6, organic acids with the carbon number not more than 6 and organic nitrides with the carbon number not more than 6, and/or water, wherein the organic nitrides are at least one of amines, ureas and alcohol amines.

Preferably, the alcohol having no more than 6 carbon atoms is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, n-pentanol, and cyclohexanol.

Preferably, the ketone having no more than 6 carbon atoms is acetone and/or methyl ethyl ketone.

Preferably, the organic acid with the carbon number not more than 6 is at least one of isobutyric acid, oxalic acid, malonic acid and succinic acid.

Preferably, the organic nitrogen compound having not more than 6 carbon atoms is selected from at least one of urea, ethylenediamine, monoethanolamine, N-methyl monoethanolamine, N-ethyl monoethanolamine, N-dimethylethanolamine, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, N-propanolamine, isopropanolamine, and diglycolamine.

More preferably, the auxiliary agent is selected from at least one of water, methanol, ethanol, N-propanol, isopropanol, acetone, methyl ethyl ketone, isobutyric acid, oxalic acid, malonic acid, succinic acid, urea, ethylenediamine, monoethanolamine, N-methyl monoethanolamine, N-ethyl monoethanolamine, N-dimethylethanolamine, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, N-propanolamine, isopropanolamine, and diglycolamine. Particularly preferably, the auxiliary agent is selected from at least one of water, methanol, acetone, methyl ethyl ketone, isobutyric acid, oxalic acid, malonic acid, succinic acid, ethylenediamine, monoethanolamine, N-methyl monoethanolamine, isopropanolamine and diglycolamine.

Preferably, in the extraction solvent, the content of the auxiliary agent is 0.1-20 wt%, and more preferably 0.5-15 wt%; particularly preferably, the content of the auxiliary agent is 1-10 wt%.

Preferably, the adjuvant is a mixture containing water. However, water greatly affects the formation of multiple phases, and when the water content in the solvent is large, a multiple phase state tends to be formed in the extractive distillation column. Therefore, when the auxiliary is a mixture containing water, the content of water in the extraction solvent is preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight.

Preferably, the extraction solvent contains a defoaming agent, and the defoaming agent is selected from at least one of siloxane compounds, alkyl sulfonate compounds, polyether compounds, polyethylene glycol compounds, polyester compounds, amide compounds and fatty alcohol compounds.

The following provides solvent recovery in relation to a preferred aspect of the invention:

the sulfur-containing solvent rich in sulfide can be recycled after the absorbed sulfide is removed, and the sulfide removal mode is called solvent recovery. The solvent recovery is carried out in a distillation mode, namely, a sulfur-containing solvent from the solvent extraction process is heated to evaporate a sulfur-containing material, the sulfur-containing material comprises aromatic hydrocarbon, thiophene and thioether compounds from light fractions, and the sulfur-containing material is discharged to be the sulfur-containing material after the solvent extraction. The solvent after the sulfide removal becomes a recovered solvent and returns to the solvent extraction distillation process for recycling.

Preferably, the solvent recovery is performed by vacuum distillation, and the conditions for separating the sulfur-containing solvent from the sulfide contained therein by vacuum distillation include: the pressure at the top of the solvent recovery tower is 10 kPa-100 kPa, the temperature at the top of the tower is 50-100 ℃, the temperature at the bottom of the tower is 100-250 ℃, more preferably the temperature at the bottom of the tower is 120-200 ℃, and the weight ratio of stripping steam to the sulfur-containing solvent is (0.01-5.0): 1.

the sulfur-containing hydrocarbon materials are removed from the recovered solvent, but side reactions such as oxidation and decomposition can occur during the operation process, so that some soluble high-boiling compounds such as stable salts, organic polymers, sediments and other impurities are formed, and the existence and accumulation of the substances in the solvent can undoubtedly reduce the dissolving capacity of the extraction solvent, thereby reducing the efficiency of gasoline extraction and desulfurization, so that the solvent needs to be regenerated, and the purity of the solvent is improved.

Preferably, the method further comprises: at least part of the recovered solvent is subjected to water injection purification treatment in a solvent regeneration tower for regeneration.

The following provides solvent regeneration in relation to a preferred aspect of the invention:

the water-injected purification treatment can be carried out by distilling the solvent under reduced pressure with water injected, wherein the residual hydrocarbon material of relatively light weight in the recovered solvent is azeotroped with water and discharged from the top of the column, the high boiling point compound impurity of relatively heavy weight in the recovered solvent is discharged as a residue from the bottom of the solvent regeneration column, and the purified solvent is discharged from the lower side of the solvent regeneration column to be used as the regenerated solvent. Preferably, the water in the water injection purification treatment is from condensed water collected in the solvent extraction distillation process and the solvent recovery process. The regenerated solvent can be directly returned to the solvent recovery tower or directly mixed with the recovered solvent flowing out of the solvent recovery tower for recycling.

Preferably, the regeneration conditions in the solvent regeneration column include: the pressure at the top of the tower is 1 kPa-10 kPa, the temperature at the top of the tower is 90-110 ℃, the temperature at the top of the tower is preferably 96-105 ℃, the temperature at the bottom of the tower is 120-200 ℃, the temperature at the bottom of the tower is preferably 150-200 ℃, and the weight ratio of the injected water to the recovered solvent is (0.1-10): 1, preferably the weight ratio of (0.5-5): 1.

preferably, the recovery solvent used for regeneration accounts for 1 to 10 wt% of the total recovery solvent, and more preferably accounts for 1 to 5 wt% of the total recovery solvent.

Preferably, the method of the present invention further comprises: before mixing with the hydrogenated heavy fraction obtained in the step (4), carrying out etherification reaction on the light fraction obtained in the step (3) after solvent extraction to obtain an etherified light fraction; and then mixing the etherified light fraction with the hydrogenated heavy fraction of step (4) to obtain the gasoline product.

The etherification reaction of the present invention allows the production of etherified light fractions with reduced olefin content and increased octane number.

The following provides the etherification reactions in the preferred case of the present invention:

preferably, the etherification reaction is carried out by contacting the light fraction after solvent extraction with a lower alcohol having no more than 6 carbon atoms.

Preferably, the lower alcohol used for the etherification reaction is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, n-pentanol and cyclohexanol; methanol is particularly preferred.

Preferably, the etherification reaction conditions include: the mol ratio of the low-carbon alcohol to the olefin in the light fraction after solvent extraction is (0.5-3): 1, preferably (1.0-1.2): 1, the contact temperature is 20-100 ℃, and the pressure is 0.3-2.0 MPa.

Preferably, the etherification reaction is carried out in the presence of an etherification catalyst which is a strongly acidic ion exchange resin. The strongly acidic ion exchange resin may be, for example, a sulfonic acid type ion exchange resin.

More preferably, the conditions under which the light fraction is contacted with the lower alcohol after the solvent extraction are such that the olefin removal rate in the light fraction after etherification is not less than 35%.

Preferably, the method of the present invention further comprises: before the etherification reaction, the light fraction after the solvent extraction is subjected to adsorption pretreatment and/or selective hydrogenation pretreatment.

In the invention, after the light fraction after oxidation and deodorization is extracted by a solvent, most sulfides are removed, and the selective hydrogenation pretreatment can be carried out under more moderate conditions, for example, a high-activity noble metal catalyst which is easily poisoned by sulfur can be adopted to carry out the pretreatment under the conditions of lower temperature, lower pressure and lower hydrogen-oil volume ratio so as to effectively avoid the loss of octane number caused by the hydrogenation of monoolefine.

Preferably, the selective hydrogenation pretreatment is carried out in the presence of a transition metal supported catalyst. The selective hydrogenation pretreatment catalyst used for selective hydrogenation pretreatment can be a hydrogenation or hydrogenation catalyst capable of saturating diolefins and avoiding mono-olefin saturation under certain reaction conditions, and the selective hydrogenation pretreatment catalyst comprises a transition metal supported catalyst, a non-noble metal supported catalyst, a noble metal supported catalyst or a combination of the two catalysts. The transition metal supported catalyst comprises a carrier and a metal active component supported on the carrier, wherein the carrier is selected from at least one of alumina, silicon oxide, aluminosilicate, titanium oxide, zeolite and activated carbon, and the metal active component is selected from at least one of nickel, cobalt, molybdenum, platinum and palladium.

According to a preferred embodiment, the carrier in the transition metal supported catalyst is alumina, and the loading amount of the metal active component in terms of oxide is 0.05-15 wt%.

Preferably, the conditions of the selective hydrogenation pretreatment include: the hydrogen partial pressure is 0.1MPa to 2.0MPa, the temperature is room temperature to 250 ℃, and the liquid hourly volume space velocity is 1.0h^-1～10.0h^-1The volume ratio of hydrogen to oil is 1-100.

According to another preferable condition, the light fraction after solvent extraction can also be subjected to adsorption pretreatment by adopting an adsorbent adsorption mode, so as to remove components harmful to the etherification catalyst in the light fraction after solvent extraction. The adsorbent is preferably an acidic porous molecular sieve material, and the adsorption can be carried out at normal temperature and pressure.

According to a preferred embodiment of the present invention, the method of the present invention further comprises: and (4) carrying out selective hydrodesulfurization reaction on the sulfur-containing material extracted by the solvent in the step (3) and the heavy fraction.

According to another preferred embodiment of the present invention, the method of the present invention further comprises: introducing the sulfur-containing material extracted by the solvent in the step (3) into a catalytic cracking device for catalytic cracking reaction to obtain at least part of the gasoline raw material used in the step (1).

The following provides a selective hydrodesulfurization reaction in a preferred case in connection with the present invention:

preferably, the selective hydrodesulfurization reaction is performed in a first reaction zone and a second reaction zone which are connected in sequence, a first hydrodesulfurization catalyst and a second hydrodesulfurization catalyst are respectively filled in the first reaction zone and the second reaction zone, the first hydrodesulfurization catalyst and the second hydrodesulfurization catalyst respectively and independently contain an alumina carrier and/or a silica-alumina carrier and a hydrogenation active metal component loaded on the carrier, and the hydrogenation active metal component is a non-noble metal element from group VIB of molybdenum and/or tungsten and/or a non-noble metal element from group VIII of nickel and/or cobalt.

Preferably, the first and second hydrodesulfurization catalysts each independently contain molybdenum and/or tungsten, nickel and/or cobalt, an alumina matrix, and a large pore zeolite and/or a medium pore zeolite.

Preferably, based on the total amount of the hydrodesulfurization catalyst, the content of the group VIB non-noble metal element calculated by oxides is 2 to 25 wt%, and the content of the group VIII non-noble metal element calculated by oxides is 0.2 to 6 wt%. The "hydrodesulfurization catalyst" here is the first hydrodesulfurization catalyst or the second hydrodesulfurization catalyst.

Preferably, the desulfurization activity of the first hydrodesulfurization catalyst is lower than the desulfurization activity of the second hydrodesulfurization catalyst. The desulfurization activity of the present invention is expressed by "the reaction temperature (T) per unit volume of the hydrodesulfurization catalyst when the same feedstock is treated to achieve the same desulfurization effect", and the greater the T, the lower the activity.

Preferably, the reaction conditions of the first reaction zone and the second reaction zone each independently comprise: the hydrogen partial pressure is 0.1MPa to 4.0MPa, the reaction temperature is 200 ℃ to 440 ℃, and the liquid hourly volume space velocity is 1.0h^-1～10.0h^-1The volume ratio of hydrogen to oil is 200-1000. More preferably, the reaction conditions of the first reaction zone and the second reaction zone each independently comprise: the hydrogen partial pressure is 1.0MPa to 3.2MPa, the reaction temperature is 200 ℃ to 300 ℃, and the liquid hourly volume space velocity is 2.0h^-1～6.0h^-1The volume ratio of hydrogen to oil is 200-600.

Preferably, the conditions of the selective hydrodesulfurization reaction are such that the sulfur content in the obtained hydrogenated heavy fraction is no more than 10 mu g/g.

Preferably, the cut points of the light fraction and the heavy fraction are 80-120 ℃.

Preferably, the dry point of the light fraction is not higher than the lower limit of the boiling range temperature range of the extraction solvent.

Preferably, the yield of the light fraction is 40-60 wt% and the yield of the heavy fraction is 40-60 wt% based on the gasoline raw material.

Preferably, the gasoline feedstock is selected from at least one of catalytically cracked gasoline, straight run gasoline, coker gasoline, pyrolysis gasoline, and thermally cracked gasoline.

Preferably, in step (5), the sulfur content of the obtained gasoline product is not more than 10 mu g/g. In particular, the gasoline product of step (5) of the present invention is a product obtained by mixing a heavy fraction after hydrogenation with a light fraction after solvent extraction, or a product obtained by mixing a heavy fraction after hydrogenation with a light fraction after etherification.

Preferably, the equipment further comprises an etherification system, and the light fraction after solvent extraction from the solvent extraction system is firstly introduced into the etherification system through a pipeline to carry out etherification reaction so as to obtain light fraction after etherification; and then mixing the etherified light fraction with the hydrogenated heavy fraction to be taken as a gasoline product to be led out through a pipeline.

According to a preferred aspect, the apparatus further comprises a line for introducing said solvent extracted sulfur-containing feed to a selective hydrogenation system.

According to another preferred aspect, the apparatus further comprises a cracking system, the sulfur-containing material extracted by the solvent from the solvent extraction system is introduced into the cracking system through a pipeline to perform catalytic cracking reaction, and the product in the cracking system is introduced into the fractionation system through a pipeline.

Preferably, the solvent extraction system further comprises a solvent regeneration unit, and the solvent regeneration unit is used for introducing the recovered solvent from the solvent recovery unit into the solvent regeneration unit through a pipeline for water injection purification treatment so as to regenerate.

Preferably, the selective hydrogenation system comprises a first reaction zone and a second reaction zone connected in series to perform the selective hydrodesulfurization reaction.

According to a preferred embodiment, the device for the deep desulfurization of gasoline according to the invention has a schematic structural diagram shown in fig. 1, in particular:

the gasoline raw material 1 enters a fractionation system 2 through a pipeline, and heavy fraction 3 and light fraction 4 are fractionated. The heavy fraction 3 flows out through a pipeline, is mixed with hydrogen to enter a selective hydrogenation system 13, is subjected to selective hydrogenation reaction under the action of a first hydrodesulfurization catalyst with relatively low activity in a first reaction zone, then enters a second reaction zone to be subjected to selective hydrogenation reaction under the action of a second hydrodesulfurization catalyst with relatively high activity, and flows out of the pipeline to obtain the hydrogenated heavy fraction 10. And (3) the light fraction 4 from the fractionation system 2 enters an oxidation deodorization system 5 through a pipeline, and is contacted with air under the action of a supported metal phthalocyanine catalyst, so that mercaptan in the light fraction is oxidized into disulfide, and an oxidation deodorized light fraction 6 is obtained.

The oxidized and deodorized light fraction 6 enters a solvent extraction system 7 to contact with an extraction solvent, and sulfides remaining in the light fraction are transferred to the extraction solvent to obtain a solvent-extracted light fraction 9, and preferably, the solvent-extracted light fraction 9 enters an etherification system 11 through a pipeline.

The sulfur-containing solvent absorbing the sulfide enters a solvent recovery unit for solvent recovery, the absorbed sulfide is separated from the extraction solvent under the distillation condition to obtain a sulfur-containing material 8 after solvent extraction, the sulfur-containing material 8 after solvent extraction and the heavy fraction 3 enter a selective hydrogenation system 13 together or are merged into a cracking system for cracking reaction, and the gasoline fraction obtained after cracking is used as a part of the gasoline raw material 1. Meanwhile, a part of the recovered solvent flows into a solvent regeneration unit to contact with water for purification and regeneration, the absorbed hydrocarbons (azeotropic with water) in the solvent, the heavy residual liquid rich in impurities and the regenerated solvent are separated, the regenerated solvent is merged into the recovered solvent, and the recovered solvent is continuously contacted with the light fraction after solvent extraction for recycling.

The light fraction 9 after the solvent extraction in the etherification system 11 is preferably subjected to pre-hydrogenation treatment, and is contacted with a lower alcohol after the treatment, so that the olefin in the light fraction reacts with the lower alcohol to generate ether, and the light fraction 12 after the etherification is obtained.

The hydrogenated heavy fraction 10 and the etherified light fraction 12 are mixed to form a gasoline product with low sulfur, low olefin and increased octane number; or the hydrogenated heavy fraction 10 and the solvent extracted light fraction 9 are mixed to form a gasoline product with low sulfur, low olefin and less octane number loss.

The gasoline deep desulfurization process provided by the invention has the following advantages:

the invention adopts a way of sectionalized treatment of sulfur-containing gasoline, and adopts treatment ways of oxidation deodorization, solvent extraction and selective hydrogenation respectively for gasoline of each sectionalized treatment.

In order to effectively reduce the sulfur content of gasoline fractions, the invention adopts an extraction solvent combination which has obvious selective absorption on sulfides on the basis of oxidation deodorization, and adopts an extraction distillation mode to extract and remove the sulfides in the gasoline fractions and a reduced pressure distillation mode to recover the extraction solvent, the light fraction after solvent extraction is completely separated from the extraction solvent (basically without entrainment) without subsequent treatment, the extraction solvent can be well separated from the absorbed sulfides and sulfur-containing materials during recovery, and a part of the recovered solvent is regenerated, thereby overcoming the defect of incomplete regeneration of the conventional solvent, not only separating residual hydrocarbon materials dissolved in the solvent through the azeotropic action with water, but also removing the high-boiling point polymers, sediments and other impurities accumulated in the solvent, having obvious purification effect during solvent regeneration, and effectively recovering the cyclic extraction capability after the recovered solvent is mixed with a part of the regenerated solvent And (5) repeating. The dry point of the light fraction can be properly increased due to the improvement of the desulfurization efficiency, so that the yield of the light fraction can be increased and the yield of the heavy fraction can be reduced during the gasoline fractionation, the treatment amount of the heavy fraction entering a hydrogenation system is reduced, and the octane number loss caused by the hydrogenation of the heavy fraction can be effectively reduced.

If the modes of liquid-liquid solvent extraction and positive pressure solvent distillation recovery are adopted, the solvent with higher selective absorption efficiency on the thiophene compounds generally has poor effect on the aspect of sulfur sulfide absorption, deep desulfurization is difficult to realize, extracted gasoline fractions often need subsequent treatment such as water washing and the like due to mutual entrainment, and the extracted solvent is difficult to completely recover due to relatively more absorbed materials, so that the effective use of the solvent is not facilitated.

The invention adopts oxidation deodorization to pre-treat the light fraction, can avoid the problem of caustic sludge treatment caused by adopting alkali liquor extraction, has relatively simple flow, and can be put into use after being slightly modified because a refinery is generally provided with a gasoline deodorization device.

In the present invention, solvent extraction produces a sulfur-rich feedstock. Under the conditions of the invention, the sulfur-rich materials can enter the step 2) for selective hydrodesulfurization reaction, and the influence on a hydrogenation system is small, and the great loss of octane number cannot be caused. At the same time, the sulfur-rich materials can be preferably combined into a catalytic cracking riser tube for cracking reaction, and the operation is more beneficial.

The gasoline desulfurization process provided by the invention has the following other remarkable advantages: the selective hydrodesulfurization system provided by the invention adopts two hydrogenation catalysts to be matched, and the catalytic hydrodesulfurization reaction is respectively carried out in the first reaction zone and the second reaction zone, so that a gasoline product with the sulfur content of not more than 10 mu g/g can be stably obtained, and the octane number loss is smaller.

In order to reduce the loss of octane number, the invention preferably configures a light fraction etherification step after the solvent extraction step, so that the olefin in the light fraction reacts with the lower alcohol to generate ether compounds with high octane number. Because most of sulfide and other heteroatom compounds in the light fraction are removed by solvent extraction, pretreatment before etherification can be carried out under mild conditions, and the operation cost is favorably reduced.

Compared with the conventional process containing conventional liquid-liquid extraction, the method of the invention has the advantage that the liquid yield of the obtained gasoline product is higher by adopting extraction distillation and matching with other process means. Moreover, in the prior art, the situation of oil carrying agent and carrier oil is easy to occur in the liquid-liquid extraction process, further treatment by water washing and the like is needed, and the liquid recovery loss is easy to cause.

In summary, the deep desulfurization process of the present invention is superior in terms of desulfurization effect, reduction of octane number loss, feasibility and stability of plant operation, and environmental protection effect, which cannot be compared with the prior art.

The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.

One of the selective hydrodesulfurization catalysts used below is a commercial RSDS-11 catalyst provided by catalyst division ChangLing catalyst works of petrochemical Co., Ltd.

Composition of another selective hydrodesulfurization catalyst Cat 1: the content of cobalt oxide was 4.3 wt%, the content of molybdenum oxide was 12.4 wt%, and the balance was an alumina carrier.

The composition of the selective hydrogenation pretreatment catalyst Cat2 used below was: 0.5 wt% Pd, balance Al₂O₃And (3) a carrier.

The oxidation deodorization catalyst and the oxidation deodorization auxiliary agent used in the following are provided by Guangzhou Daojinghu refining factory, and the trade marks are HUS-C01 and HUS-P01 respectively.

Example 1

This example uses the apparatus shown in FIG. 1 to carry out a deep desulfurization treatment of a gasoline feedstock A in Table 1.

Gasoline feed a was fractionated at a cut point temperature of 95 ℃ to give a light fraction with a yield of 50 wt% and a heavy fraction with a yield of 50 wt%.

In an oxidation deodorization system aiming at the light fraction after fractionation, the light fraction after fractionation is oxidized under the action of a HUS-C01 catalyst, the reaction temperature is 40 ℃, the pressure is 0.6MPa, and the liquid hourly space velocity is 1.0h^-1The injection amount of air is 2.4 times of the theoretical amount required for oxidizing mercaptan, and the injection amount of the oxidation deodorization auxiliary agent HUS-P01 is 5 mu g/g (compared with light fraction); the sulfur content of mercaptan in the light fraction after oxidation and deodorization is not more than 1 mu g/g.

And in a solvent extraction system, carrying out solvent extraction distillation on the oxidized and deodorized light fraction in a solvent extraction distillation tower to obtain the solvent extracted light fraction and a sulfur-containing solvent, wherein the sulfur-containing solvent accounts for 5 wt% of the total amount of the oxidized and deodorized light fraction. Then separating the sulfur-containing solvent from the sulfides contained therein in a solvent recovery column by distillation under reduced pressure to obtain a solvent-extracted sulfur-containing material and a sulfide-removed recovered solvent:

in a solvent extractive distillation column: the weight ratio of the extraction solvent to the oxidized and deodorized light fraction is 3: 1, the bottom temperature of the tower is 170 ℃, the top temperature of the tower is 80 ℃, the pressure of the top of the tower is 180kPa, the main extraction solvent in the extraction solvent is N-formyl morpholine, the auxiliary agent is water and methanol, the content of the auxiliary agent is 5 wt% of the extraction solvent, and the content of water in the extraction solvent is 1 wt%.

In the solvent recovery column: the bottom temperature of the tower is 180 ℃, the top temperature of the tower is 80 ℃, the top pressure of the tower is 40kPa, and the weight ratio of the steam stripping steam to the sulfur-containing solvent is 0.2: 1.

in a solvent regeneration column: the recovered solvent used for regeneration is 3 weight percent of the total recovered solvent, the temperature at the bottom of the tower is 180 ℃, the temperature at the top of the tower is 100 ℃, the pressure at the top of the tower is 10kPa, residual liquid is discharged from the bottom of the tower, the regenerated solvent and the recovered solvent are mixed and then recycled, and the used stripping water is from condensed water collected by a solvent extraction distillation tower and a solvent recovery tower. The sulfur content in the light fraction after solvent extraction is not more than 5 mu g/g.

And (3) carrying out selective hydrogenation pretreatment and etherification treatment on the light fraction after solvent extraction, wherein the selective hydrogenation pretreatment conditions are as follows: the catalyst Cat2 is pretreated by selective hydrogenation, the reaction temperature is 80 ℃, the reaction pressure is 1.0MPa, and the liquid hourly space velocity is 4.0h^-1And the volume ratio of hydrogen to oil is 5. The etherification reaction is carried out by contacting the light fraction after the solvent extraction with methanol under the etherification conditions: using sulfonic acid type ion exchange resin as an etherification catalyst, wherein the molar ratio of methanol to olefin in the light fraction after solvent extraction is 1.02: 1, liquid hourly space velocity of 2.0h^-1The reaction temperature is 70 ℃, and the reaction pressure is 1.0MPa, so as to obtain the etherified light fraction.

In a selective hydrogenation system aiming at heavy fractions, carrying out selective hydrodesulfurization reaction on the sulfur-containing material subjected to solvent extraction and the heavy fractions subjected to fractionation, wherein the conditions of the selective hydrodesulfurization reaction are as follows: the hydrogen partial pressure is 1.6MPa, the first reaction zone adopts RSDS-11 catalyst, the reaction temperature is 200 ℃, the second reaction zone adopts Cat1 catalyst, the reaction temperature is 300 ℃, and the liquid hourly space velocity is 3.0h^-1The volume ratio of hydrogen to oil was 400. And (3) selectively hydrogenating to obtain hydrogenated heavy fraction, wherein the sulfur content in the hydrogenated heavy fraction is 8 mu g/g.

Mixing the light fraction after solvent extraction and the hydrogenated heavy fraction into a low-sulfur gasoline product B; or the etherified light fraction and the hydrogenated heavy fraction are mixed into a low-sulfur low-olefin gasoline product C.

The properties of gasoline product B and gasoline product C are shown in table 1.

As can be seen from Table 1, the desulfurization rate of the gasoline product B is as high as 99.2%, the sulfur content of the product is only 7 mug/g, the requirement that the sulfur content of the national emission standard V gasoline product is not more than 10 mug/g is met, the olefin saturation rate is 15.6%, and the RON loss value is 1.4 units.

As can be seen from Table 1, the desulfurization rate of the gasoline product C is as high as 99.3%, the sulfur content of the product is only 6 mug/g, the requirement that the sulfur content of the national emission standard V gasoline product is not more than 10 mug/g is met, the olefin removal rate is 45.3%, and the RON is increased by 0.5 unit.

Therefore, the combined process has good desulfurization effect and octane number loss reduction effect, the olefin saturation rate is low and the octane number loss is low if the light fraction etherification treatment is not carried out, and the olefin content can be greatly reduced and the octane number can be effectively recovered and even increased after the light fraction etherification treatment.

In addition, in this embodiment, the extraction solvent containing the auxiliary agent is used during the extractive distillation, so that the effective utilization rate of the extraction solvent is significantly increased, the regeneration frequency of the solvent is reduced, and the relative reduction of energy consumption and the relative reduction of operation cost are caused.

TABLE 1

Comparative example 1

The comparative example, which was carried out using parameters similar to those of example 1, was a gasoline feedstock as feedstock a in table 1, except that the gasoline feedstock was fractionated first to obtain a light fraction and a heavy fraction, then the light fraction was subjected to alkali extraction, and the heavy fraction was subjected to hydrodesulfurization:

the cut point of the gasoline feedstock in example 1 was defined as 60 ℃ and the yield after fractionation was 20 wt% for the light fraction and 80 wt% for the heavy fraction;

and treating the light fraction by adopting an alkali liquor extraction method, wherein the alkali liquor extraction conditions are as follows: the volume ratio of the light fraction to the alkali liquor is 8: 2, obtaining light fraction after alkali liquor extraction at the temperature of 25 ℃ and the pressure of 0.6 MPa; the sulfur-containing alkali liquor absorbing the mercaptan is oxidized under the action of a metal phthalocyanine catalyst suspended in the alkali liquor, the adding amount of the metal phthalocyanine (sulfonated cobalt phthalocyanine, a commercial product) in the alkali liquor is 500 mu g/g, the injection amount of air in the oxidation process is 2.4 times of the theoretical amount, the pressure in the oxidation process is 0.5MPa, and the temperature is 40 ℃; the oxidized sulfur-containing alkali liquor is prepared by mixing the following components in a volume ratio of 1: 10, mixing the heavy fraction with hydrogenation from a selective hydrogenation system to reversely extract and remove disulfide in the oxidized sulfur-containing alkali liquor to obtain regenerated alkali liquor and alkali liquor extracted sulfur-containing materials, wherein the regenerated alkali liquor is recycled; and continuously discharging the sulfur-containing materials extracted by the alkali liquor.

The comparative example only uses the combination of the alkali extraction step of the light fraction and the selective hydrogenation step of the heavy fraction, and does not carry out solvent extraction and etherification treatment on the light fraction.

Only one hydrogenation catalyst RSDS-11 is used in the selective hydrogenation system aiming at the heavy fraction, and the hydrogenation temperature is 320 ℃.

The sulfur content of the light fraction is not more than 10 mu g/g after the alkali liquor extraction, and the sulfur content of the heavy fraction is 9 mu g/g after the hydrogenation.

In this comparative example, the light fraction after the alkali extraction and the heavy fraction after the hydrogenation were mixed to produce a low sulfur gasoline product D, and the results are shown in table 2.

As can be seen from Table 2, in order to obtain a gasoline product D having a sulfur content of not more than 10. mu.g/g, the combined process of comparative example 1 had an olefin saturation of up to 50.0% and an octane RON loss of up to 5.5 units, as compared to the combined process of example 1, which obtained gasoline product B.

TABLE 2

Oil name	Starting materials A	Light fraction after fractionation	Heavy fraction after fractionation	Gasoline product D
					Density (20 ℃ C.)/(g/cm)³)	0.7242	0.6205	0.7481	0.7225
Sulfur content/(μ g/g)	878	135	1064	9
					Mercaptan sulfur content/(μ g/g)	50	127	31	4
Olefin content/volume%	32.0	45.0	28.6	16.0
					RON	90.2	-	-	84.7
Desulfurization rate/%)	-	-	-	99.0
					Olefin saturation/removal rate/%)	-	-	-	50.0
△RON	-	-	-	-5.5

Example 2

This example uses the apparatus shown in FIG. 1 to carry out a deep desulfurization treatment of a gasoline feedstock E.

Gasoline feedstock E was fractionated at a cut point temperature of 120 ℃ to give a light fraction with a yield of 60 wt% and a heavy fraction with a yield of 40 wt%.

In an oxidation deodorization system aiming at the light fraction after fractionation, the light fraction after fractionation is oxidized under the action of a HUS-C01 catalyst, the reaction temperature is 55 ℃, the pressure is 0.6MPa, and the liquid hourly space velocity is 1.2h^-1The injection amount of air is 2.4 times of the theoretical amount required for oxidizing mercaptan, and the injection amount of the oxidation deodorization auxiliary agent HUS-P01 is 5 mu g/g (compared with light fraction); the sulfur content of mercaptan in the light fraction after oxidation and deodorization is not more than 1 mu g/g.

In a solvent extraction system, the light fraction after oxidation and deodorization is subjected to solvent extraction distillation in a solvent extraction distillation tower to obtain the light fraction after solvent extraction and a sulfur-containing solvent, wherein the sulfur-containing solvent accounts for 7 wt% of the total amount of the light fraction after oxidation and deodorization. Then separating the sulfur-containing solvent from the sulfides contained therein in a solvent recovery column by distillation under reduced pressure to obtain a solvent-extracted sulfur-containing material and a sulfide-removed recovered solvent:

in a solvent extractive distillation column: the weight ratio of the extraction solvent to the oxidized and deodorized light fraction is 4: 1, the temperature of the bottom of the tower is 150 ℃, the temperature of the top of the tower is 95 ℃, the pressure of the top of the tower is 200kPa, the main extraction solvent in the extraction solvent is N-methyl-2-pyrrolidone, the auxiliary agent is acetone, and the content of the auxiliary agent is 4.2 percent by weight of the extraction solvent.

In the solvent recovery column: the bottom temperature is 200 ℃, the top temperature is 90 ℃, the top pressure is 40kPa, the weight ratio of the stripping steam to the sulfur-containing solvent is 0.25: 1.

in a solvent regeneration column: the recovered solvent used for regeneration is 5 weight percent of the total recovered solvent, the temperature at the bottom of the tower is 170 ℃, the temperature at the top of the tower is 100 ℃, the pressure at the top of the tower is 8kPa, residual liquid is discharged from the bottom of the tower, the regenerated solvent and the recovered solvent are mixed and then recycled, and the used stripping water is from condensed water collected by a solvent extraction distillation tower and a solvent recovery tower. The sulfur content in the light fraction after solvent extraction was 3. mu.g/g.

And (3) carrying out selective hydrogenation pretreatment and etherification treatment on the light fraction after solvent extraction, wherein the selective hydrogenation pretreatment conditions are as follows: the catalyst Cat2 is pretreated by selective hydrogenation, the reaction temperature is 100 ℃, the reaction pressure is 1.2MPa, and the liquid hourly space velocity is 5h^-1And the volume ratio of hydrogen to oil is 5. The etherification reaction is carried out by contacting the light fraction after the solvent extraction with methanol under the etherification conditions: using sulfonic acid type ion exchange resin as etherification catalyst, the mol ratio of methanol to olefin in the light fraction after solvent extraction is 1.05: 1, the reaction temperature is 80 ℃, and the reaction pressure is 1.0MPa, so as to obtain the etherified light fraction.

In a selective hydrogenation system aiming at heavy fractions, carrying out selective hydrodesulfurization reaction on the sulfur-containing material subjected to solvent extraction and the heavy fractions subjected to fractionation, wherein the conditions of the selective hydrodesulfurization reaction are as follows: hydrogen partial pressure is 1.6MPa, RSDS-11 catalyst is adopted in the first reaction zone, reaction temperature is 220 ℃, and the second reaction zone adoptsThe catalyst Cat1, the reaction temperature is 295 ℃, and the liquid hourly volume space velocity is 3.0h^-1The volume ratio of hydrogen to oil was 400. And (3) selectively hydrogenating to obtain hydrogenated heavy fraction, wherein the sulfur content in the hydrogenated heavy fraction is 6 mu g/g.

Mixing the light fraction after solvent extraction and the hydrogenated heavy fraction into a low-sulfur gasoline product F; or the etherified light fraction and the hydrogenated heavy fraction are mixed into a low-sulfur low-olefin gasoline product G.

The properties of gasoline product F and gasoline product G are shown in table 3.

As can be seen from Table 3, the desulfurization rate of the gasoline product F is as high as 98.7%, the sulfur content of the product is only 4 mug/g, the requirement that the sulfur content of the national emission standard V gasoline product is not more than 10 mug/g is met, the olefin saturation rate is 13.5%, and the RON loss value is 0.5 unit.

As can be seen from Table 3, the desulfurization rate of the gasoline product G is as high as 99.0%, the sulfur content of the product is only 3 mug/G, the requirement that the sulfur content of the national emission standard V gasoline product is not more than 10 mug/G is met, the olefin removal rate is 59.6%, and the RON is increased by 0.7 unit.

TABLE 3

Example 3

This example was carried out using the same feedstock E and the same combined desulfurization process and the same process parameters as in example 2, except that:

the extraction solvent used in the solvent extraction of this example contained no auxiliary agent, and the rest was the same as in example 2, with the result that the sulfur content in the light fraction after solvent extraction was 6. mu.g/g.

And (3) selectively hydrogenating to obtain hydrogenated heavy fraction, wherein the sulfur content in the hydrogenated heavy fraction is 6 mu g/g.

Mixing the light fraction after solvent extraction and the hydrogenated heavy fraction into a low-sulfur gasoline product H; or the etherified light fraction and the hydrogenated heavy fraction are mixed into a low-sulfur low-olefin gasoline product I.

The properties of gasoline product H and gasoline product I are shown in table 4.

As can be seen from Table 4, the desulfurization rate of the gasoline product H is as high as 98.0%, the sulfur content of the product is only 6 mug/g, the requirement that the sulfur content of the national emission standard V gasoline product is not more than 10 mug/g is met, the olefin saturation rate is 13.5%, and the RON loss value is 0.5 unit.

As can be seen from Table 4, the desulfurization rate of the gasoline product I is as high as 98.3%, the sulfur content of the product is only 5 mug/g, the requirement that the sulfur content of the national emission standard V gasoline product is not more than 10 mug/g is met, the olefin removal rate is 59.6%, and the RON is increased by 0.7 unit.

Comparing the results of this example with those of example 2, it can be seen that the use of an extraction solvent containing an adjuvant during the solvent extraction process enables the gasoline product obtained by the process of the present invention to have a somewhat lower sulfur content. If the sulfur content of the product is to be made completely uniform, the hydrogenation degree of the heavy fraction is increased in this example, which results in a decrease in the olefin content of the product H (as compared with the product I), and a greater octane number loss than in example 2.

In addition, in this embodiment, since no auxiliary agent is used, the effective utilization rate of the extraction solvent is lowered during the extractive distillation, which is not favorable for the long-term extraction.

TABLE 4

From the above results, it can be seen that the process of the present invention can obtain a lower sulfur gasoline product while avoiding a large loss in octane number. In addition, in the solvent extraction process, the use of the auxiliary agent has a certain promotion effect on the solvent extraction, and further, when the solvent is recycled for a long time, the effect of the auxiliary agent on the solvent extraction of the sulfide is more favorable particularly when the solvent is decomposed and the content of impurities is increased. Particularly, the matching of the etherification reaction process can lead the octane number of the gasoline product to be increased, the sulfur content to be further reduced, and simultaneously, the olefin is greatly reduced, thereby being beneficial to meeting the requirements of the VI gasoline standard of the future.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A method for deep desulfurization of gasoline, comprising:

(3) contacting the oxidized and deodorized light fraction with an extraction solvent to perform solvent extraction through distillation to obtain a sulfur-containing solvent and a solvent-extracted light fraction, and then separating the sulfur-containing solvent from sulfides contained in the sulfur-containing solvent through reduced pressure distillation to obtain a solvent-extracted sulfur-containing material and a recovered solvent from which the sulfides are removed, wherein in the solvent extraction process, the weight ratio of the extraction solvent to the oxidized and deodorized light fraction is (0.5-20): 1; the solvent extraction is carried out in an extractive distillation column under conditions comprising: the pressure at the top of the tower is 100 kPa-500 kPa; the temperature of the tower top is 65-180 ℃; the temperature of the tower bottom is 80-260 ℃; the extraction solvent contains a main extraction solvent and 0.1-20 wt% of an auxiliary agent, wherein the main extraction solvent is at least one of tetraethyleneglycol, pentaethylene glycol, furfural, furfuryl alcohol, dimethylformamide, triethylene glycol monomethyl ether, acetonitrile and a solvent with a boiling point of 175-320 ℃; the auxiliary agent is at least one of alcohols, ketones, organic acids and organic nitrides which can be mutually dissolved with the main extraction solvent and have the boiling point or the dry point not higher than that of the main extraction solvent and/or water, and the organic nitrides are at least one of amines, ureas and alcohol amines;

the conditions for separating the sulfur-containing solvent from the sulfides contained therein by distillation under reduced pressure include: the pressure at the top of the solvent recovery tower is 10-100 kPa, the temperature at the top of the tower is 50-100 ℃, the temperature at the bottom of the tower is 100-250 ℃, and the weight ratio of stripping steam to the sulfur-containing solvent is (0.01-5.0): 1;

(5) mixing the hydrogenated heavy fraction of step (4) with the solvent extracted light fraction of step (3) to obtain a gasoline product;

the method further comprises the following steps: at least part of the recovered solvent is subjected to water injection purification treatment in a solvent regeneration tower to be regenerated; the regeneration conditions in the solvent regeneration column include: the pressure at the top of the tower is 1 kPa-10 kPa, the temperature at the top of the tower is 90-110 ℃, the temperature at the bottom of the tower is 120-200 ℃, and the weight ratio of the injected water to the recovered solvent is (0.1-10): 1.

2. the method of claim 1, wherein the method further comprises: before mixing with the hydrogenated heavy fraction obtained in the step (4), carrying out etherification reaction on the light fraction obtained in the step (3) after solvent extraction to obtain an etherified light fraction; and then mixing the etherified light fraction with the hydrogenated heavy fraction of step (4) to obtain the gasoline product.

3. The process of claim 2, wherein the etherification reaction is carried out by contacting the solvent extracted light fraction with a lower alcohol having no more than 6 carbon atoms.

4. The method according to claim 3, wherein the lower alcohol is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, n-pentanol, and cyclohexanol.

5. The process of claim 3, wherein the etherification reaction conditions include: the mol ratio of the low-carbon alcohol to the olefin in the light fraction after solvent extraction is (0.5-3): 1, the contact temperature is 20-100 ℃, and the pressure is 0.3-2.0 MPa.

6. The process of claim 5, wherein the etherification reaction conditions comprise: the mol ratio of the low-carbon alcohol to the olefin in the light fraction after solvent extraction is (1.0-1.2): 1.

7. the process according to claim 2, wherein the etherification reaction is carried out in the presence of a strongly acidic ion exchange resin as etherification catalyst.

8. The method of any of claims 2-7, wherein the method further comprises: before the etherification reaction, the light fraction after the solvent extraction is subjected to adsorption pretreatment and/or selective hydrogenation pretreatment.

9. The method according to claim 8, wherein the selective hydrogenation pretreatment is carried out in the presence of a transition metal supported catalyst comprising a carrier selected from at least one of alumina, silica, aluminosilicate, titania, zeolite and activated carbon and a metal active component selected from at least one of nickel, cobalt, molybdenum, platinum and palladium supported on the carrier.

10. The method according to claim 9, wherein the carrier in the transition metal supported catalyst is alumina, and the loading amount of the metal active component in terms of oxide is 0.05-15 wt%.

11. The method of claim 9, wherein the conditions of the selective hydrogenation pretreatment comprise: the hydrogen partial pressure is 0.1MPa to 2.0MPa, the temperature is room temperature to 250 ℃, and the liquid hourly volume space velocity is 1.0h^-1～10.0h^-1The volume ratio of hydrogen to oil is 1-100.

12. The method of any of claims 1-7, wherein the method further comprises: carrying out selective hydrodesulfurization reaction on the sulfur-containing material extracted by the solvent in the step (3) and the heavy fraction; or

Introducing the sulfur-containing material extracted by the solvent in the step (3) into a catalytic cracking device for catalytic cracking reaction to obtain at least part of the gasoline raw material used in the step (1).

13. The method according to any one of claims 1 to 7, wherein in the solvent extraction process, the weight ratio of the extraction solvent to the oxidized deodorized light fraction is (1-5): 1.

14. the method of any of claims 1-7, wherein the conditions in the extractive distillation column comprise: the pressure at the top of the tower is 110 kPa-300 kPa; the temperature of the tower bottom is 140-200 ℃.

15. The process of any one of claims 1-7, wherein the main extraction solvent has a boiling point of 175 to 250 ℃.

16. The method of any one of claims 1-7, the main extraction solvent is at least one selected from sulfolane, 3-methyl sulfolane, 2, 4-dimethyl sulfolane, 3-ethyl sulfolane, methyl ethyl sulfone, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dibutyl sulfone, dimethyl sulfoxide, alpha-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-formyl morpholine, triethylene glycol, tetraethylene glycol, pentaethylene glycol, triethylene glycol methyl ether, ethylene carbonate, propylene carbonate, nitrobenzene, polyethylene glycol with the relative molecular mass of 200-400 and polyethylene glycol methyl ether with the relative molecular mass of 200-400.

17. The process of claim 16, wherein the primary extraction solvent is selected from at least one of sulfolane, N-formylmorpholine, N-methyl-2-pyrrolidone, tetraethylene glycol, and pentaethylene glycol.

18. The method according to any one of claims 1 to 7, wherein the extraction solvent contains an auxiliary agent in which the number of carbon atoms of the alcohol, ketone, organic acid, and organonitride is not more than 6.

19. The method according to any one of claims 1 to 7, wherein the content of the auxiliary in the extraction solvent is 0.5 to 15% by weight.

20. The method of any one of claims 1-7, wherein the adjuvant is selected from at least one of water, methanol, ethanol, N-propanol, isopropanol, acetone, methyl ethyl ketone, isobutyric acid, oxalic acid, malonic acid, succinic acid, urea, ethylenediamine, monoethanolamine, N-methyl monoethanolamine, N-ethyl monoethanolamine, N-dimethylethanolamine, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, N-propanolamine, isopropanolamine, and diglycolamine.

21. The method of claim 20, wherein the adjuvant is selected from at least one of water, methanol, acetone, methyl ethyl ketone, isobutyric acid, oxalic acid, malonic acid, succinic acid, ethylenediamine, monoethanolamine, N-methyl monoethanolamine, isopropanolamine, and diglycolamine.

22. The method according to any one of claims 1 to 7, wherein the auxiliary is a mixture containing water, and the content of water in the extraction solvent is 0.1 to 5 wt%.

23. The method according to claim 22, wherein the content of water in the extraction solvent is 0.1 to 3% by weight.

24. The process according to any one of claims 1 to 7, wherein the conditions for separating the sulfur-containing solvent from the sulfides contained therein by distillation under reduced pressure comprise: the temperature of the tower bottom is 120-200 ℃.

25. The method of any of claims 1-7, wherein the regeneration conditions in the solvent regeneration column comprise: the temperature of the top of the tower is 96-105 ℃, the temperature of the bottom of the tower is 150-200 ℃, and the weight ratio of the injected water to the recovered solvent is (0.5-5): 1.

26. the method according to any one of claims 1 to 7, wherein the recovered solvent used for regeneration accounts for 1 to 10 wt% of the total recovered solvent.

27. The method of claim 26, wherein the recovered solvent used for regeneration comprises 1-5 wt% of the total recovered solvent.

28. The method according to any one of claims 1 to 7, wherein the selective hydrodesulfurization reaction is carried out in a first reaction zone and a second reaction zone which are connected in sequence, wherein the first reaction zone and the second reaction zone are respectively filled with a first hydrodesulfurization catalyst and a second hydrodesulfurization catalyst, and the first hydrodesulfurization catalyst and the second hydrodesulfurization catalyst respectively and independently comprise an alumina carrier and/or a silica-alumina carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component is a non-noble metal element from the group VIB of molybdenum and/or tungsten and/or a non-noble metal element from the group VIII of nickel and/or cobalt.

29. The process of claim 28, wherein the first and second hydrodesulfurization catalysts each independently contain molybdenum and/or tungsten, nickel and/or cobalt, an alumina matrix, and a large pore zeolite and/or a medium pore zeolite.

30. The process of claim 28, wherein the group VIB non-noble metal element is present in an amount of 2 to 25 wt.% as oxide and the group VIII non-noble metal element is present in an amount of 0.2 to 6 wt.% as oxide, based on the total amount of the hydrodesulfurization catalyst.

31. The process of claim 28, wherein the reaction conditions of the first and second reaction zones each independently comprise: the hydrogen partial pressure is 0.1MPa to 4.0MPa, the reaction temperature is 200 ℃ to 440 ℃, and the liquid hourly volume space velocity is 1.0h^-1～10.0h^-1The volume ratio of hydrogen to oil is 200-1000.

32. The process of claim 31, wherein the reaction conditions of the first and second reaction zones each independently comprise: the hydrogen partial pressure is 1.0MPa to 3.2MPa, the reaction temperature is 200 ℃ to 300 ℃, and the liquid hourly volume space velocity is 2.0h^-1～6.0h^-1The volume ratio of hydrogen to oil is 200-600.

33. The method of claim 1, wherein the oxidant is oxygen and/or air.

34. The method of claim 33, wherein the conditions of the oxidative deodorization reaction comprise: the reaction temperature is 0-300 ℃; the reaction pressure is 0.01MPa to 7.0 MPa; liquid hourly volume airspeedIs 0.05 to 10 hours^-1。

35. The method of claim 34, wherein the conditions of the oxidative deodorization reaction comprise: the reaction temperature is between room temperature and 200 ℃; the reaction pressure is 0.1MPa to 2.0 MPa; the liquid hourly space velocity is 0.5h^-1～5.0h^-1。

36. The method according to claim 1, wherein the oxidative deodorization catalyst is a supported metal phthalocyanine catalyst, the supported metal phthalocyanine catalyst comprises a carrier and metal phthalocyanine supported on the carrier, the carrier is a porous material, and the supported amount of the metal phthalocyanine is 0.05-10 wt%.

37. The method according to claim 36, wherein the loading amount of the metal phthalocyanine is 0.1 to 5% by weight.

38. The method according to claim 1, wherein the cut points of the light fraction and the heavy fraction are 80-120 ℃.

39. The process of claim 38, wherein the yield of the light fraction is 40 to 60 wt% and the yield of the heavy fraction is 40 to 60 wt% based on the gasoline feedstock;

the gasoline raw material is at least one of catalytic cracking gasoline, straight run gasoline, coking gasoline, pyrolysis gasoline and thermal cracking gasoline.

40. The method according to any one of claims 1 to 7, wherein in step (5), the sulfur content of the obtained gasoline product is no more than 10 μ g/g.