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

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 present invention relates to the refining field of hydrocarbon materials, in particular, to a method for deep desulfurization of gasoline and a device for deep desulfurization of gasoline, and more particularly, to a kind of sulfur-containing gasoline that is combined with non-hydrogenated gasoline by hydrogenation A deep desulfurization process formed by a combination of methods.

Background technique

As we all know, the emission of toxic and harmful substances in automobile exhaust seriously affects air quality. Therefore, countries around the world have set more and more stringent standards for the quality of oil used as engine fuel. my country has implemented No. IV emission standards nationwide since January 1, 2013, and has implemented No. V emission standards in large cities such as Beijing and Shanghai. IV and V emission standards stipulate that the sulfur content in motor gasoline should not exceed 50 μg/g and 10 μg/g, respectively.

The sulfur in gasoline mainly comes from catalytically cracked gasoline. With the development of oil processing raw materials to the direction of heaviness, the sulfur content of catalytically cracked gasoline will further increase. 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 includes mercaptans, sulfides, disulfides and thiophenes (including thiophene and thiophene derivatives). In the gasoline standard as a fuel, the mercaptan sulfur content and the total sulfur content are stipulated with maximum limits. When the mercaptan sulfur content exceeds the standard or the total sulfur content exceeds the standard, the gasoline must be desulfurized or desulfurized.

Since the catalytically cracked gasoline, which is used as a blending component of the gasoline pool for vehicles, is rich in olefins, the conventional hydrogenation method is prone to cause a large loss of octane number due to the saturation of olefins. In order to avoid the large loss of octane number in the process, people usually use staged treatment to desulfurize and refine the catalytically cracked gasoline.

US3957625 reports a method for gasoline desulfurization. The method is to cut gasoline into light and heavy parts, and reduce the sulfur content in the gasoline by selectively hydrotreating the heavy gasoline fraction. And US6610197 has reported a kind of method for gasoline desulfurization, and this method is to cut gasoline into light and heavy parts, carry out non-hydroprocessing to light fractions, and carry out hydroprocessing to heavy fractions to reduce the sulfur content in the gasoline with this .

US6623627 reports a method for producing low-sulfur gasoline. The method is to cut gasoline into three fractions of low, medium and high boiling points, wherein the low-boiling fractions containing mercaptans are contacted with lye to selectively remove mercaptans and thiophene-containing fractions. The middle boiling point fraction is desulfurized by extraction, the thiophene-containing extract of the middle boiling point fraction and the high boiling point fraction are subjected to desulfurization reaction in the hydrodesulfurization zone, and then the separately treated light, medium and heavy fractions are mixed to obtain a reduced sulfur content. gasoline products. The contact between the low-boiling fraction and the lye is carried out by means of lye extraction, the lye is oxidized and regenerated after the mercaptan is extracted, and the disulfides produced by the oxidation process are separated by sedimentation and then recycled. use. However, the prior art does not disclose a solvent extraction process for thiophene-containing middle boiling fractions.

CN102851069A reports a method for desulfurization of gasoline, which comprises cutting gasoline to fractionate heavy fractions with relatively high boiling range and light fractions with relatively low boiling range; The desulfurization catalyst is contacted to carry out selective hydrodesulfurization to obtain heavy fractions after desulfurization; the light fractions are contacted with lye to carry out light fraction desulfurization, and the obtained lye and oxidant that have absorbed sulfides are combined with the oxidation catalyst and a part of the desulfurized The heavy fractions of the lye are contacted to carry out lye regeneration and lye desulfurization simultaneously, so that the salt of the sulfide in the lye is oxidized into disulfide, and simultaneously the disulfide in the lye is extracted into the heavy fraction after the desulfurization, Then phase separation is carried out, and the tail gas is discharged; at least a part of the obtained disulfide-absorbed heavy fraction is returned for the selective hydrodesulfurization; the desulfurized heavy fraction is mixed with the desulfurized light fraction get product.

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

CN103740405A discloses a combined process of alkali washing-extraction-hydrogenation for producing low-sulfur gasoline. The process is to cut gasoline into light and heavy fractions, and then carry out extraction and desulfurization after the light fractions are purified by alkali, and the extracted sulfur-containing fractions are subjected to extraction and desulfurization. The components are mixed with heavy fractions for selective hydrogenation, and the light fractions after extraction and desulfurization are mixed with heavy fractions after selective hydrogenation to form low-sulfur gasoline products. The alkali refining is carried out by means of simple alkali washing, which inevitably consumes serious alkali. The extraction desulfurization method also adopts the liquid-liquid extraction method.

In the desulfurization method or process disclosed above, the purpose of alkali treatment is to remove mercaptans with relatively small molecular weights in gasoline fractions, such as mercaptans with a carbon number not greater than 4, while the purpose of solvent extraction is to remove gasoline The non-thiol sulfides in the fraction are mainly thiophene compounds. When the mass fraction of gasoline fractions treated by alkali treatment and solvent treatment increases, the mass fraction of gasoline fractions subjected to hydrotreating will decrease accordingly, and the loss of octane number caused by hydrotreating will undoubtedly be relatively reduced. However, conventional liquid-liquid solvent extraction usually has a low desulfurization efficiency, and absorbs more non-sulfide hydrocarbons, which requires subsequent washing and separation, and the separated sulfur-containing materials carry more impurities, which is not conducive to sending In particular, the recovered solvent is often not fully regenerated, resulting in a decrease in the ability to extract sulfides when the solvent is recycled.

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

SUMMARY OF THE INVENTION

The object of the present invention is to overcome the defects of the prior art, and under the premise of avoiding the larger loss of octane number, a new method for deep desulfurization of gasoline that can obtain a lower sulfur gasoline product and a method for the method are provided. equipment.

The inventors of the present invention found that, compared with conventional liquid-liquid extraction, extractive distillation has higher removal efficiency of sulfides, and the extraction solvent absorbs olefins in the process of extractive distillation. -Liquid extraction is less, so on the one hand it is beneficial to retain more olefins and reduce the octane number loss caused by the subsequent (incorporated into heavy ends) hydroprocessing of olefins after sulfide extraction, and on the other hand On the one hand, less olefins are dissolved in the extraction solvent, which can reduce the harmful effects of olefins on solvent recycling due to oxidative polymerization, and avoid frequent regeneration of the extraction solvent due to the accumulation of harmful impurities. It is also found that small molecular mercaptans are difficult to be completely extracted by the extraction solvent, but after low-boiling mercaptans are converted into high-boiling thioether disulfides, although conventional liquid-liquid extraction methods are still difficult to remove However, under the condition of extractive distillation, it is easy to separate high-boiling disulfides from gasoline fractions and remove them together with the extraction solvent that absorbs thiophene sulfur, depending on the temperature difference between the upper and lower temperature of the distillation column. The inventors of the present invention provide the following method for deep desulfurization of gasoline of the present invention based on the aforementioned research.

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

(1) fractional distillation of gasoline feedstock at a cut-point temperature of 70 to 140° C. to obtain light ends and heavy ends;

(2) in the presence of an oxidative deodorization catalyst, contacting the light fraction with an oxidant to carry out an oxidative deodorization reaction to obtain the light fraction after oxidative deodorization;

(3) contacting the light fraction after the oxidative deodorization with an extraction solvent to carry out solvent extraction by distillation, obtaining a sulfur-containing solvent and the light fraction after solvent extraction, and then distilling the sulfur-containing solvent with the solvent containing The sulfide is separated to obtain the sulfur-containing material after solvent extraction and the recovery solvent from which the sulfide has been removed;

(4) contacting the heavy fraction with a hydrodesulfurization catalyst to carry out a selective hydrodesulfurization reaction to obtain a heavy fraction after hydrogenation;

(5) Mixing the hydrogenated heavy fraction of step (4) with the solvent extraction light fraction of step (3) to obtain a gasoline product.

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

A fractionation system through which the gasoline feedstock is fractionated to obtain light ends and heavy ends;

an oxidative deodorization system, which is used for carrying out an oxidative deodorization reaction on the light fraction to obtain a light fraction after oxidative deodorization;

A solvent extraction system, including a solvent extraction distillation unit and a solvent recovery unit, the solvent extraction and distillation unit is used to perform solvent extraction on the light fractions after oxidative deodorization from the oxidative deodorization system to obtain a sulfur-containing solvent and a solvent-extracted Light ends; the solvent recovery unit is used to separate the sulfur-containing solvent from the sulfide contained therein to obtain the sulfur-containing material after solvent extraction and the recovered solvent from which the sulfide has been removed;

A selective hydrogenation system, the heavy fractions from the fractionation system are introduced into the selective hydrogenation system through pipelines for selective hydrodesulfurization reaction to obtain the heavy fractions after hydrogenation;

The hydrogenated heavy fraction is mixed with the solvent-extracted light fraction and withdrawn as gasoline product through a pipeline.

In order to obtain lower-sulfur gasoline products and avoid a large loss of octane number, the present invention flexibly utilizes non-hydrogenation methods such as oxidative deodorization and solvent extraction while adopting a hydrogenation method, so that the method provided by the present invention is provided above. A lower sulfur gasoline product can be obtained on the premise of avoiding a large loss of octane number.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the specification, and together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached image:

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

Description of reference numerals

1. Gasoline raw material 2. Fractionation system

3. Heavy fraction 4. Light fraction

5. Oxidative deodorization system 6. Light fractions after oxidative deodorization

7. Solvent extraction system 8. Sulfur-containing material after solvent extraction

9. Light fraction after solvent extraction 10. Heavy fraction after hydrogenation

11. Etherification system 12. Light fractions after etherification

13. Selective hydrogenation system

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, but not to limit the present invention.

The endpoints of ranges and any values disclosed herein are not limited to the precise ranges or values, which are to be understood to encompass values proximate to those ranges or values. For ranges of values, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein.

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

(1) fractional distillation of gasoline feedstock at a cut-point temperature of 70 to 140° C. to obtain light ends and heavy ends;

(2) in the presence of an oxidative deodorization catalyst, contacting the light fraction with an oxidant to carry out an oxidative deodorization reaction to obtain the light fraction after oxidative deodorization;

(3) contacting the light fraction after the oxidative deodorization with an extraction solvent to carry out solvent extraction by distillation, obtaining a sulfur-containing solvent and the light fraction after solvent extraction, and then distilling the sulfur-containing solvent with the solvent containing The sulfide is separated to obtain the sulfur-containing material after solvent extraction and the recovery solvent from which the sulfide has been removed;

(4) contacting the heavy fraction with a hydrodesulfurization catalyst to carry out a selective hydrodesulfurization reaction to obtain a heavy fraction after hydrogenation;

(5) Mixing the hydrogenated heavy fraction of step (4) with the solvent extraction light fraction of step (3) to obtain a gasoline product.

The light fractions are fractions with a relatively light distillation range, and the heavy fractions are fractions with a relatively heavy distillation range. Most of the mercaptans and olefins in the gasoline raw material are concentrated in the light fraction of the present invention, and most of the other relatively high-boiling sulfides are mainly thiophenes in the gasoline raw material are concentrated in the heavy fraction.

In the present invention, the fractionated light fraction is contacted with an oxidant in the presence of an oxidative deodorization catalyst to carry out an oxidative deodorization reaction to become the light fraction after oxidative deodorization, and the mercaptan in the light fraction is oxidized to a relatively high boiling point disulfide.

It is well known that the mercaptans rich in the light ends can be removed by lye extraction and the sulfur content of the light ends can be reduced. However, lye extraction usually requires the use of a large amount of caustic lye, which will result in the production of caustic residues that are difficult to handle, and a back-extraction operation is usually required to remove the disulfide converted from mercaptans from the lye. material, which will produce a sulphur-containing material that requires additional treatment. In order to overcome the technical defects brought by the extraction of alkali liquor, the present invention adopts an oxidative deodorization method to treat the light fraction, so that the mercaptans in the light fraction are converted into disulfides. Due to the relatively high boiling point of disulfides, they can be easily removed in subsequent solvent extraction distillation.

The oxidative deodorization step in the preferred case of the present invention is provided below:

According to the present invention, the light fraction is contacted with an oxidant under the action of an oxidative deodorization catalyst to carry out an oxidative deodorization reaction. Such as copper chloride salt) type catalyst, metal oxide (such as iron oxide, manganese oxide, lead oxide, copper oxide, zinc oxide, etc.) catalyst, copper molecular sieve or copper ion exchange resin catalyst, perovskite type oxidative deodorization catalyst, various A molecular sieve catalyst with oxidation function, organic compound type catalyst with oxidizing property, heteropolyacid type oxidative deodorization catalyst, etc. Metal phthalocyanine catalysts are preferred, and supported metal phthalocyanine catalysts are more preferred. The oxidant is oxygen, air, ozone, peroxide and other reactants capable of oxidizing mercaptan to disulfide, more preferably, the oxidant is oxygen and/or air. The injection amount of the air is usually 1.0-10 times, preferably 1.5-4 times, the theoretical oxygen demand of the desulfanization reaction.

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

An activator can also be added in the oxidative deodorization reaction, and the activator is an oxidative deodorization auxiliary agent capable of improving the efficiency of the oxidative deodorization reaction. The activator 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 the solvent and participates in the oxidative deodorization reaction in the form of the activator solution. The solvent is one or more of water, alcohol and liquid hydrocarbon, and the alcohol includes C _1-6 monohydric alcohol and C _1-6 polyhydric alcohol, preferably methanol, ethanol or isopropanol.

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

Preferably, the metal phthalocyanine is selected from magnesium phthalocyanine, titanium phthalocyanine, hafnium phthalocyanine, vanadium phthalocyanine, tantalum phthalocyanine, molybdenum phthalocyanine, manganese phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, platinum phthalocyanine, At least one of palladium phthalocyanine, copper phthalocyanine, silver phthalocyanine, zinc phthalocyanine and tin phthalocyanine; more preferably, the metal phthalocyanine is cobalt phthalocyanine and/or vanadium phthalocyanine. Wherein, the phthalocyanine ring constituting the metal phthalocyanine may be a single ring, a bicyclic ring or a polycyclic ring, in particular, the phthalocyanine ring is connected with a substituent, and the substituent may be selected from a sulfo group, a carboxyl group, an amide group At least one of the group, an acid halide group, a quaternary ammonium compound, an onium compound, and a halogen. The cobalt phthalocyanine is preferably cobalt phthalocyanine sulfonate and/or cobalt phthalocyanine carboxylate, the cobalt phthalocyanine sulfonate includes cobalt phthalocyanine sulfonic acid and cobalt phthalocyanine sulfonate, and the cobalt phthalocyanine sulfonic acid is Sulfonated cobalt phthalocyanine, including monosulfonic acid of cobalt phthalocyanine (monosulfonated cobalt phthalocyanine), disulfonic acid of cobalt phthalocyanine (bissulfonated cobalt phthalocyanine), trisulfonic acid of cobalt phthalocyanine (trisulfonated cobalt phthalocyanine) Cobalt phthalocyanine) and a mixture of one or more of the tetrasulfonic acids (tetrasulfonated cobalt phthalocyanine) of cobalt phthalocyanine, said cobalt phthalocyanine sulfonate, also including bicyclic polysulfonated cobalt phthalocyanine, said The cobalt phthalocyanine carboxylate includes cobalt phthalocyanine carboxylic acid and cobalt phthalocyanine carboxylate, preferably a bicyclic polycobalt phthalocyanine having a carboxylic acid group as a substituent.

Preferably, the porous material used as the carrier of the supported metal phthalocyanine catalyst is selected from substances containing at least one of aluminum, silicon, alkaline earth metals, transition metals, rare earth metals and carbonaceous materials, for example, can be selected from oxidation Aluminium, silica, aluminosilicates, calcium oxide, magnesium oxide, titanium oxide, natural and artificial clays, natural and artificial zeolites, derived from mineral materials (such as coal and petroleum, etc.), plant materials (such as wood chips, nut shells and nuts) etc.) and one or more of carbonaceous materials such as synthetic resins, etc., it is preferable to use activated carbon as the carrier of the supported metal phthalocyanine catalyst. More preferably, the specific surface area of the porous material used as the carrier is 10-1500 m ² /g, preferably 100-1200 m ² /g.

According to the present invention, the preparation method of the supported metal phthalocyanine catalyst is well known to those skilled in the art, for example, it can be prepared in a manner known in the literature, that is, the solution of metal phthalocyanine is impregnated into the porous support, and Made after drying.

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

Solvent extraction in the preferred case of the present invention is provided below:

The solvent extraction enables the thiophene-based sulfides in the light fraction after oxidative deodorization to be transferred into the extraction solvent to form a sulfur-containing solvent.

Preferably, the solvent extraction is carried out in an extractive distillation column, the light ends after oxidative deodorization enter the column from the middle part of the extractive distillation column, and the extraction solvent enters the column from the upper part of the extractive distillation column, and the solvent Under the selective action, the relatively high-boiling thiophene and sulfide compounds in the light fraction after oxidative deodorization enter the bottom of the extractive distillation column with the extraction solvent. A part of the low-sulfur light fraction distilled from the top of the extractive distillation tower is refluxed at the top of the tower, and a part is discharged to the light fraction after solvent extraction. Part of the sulfur-rich solvent at the bottom of the extractive distillation tower is circulated at the bottom of the tower, and part is discharged to the solvent recovery unit for processing.

The weight ratio of the extraction solvent to the light fraction after oxidative deodorization is (0.5-20):1, more preferably (1-5):1. The inventors found that, in the liquid-liquid extraction method, the sulfur-containing solvent often absorbs other components that are much more than sulfides in addition to sulfides in the light fraction, so that the solvent in the distillation method can be recovered. The system brings many problems, such as increased energy consumption, more residual components in the recovered solvent, and returning to the solvent extraction system will easily lead to a rapid decline in the solvent extraction capacity. However, in the solvent extraction distillation desulfurization method of the present invention, the extraction solvent absorbs less 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, and the conditions in the extractive distillation column include: the pressure at the top of the column is 100kPa～500kPa, preferably 110kPa～300kPa; the temperature at the top of the column is 65～180℃; The column bottom temperature is 80 to 260°C, preferably 140 to 200°C.

Preferably, the sulfur content in the solvent-extracted light fraction obtained after the solvent extraction is ≯ 10 μg/g.

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

Preferably, the main extraction solvent is 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, furfural, furfuryl alcohol, α-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 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, propylene carbonate At least one of esters, acetonitrile, nitrobenzene, polyethylene glycol with a relative molecular mass between 200 and 400, and polyethylene glycol methyl ether with a relative molecular mass between 200 and 400; more preferably, the The main extraction solvent is selected from at least one of sulfolane, N-formylmorpholine, N-methyl-2-pyrrolidone, tetraethylene glycol and pentaethylene glycol.

In the solvent extraction distillation column, there are both a gas phase and a liquid phase, and the liquid phase is a single liquid phase, that is, in the liquid phase interval, the solvent in the liquid phase and the light fraction in the liquid phase are in a dissolved state, which is conducive to light The sulfide in the fraction is transferred into the extraction solvent, and once a multi-liquid phase state is formed, it is not conducive to the extraction of the sulfide. In order to improve the absorption capacity of the extraction solvent for sulfides, and to help keep a single liquid phase in the liquid phase region of the extraction distillation column, preferably, the extraction solvent further contains an auxiliary agent, and the auxiliary agent is capable of At least one of alcohols, ketones, organic acids and organic nitrides that are miscible with the main extraction solvent and whose boiling point or dry point is not higher than that of the main extraction solvent and/or or water, and the organic nitrogen compound is at least one of amines, ureas and alcoholamines.

Preferably, the auxiliary agent is an alcohol or carbon atom having a carbon atom number of not more than 6 that can be miscible with the main extraction solvent and whose boiling point or dry point is not higher than the boiling point or dry point of the main extraction solvent. At least one substance and/or water among ketones with no more than 6 carbon atoms, organic acids with no more than 6 carbon atoms, and organic nitrides with no more than 6 carbon atoms, the organic nitrides are amines, urea At least one of alkanolamines and alkanolamines.

Preferably, the alcohols with no more than 6 carbon atoms are at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-pentanol and cyclohexanol.

Preferably, the ketones with no more than 6 carbon atoms are acetone and/or methyl ethyl ketone.

Preferably, the organic acid having no more than 6 carbon atoms is at least one of isobutyric acid, oxalic acid, malonic acid and succinic acid.

Preferably, the organic nitrogen compound with no more than 6 carbon atoms is selected from urea, ethylenediamine, monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, N,N-dimethylethanolamine, N , at least one of N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, n-propanolamine, isopropanolamine and diethylene glycol amine.

More preferably, the auxiliary agent is selected from water, methanol, ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, isobutyric acid, oxalic acid, malonic acid, succinic acid, urea, ethylenediamine, Monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, n-propyl At least one of alkanolamine, isopropanolamine and diethylene glycol amine. Particularly preferably, the auxiliary agent is selected from water, methanol, acetone, methyl ethyl ketone, isobutyric acid, oxalic acid, malonic acid, succinic acid, ethylenediamine, monoethanolamine, N-methylmonoethanolamine, isopropyl At least one of alkanolamine and diethylene glycol amine.

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

Preferably, the adjuvant is a mixture containing water. However, water has a great influence on the formation of multiphase. Once the water content in the solvent is large, it is often easy to form a multiphase state in the extractive distillation column. Therefore, when the auxiliary agent is a mixture containing water, the content of water in the extraction solvent is preferably 0.1-5 wt %, more preferably 0.1-3 wt %.

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

Solvent recovery in the preferred case of the present invention is provided below:

The sulfur-containing solvent rich in sulfide can be recycled after removing the absorbed sulfide. The method of removing sulfide is called solvent recovery. The solvent recovery is carried out by means of distillation, that is, the sulfur-containing solvent from the solvent extraction process is distilled under heating conditions to extract the sulfur-containing material, and the sulfur-containing material includes aromatic hydrocarbons, thiophenes, and thioether compounds from the light ends. , the sulfur-containing material is discharged into the sulfur-containing material after solvent extraction. The solvent after removing the sulfide becomes the recovered solvent and returns to the solvent extraction and distillation process for recycling.

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

Sulfur-containing hydrocarbon materials are removed from the recovered solvent, but side reactions such as oxidation and decomposition will occur during operation, resulting in the formation of some soluble high-boiling compounds such as steady-state salts, organic polymers, sediments and other impurities. The existence and accumulation in the solvent will undoubtedly reduce the solubility of the extraction solvent, thereby reducing the efficiency of gasoline extraction and desulfurization. Therefore, it is necessary to regenerate the solvent to improve the purity of the solvent.

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

Solvent regeneration in the preferred case of the present invention is provided below:

The water injection purification treatment can be realized by carrying out water injection pressure reduction distillation on the solvent, the relatively light residual hydrocarbon material in the recovered solvent is azeotroped with water and discharged from the top of the tower, and the relatively heavy high-boiling point compound impurities in the recovered solvent are recovered as residues. The purified solvent is discharged from the bottom of the solvent regeneration tower, and the purified solvent is discharged from the lower side of the solvent regeneration tower to become the regeneration solvent. Preferably, the water in the water injection purification treatment comes from the 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 and recycled.

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

Preferably, the recovered solvent used for regeneration accounts for 1 to 10 wt % of the entire recovered solvent, more preferably 1 to 5 wt % of the entire recovered solvent.

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

The etherification reaction of the present invention makes it possible to obtain etherified light ends with a reduced olefin content and an increased octane number.

The etherification reaction in the preferred case of the present invention is provided below:

Preferably, the etherification reaction is carried out by contacting the solvent-extracted light fraction with a low-carbon alcohol having no more than 6 carbon atoms.

Preferably, the low-carbon alcohol used in the etherification reaction is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-pentanol and cyclohexanol; particularly preferably methanol.

Preferably, the conditions for the etherification reaction include: the molar ratio of the lower alcohol to the olefin in the light fraction after the 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 MPa ~ 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 can be, for example, a sulfonic acid type ion exchange resin.

More preferably, the condition of contacting the light fraction with the lower alcohol after the solvent extraction is such that the olefin removal rate in the light fraction after etherification is ≮ 35%.

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

In the present invention, after oxidative deodorization, after the light fraction is extracted by solvent, most of the sulfides are removed, and the selective hydrogenation pretreatment can be carried out under more moderate conditions. The active precious metal catalyst is carried out at lower temperature, lower pressure, and lower hydrogen-oil volume ratio to effectively avoid the loss of octane number caused by the hydrogenation of monoolefins.

Preferably, the selective hydropretreatment is carried out in the presence of a transition metal supported catalyst. The selective hydrogenation pretreatment catalyst used in the selective hydrogenation pretreatment can be a hydrogenation or hydrogenation catalyst that can saturate diolefins and avoid monoolefin saturation under certain reaction conditions. The treatment catalyst includes a transition metal supported catalyst, which can be a non-precious metal supported catalyst, a precious metal supported catalyst, or a combination of these two types of catalysts. The transition metal supported catalyst comprises a carrier and a metal active component supported on the carrier, the carrier is selected from at least one of alumina, silica, aluminosilicate, titania, zeolite and activated carbon, The metal active component is selected from at least one of nickel, cobalt, molybdenum, platinum and palladium.

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

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

According to another preferred situation, the light fraction after solvent extraction can also be subjected to adsorption pretreatment by means of adsorbent adsorption 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: subjecting the sulfur-containing material after solvent extraction in step (3) to a selective hydrodesulfurization reaction together with 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 after solvent extraction in step (3) into a catalytic cracking device to carry out catalytic cracking reaction to obtain the material used in step (1). ) at least part of the gasoline feedstock.

The selective hydrodesulfurization reaction in the preferred case of the present invention is provided below:

Preferably, the selective hydrodesulfurization reaction is carried out in a first reaction zone and a second reaction zone which are connected in sequence, and the first reaction zone and the second reaction zone are respectively filled with the first hydrodesulfurization catalyst and the second reaction zone. a second hydrodesulfurization catalyst, the first hydrodesulfurization catalyst and the second hydrodesulfurization catalyst each independently contain an alumina support and/or a silica-alumina support and a hydrogenation active metal component supported on the support, The hydrogenation active metal component is a group VIB non-noble metal element selected from molybdenum and/or tungsten and/or a group VIII non-noble metal element selected from nickel and/or cobalt.

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

Preferably, based on the total amount of the hydrodesulfurization catalyst, the content of the VIB group non-precious metal element in terms of oxides is 2-25 wt %, and the content of the VIII group non-precious metal elements in terms of oxides is 0.2 to 6% by weight. 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 represented by "the reaction temperature (T) of a unit volume of hydrodesulfurization catalyst to achieve the same desulfurization effect when treating the same raw material", and the larger the T, the lower the activity.

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

Preferably, the conditions of the selective hydrodesulfurization reaction are such that the sulfur content in the obtained hydrogenated heavy fraction is ≯ 10 μg/g.

Preferably, the cutting point of the light fraction and the heavy fraction is 80-120°C.

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

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

Preferably, the gasoline feedstock is selected from at least one of catalytically cracked gasoline, 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 ≯ 10 μg/g. Particularly, the gasoline product of step (5) of the present invention is the product obtained by mixing the heavy fraction after hydrogenation and the light fraction after solvent extraction, or the product obtained by mixing the heavy fraction after hydrogenation and the light fraction after etherification .

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

A fractionation system through which the gasoline feedstock is fractionated to obtain light ends and heavy ends;

an oxidative deodorization system, which is used for carrying out an oxidative deodorization reaction on the light fraction to obtain a light fraction after oxidative deodorization;

A solvent extraction system, including a solvent extraction distillation unit and a solvent recovery unit, the solvent extraction and distillation unit is used to perform solvent extraction on the light fractions after oxidative deodorization from the oxidative deodorization system to obtain a sulfur-containing solvent and a solvent-extracted Light ends; the solvent recovery unit is used to separate the sulfur-containing solvent from the sulfide contained therein to obtain the sulfur-containing material after solvent extraction and the recovered solvent from which the sulfide has been removed;

A selective hydrogenation system, the heavy fractions from the fractionation system are introduced into the selective hydrogenation system through pipelines for selective hydrodesulfurization reaction to obtain the heavy fractions after hydrogenation;

The hydrogenated heavy fraction is mixed with the solvent-extracted light fraction and withdrawn as gasoline product through a pipeline.

Preferably, the equipment further comprises an etherification system, and the light fraction after solvent extraction from the solvent extraction system is first introduced into the etherification system through a pipeline for etherification reaction to obtain the light fraction after etherification; then the ether The hydrogenated light ends are combined with the hydrogenated heavy ends to be withdrawn through a line as a gasoline product.

According to a preferred situation, the apparatus further comprises a pipeline for introducing the solvent-extracted sulfur-containing material into the selective hydrogenation system.

According to another preferred situation, the equipment further comprises a cracking system, and the sulfur-containing material after solvent extraction from the solvent extraction system is introduced into the cracking system through a pipeline for catalytic cracking reaction, and the sulphur-containing material in the cracking system is removed. The product is introduced into the fractionation system via a line.

Preferably, the solvent extraction system further includes a solvent regeneration unit for introducing the recovered solvent from the solvent recovery unit into the solvent regeneration unit through a pipeline for water injection purification treatment for regeneration.

Preferably, the selective hydrogenation system comprises a first reaction zone and a second reaction zone connected in sequence to carry out the selective hydrodesulfurization reaction.

According to a preferred specific embodiment, the equipment for deep desulfurization of gasoline of the present invention has the schematic structural diagram shown in FIG. 1 , specifically:

The gasoline feedstock 1 enters the fractionation system 2 through the pipeline, and the heavy fraction 3 and the light fraction 4 are fractionated. The heavy fraction 3 flows out through the pipeline, and is mixed with hydrogen into the selective hydrogenation system 13, and is subjected to selective hydrogenation reaction in the first reaction zone under the action of the relatively low activity first hydrodesulfurization catalyst, and then enters the second hydrogenation system. The second reaction zone performs selective hydrogenation reaction under the action of the second hydrodesulfurization catalyst with relatively high activity, and flows out from the pipeline to obtain the hydrogenated heavy fraction 10 . The light fraction 4 from the fractionation system 2 enters the oxidative deodorization system 5 through the pipeline, and is contacted with air under the action of the supported metal phthalocyanine catalyst, and the mercaptan in the light fraction is oxidized to disulfide, and the light fraction 6 after oxidative deodorization is obtained.

After oxidative deodorization, the light fraction 6 enters the solvent extraction system 7 and contacts with the extraction solvent, and the remaining sulfide in the light fraction is transferred to the extraction solvent to obtain the light fraction 9 after solvent extraction. Preferably, the solvent extraction The latter light fraction 9 is passed into the etherification system 11 via the pipeline.

The sulfur-containing solvent that has absorbed the sulfide enters the solvent recovery unit for solvent recovery, and the absorbed sulfide is separated from the extraction solvent under the condition of distillation to obtain a sulfur-containing material 8 after solvent extraction, and the sulfur-containing material after the solvent extraction is obtained. 8 enters the selective hydrogenation system 13 together with the heavy fraction 3, or is incorporated into the cracking system for cracking reaction, and the gasoline fraction obtained after cracking is used as a part of the gasoline feedstock 1 of the present invention. At the same time, a part of the recovered solvent flows into the solvent regeneration unit and is contacted with water for purification and regeneration. The hydrocarbons absorbed in the solvent (azeotrope with water) and the heavy raffinate rich in impurities are separated from the regeneration solvent, and the regeneration solvent is incorporated into the recovery solvent. , continue to contact with the light fraction after solvent extraction for recycling.

After entering the solvent extraction in the etherification system 11, the light fraction 9 is preferably subjected to pre-hydroprocessing, and after the treatment, it is contacted with low-carbon alcohol, so that the olefin in the light fraction is reacted with the low-carbon alcohol to generate ether, and the etherified fraction is obtained. Light Ends 12.

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

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

The present invention adopts the method of treating sulfur-containing gasoline in stages, and adopts the treatment methods of oxidative deodorization, solvent extraction and selective hydrogenation for gasoline in each fraction of the gasoline.

In order to effectively reduce the sulfur content of the gasoline fraction, the present invention adopts an extraction solvent combination with significant selective absorption of sulfides on the basis of oxidative deodorization, and adopts the method of extractive distillation to extract and remove the sulfur in the gasoline fraction. The extraction solvent is recovered by the method of organic matter and vacuum distillation, and the light fraction after solvent extraction is completely separated from the extraction solvent (basically not entrained with each other), and subsequent treatment is not required, and the extraction solvent and the absorbed sulfide are recovered during recovery. Hydrocarbons and sulfur-containing materials can also be well separated, and a part of the recovered solvent is regenerated, which overcomes the shortcomings of incomplete regeneration of conventional solvents. In addition, impurities such as high-boiling polymers and deposits accumulated in the solvent are removed, and the purification effect is remarkable during solvent regeneration, so that the recycling extraction capacity of the recovered solvent can be effectively restored after being mixed with a part of the regenerated solvent. Due to the improvement of the desulfurization efficiency, the dry point of the light ends can be appropriately increased in the present invention, so that the yield of the light ends during gasoline fractionation can be increased and the yield of the heavy ends can be reduced, and the processing capacity of the heavy ends entering the hydrogenation system can be reduced accordingly. , the octane number loss caused by the hydrogenation of heavy fractions can be effectively reduced.

If liquid-liquid solvent extraction and positive pressure solvent distillation recovery are adopted, the solvent with high selective absorption efficiency for thiophene compounds is usually not effective in absorbing sulfide sulfur, and it is difficult to deeply desulfurize. Entrainment, the gasoline fraction after extraction often needs subsequent treatment, such as water washing, etc., and the solvent after extraction is usually difficult to recover completely because of the relatively large amount of materials absorbed, which is not conducive to the effective use of the solvent.

The invention adopts oxidative deodorization to pre-treat the light fraction, which can avoid the problem of alkali residue treatment caused by the use of lye extraction, and the process is relatively simple, and the refinery usually has a gasoline deodorization device. ready to use.

In the present invention, solvent extraction produces a sulfur-rich material. Under the conditions of the present invention, these sulfur-rich materials can enter step 2) for selective hydrodesulfurization reaction, and have little impact on the hydrogenation system, and will not cause a large loss of octane number. At the same time, these sulfur-rich materials can also be preferably incorporated into the catalytic cracking riser for cracking reaction, which is more advantageous in operation.

Another significant advantage of the gasoline desulfurization process provided by the present invention is that the selective hydrodesulfurization system of the present invention adopts two kinds of hydrogenation catalysts to cooperate, and the catalytic hydrodesulfurization is carried out in the first reaction zone and the second reaction zone respectively. After the reaction, a gasoline product with a sulfur content of not more than 10 μg/g can be stably obtained, and the loss of octane number is smaller.

In order to reduce the loss of octane number, the present invention preferably configures a light end etherification step after the solvent extraction step, so that olefins in the light end are reacted with lower alcohols to generate ether compounds with high octane number. Since most of the sulfides and other heteroatom compounds in the light fraction are removed by solvent extraction, the pretreatment before etherification can be carried out under mild conditions, which is beneficial to reduce operating costs.

In the method of the present invention, the liquid yield of the gasoline product obtained by adopting extractive distillation and other process means is higher than that of the existing process including conventional liquid-liquid extraction. Moreover, in the liquid-liquid extraction process in the prior art, oil-carrying agents and oil-carrying agents are prone to occur, and further processing such as water washing is required, which is likely to cause loss of liquid recovery.

All in all, the deep desulfurization process of the present invention is superior in terms of desulfurization effect, reduction of octane number loss, feasibility and stability of device operation, and environmental protection effect, which is incomparable to the prior art. .

The present invention will be described in detail below by way of examples. In the following examples, all raw materials used are commercially available unless otherwise specified.

One of the selective hydrodesulfurization catalysts used below is the catalyst with the trade name RSDS-11 provided by the Changling Catalyst Factory of the Catalyst Branch of China Petrochemical Corporation.

The composition of another selective hydrodesulfurization catalyst Cat1: the content of cobalt oxide is 4.3% by weight, the content of molybdenum oxide is 12.4% by weight, and the balance is alumina carrier.

The composition of the selective hydrogenation pretreatment catalyst Cat2 used below is: 0.5 wt% Pd, the balance being Al ₂ O ₃ support.

The oxidative deodorization catalysts and oxidative deodorization aids used below are all provided by Guangzhou Dayou Fine Chemical Plant, and the trade names are HUS-C01 and HUS-P01, respectively.

Example 1

In this example, the equipment shown in FIG. 1 is used to perform deep desulfurization treatment on the gasoline feedstock A in Table 1.

Gasoline Feed A was fractionated at a cut point temperature of 95°C to obtain a 50 wt% yield of light ends and a 50 wt% yield of heavy ends.

In the oxidative deodorization system for light fractions after fractionation, the light fractions after fractionation are oxidized under the action of HUS-CO1 catalyst, the reaction temperature is 40°C, the pressure is 0.6MPa, the liquid hourly space velocity is 1.0h ^-1 , and the air injection amount is oxidized mercaptan. 2.4 times of the required theoretical amount, the injection amount of oxidative deodorization aid HUS-P01 is 5 μg/g (compared with light distillate); the mercaptan sulfur content of light distillate after oxidative deodorization is ≯ 1 μg/g.

In the solvent extraction system, the light fractions after oxidative deodorization are subjected to solvent extraction distillation in a solvent extraction distillation column to obtain the light fractions after solvent extraction and sulfur-containing solvent, and the sulfur-containing solvent is the total amount of light fractions after oxidative deodorization. 5% by weight. Then in the solvent recovery tower by vacuum distillation, the sulfur-containing solvent and the sulfide contained therein are separated to obtain the sulfur-containing material after solvent extraction and the recovery solvent from which the sulfide has been removed:

In the solvent extraction distillation column: the feed weight ratio of the extraction solvent to the light fraction after oxidative deodorization is 3:1, the temperature at the bottom of the column is 170 °C, the temperature at the top of the column is 80 °C, the pressure at the top of the column is 180 kPa, and the extraction solvent The main extraction solvent is N-formylmorpholine, the auxiliary agent is water and methanol, and the content of the auxiliary agent is 5% by weight of the extraction solvent, and the content of water in the extraction solvent is 1% by weight.

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

In the solvent regeneration tower: the recovered solvent used for regeneration is 3% by weight of the total recovered solvent, the temperature at the bottom of the tower is 180°C, the temperature at the top of the tower is 100°C, the pressure at the top of the tower is 10kPa, the residual liquid is discharged from the bottom of the tower, and the solvent is regenerated. After mixing with the recovered solvent, it is recycled. The stripping water used comes from the condensed water collected by the solvent extraction distillation column and the solvent recovery column. The sulfur content in the light ends after solvent extraction was ≯ 5 μg/g.

The light fractions after solvent extraction are subjected to selective hydrogenation pretreatment and etherification treatment. The selective hydrogenation pretreatment conditions are as follows: the selective hydrogenation pretreatment catalyst Cat2 is used, the reaction temperature is 80 °C, and the reaction pressure is 1.0 MPa, The liquid hourly volume space velocity is 4.0h ^-1 , and 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, and the etherification conditions are: using a sulfonic acid type ion exchange resin as the etherification catalyst, methanol and the olefin in the solvent extraction light fraction are separated. The molar ratio was 1.02:1, the liquid hourly space velocity was 2.0h ^-1 , the reaction temperature was 70°C, and the reaction pressure was 1.0MPa to obtain etherified light fractions.

In the selective hydrogenation system for heavy fractions, the sulfur-containing material after solvent extraction is subjected to selective hydrodesulfurization reaction together with the fractionated heavy fraction. RSDS ^- 11 catalyst was used in the first reaction zone at a reaction temperature of 200°C, and a catalyst Cat1 was used in the second reaction zone at a reaction temperature of 300°C. After selective hydrogenation, a heavy fraction after hydrogenation is obtained, and the sulfur content in the heavy fraction after hydrogenation is 8 μg/g.

The light fraction after solvent extraction and the heavy fraction after hydrogenation are mixed into low-sulfur gasoline product B; or the light fraction after etherification and the heavy fraction after hydrogenation are mixed into low-sulfur and low-olefin gasoline product C.

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

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

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

It can be seen from this that the combined process of the present invention has a good desulfurization effect and the effect of reducing the loss of octane number. After etherification of light ends, the olefin content can be greatly reduced, and the octane number can be effectively recovered or even increased.

In addition, in this embodiment, since the extraction solvent containing auxiliary agents is used in the extraction and distillation, the effective utilization rate of the extraction solvent is significantly improved, the frequency of solvent regeneration is reduced, and the relative reduction in energy consumption and operating costs are caused. relative reduction.

Table 1

Comparative Example 1

In this comparative example, the gasoline feedstock is first fractionated to obtain light ends and heavy ends, then the light ends are subjected to lye extraction, and the heavy ends are subjected to hydrodesulfurization. The gasoline raw material of this comparative example is the raw material oil A in Table 1, the difference is:

The cutting point of the gasoline raw material in Example 1 is limited to 60 ° C, and the yield of the light fraction with a yield of 20 wt % and the yield of the heavy fraction with a yield of 80 wt % is obtained after fractionation;

The light fraction is treated by lye extraction, and the lye extraction conditions are as follows: the volume ratio of the light fraction and the lye in contact is 8:2, the temperature is 25 ° C, and the pressure is 0.6 MPa. Fraction; the sulfur-containing lye that has absorbed thiol is oxidized under the action of metal phthalocyanine catalyst suspended in the lye, and the amount of metal phthalocyanine (sulfonated cobalt phthalocyanine, commercially available product) in the lye is 500 μg /g, the injection amount of air in the oxidation process is 2.4 times the theoretical amount, the pressure during oxidation is 0.5MPa, and the temperature is 40 °C; The hydrogenated heavy fractions are mixed to remove the disulfides in the oxidized sulfur-containing lye by reverse extraction to obtain regenerated lye and lye to extract sulfur-containing materials, and the regenerated lye is recycled for use; Sulfur-containing materials are continuously discharged.

In this comparative example, only the combination of the lye extraction step of the light fraction and the selective hydrogenation step of the heavy fraction is adopted, and the solvent extraction and etherification treatment of the light fraction is not performed.

Only one hydrogenation catalyst, RSDS-11, was used in the selective hydrogenation system for heavy ends, and the hydrogenation temperature was 320°C.

The sulfur content of the light distillate after lye extraction is ≯ 10 μg/g, while the sulfur content of the heavy distillate after hydrogenation is 9 μg/g.

In this comparative example, the light fractions after lye extraction and the heavy fractions after hydrogenation are mixed into low-sulfur gasoline product D, and the results are shown in Table 2.

As can be seen from Table 2, in order to obtain gasoline product D with sulfur content ≯ 10 μg/g, compared with the combined process of obtaining gasoline product B in Example 1, the olefin saturation rate of the combined process of Comparative Example 1 is as high as 50.0%, and the Alkane RON losses are as high as 5.5 units.

Table 2

Oil name Raw material A Light ends after fractionation heavy fractions after fractionation gasoline product D Density(20℃)/(g/cm³) 0.7242 0.6205 0.7481 0.7225 Sulfur content/(μg/g) 878 135 1064 9 Thiol sulfur content/(μg/g) 50 127 31 4 Olefin content/vol% 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

In this example, the equipment shown in FIG. 1 is used to carry out deep desulfurization treatment on the gasoline raw material E.

The gasoline feedstock E was fractionated at a cut point temperature of 120°C to obtain a yield of 60% by weight of light ends and a yield of 40% by weight of heavy ends.

In the oxidative deodorization system for light fractions after fractionation, the light fractions after fractionation are oxidized under the action of HUS-C01 catalyst, the reaction temperature is 55°C, the pressure is 0.6MPa, the liquid hourly space velocity is 1.2h ^-1 , and the air injection amount is oxidized mercaptan. 2.4 times of the required theoretical amount, the injection amount of oxidative deodorization aid HUS-P01 is 5 μg/g (compared with light distillate); the mercaptan sulfur content of light distillate after oxidative deodorization is ≯ 1 μg/g.

In the solvent extraction system, the light fractions after oxidative deodorization are subjected to solvent extraction distillation in a solvent extraction distillation column to obtain the light fractions after solvent extraction and sulfur-containing solvent, and the sulfur-containing solvent is the total amount of light fractions after oxidative deodorization. 7% by weight. Then in the solvent recovery tower by vacuum distillation, the sulfur-containing solvent and the sulfide contained therein are separated to obtain the sulfur-containing material after solvent extraction and the recovery solvent from which the sulfide has been removed:

In the solvent extraction distillation column: the feed weight ratio of the extraction solvent to the light fraction after oxidative deodorization is 4:1, the temperature at the bottom of the column is 150 °C, the temperature at the top of the column is 95 °C, the pressure at the top of the column is 200 kPa, and the extraction solvent The main extraction solvent is N-methyl-2-pyrrolidone, the auxiliary agent is acetone, and the content of the auxiliary agent is 4.2% by weight of the extraction solvent.

In the solvent recovery tower: the temperature at the bottom of the tower is 200°C, the temperature at the top of the tower is 90°C, the pressure at the top of the tower is 40kPa, and the weight ratio of the stripping steam to the sulfur-containing solvent is 0.25:1.

In the solvent regeneration tower: the recovered solvent used for regeneration is 5% by weight of the total recovered solvent, the temperature at the bottom of the tower is 170°C, the temperature at the top of the tower is 100°C, the pressure at the top of the tower is 8kPa, the residual liquid is discharged from the bottom of the tower, and the solvent is regenerated. After mixing with the recovered solvent, it is recycled. The stripping water used comes from the condensed water collected by the solvent extraction distillation column and the solvent recovery column. The sulfur content in the light ends after solvent extraction was 3 μg/g.

The light fractions after solvent extraction are subjected to selective hydrogenation pretreatment and etherification treatment. The selective hydrogenation pretreatment conditions are: use the selective hydrogenation pretreatment catalyst Cat2, the reaction temperature is 100 ° C, the reaction pressure is 1.2 MPa, The liquid hourly volume space velocity is 5h ^-1 , and 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, and the etherification conditions are: using a sulfonic acid type ion exchange resin as the etherification catalyst, methanol and the olefin in the solvent extraction light fraction are separated. The molar ratio was 1.05:1, the reaction temperature was 80° C., and the reaction pressure was 1.0 MPa to obtain light fractions after etherification.

In the selective hydrogenation system for heavy fractions, the sulfur-containing material after solvent extraction is subjected to selective hydrodesulfurization reaction together with the fractionated heavy fraction. The RSDS-11 catalyst was used in the first reaction zone at a reaction temperature of 220°C, the second reaction zone was a catalyst Cat1 at a reaction temperature of 295°C, the liquid hourly volume space velocity was 3.0h ^-1 , and the volume ratio of hydrogen to oil was 400. After selective hydrogenation, a heavy fraction after hydrogenation is obtained, and the sulfur content in the heavy fraction after hydrogenation is 6 μg/g.

The light fraction after solvent extraction and the heavy fraction after hydrogenation are mixed to form low-sulfur gasoline product F;

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 gasoline product F is as high as 98.7%, and the sulfur content of the product is only 4 μg/g, which meets the requirement of national V emission standard that the sulfur content of gasoline products is not more than 10 μg/g, and the olefin saturation rate is 13.5 %, the RON loss value is 0.5 units.

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

In addition, in this embodiment, since the extraction solvent containing auxiliary agents is used in the extraction and distillation, the effective utilization rate of the extraction solvent is significantly improved, the frequency of solvent regeneration is reduced, and the relative reduction in energy consumption and operating costs are caused. relative reduction.

table 3

Example 3

This embodiment is carried out using the same raw material oil E and the same combined desulfurization process and the same process parameters as in Example 2, and the difference is:

The extraction solvent used in the solvent extraction process of this example does not contain auxiliary agents, and the rest are the same as those in Example 2. As a result, the sulfur content in the light ends after solvent extraction is 6 μg/g.

After selective hydrogenation, a heavy fraction after hydrogenation is obtained, and the sulfur content in the heavy fraction after hydrogenation is 6 μg/g.

The light fraction after solvent extraction and the heavy fraction after hydrogenation are mixed into a low-sulfur gasoline product H; or the light fraction after etherification and the heavy fraction after hydrogenation 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.

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

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

Comparing the results of this example and Example 2, it can be seen that the use of an extraction solvent containing an auxiliary agent in the solvent extraction process can make the sulfur content of the gasoline product obtained by the method of the present invention lower. If the sulfur content of the product is to be completely consistent, the degree of hydrogenation of the heavy fraction in this example needs to be increased, which will cause the olefin content of product H (and product I) to decrease, and the loss of octane number will be higher than that of Example 2. big.

In addition, in this embodiment, since no auxiliary agent is used, the effective utilization rate of the extraction solvent will be reduced during the extraction and distillation, which is not conducive to the long-term extraction.

Table 4

It can be seen from the above results that the method provided by the present invention can obtain a gasoline product with lower sulfur on the premise of avoiding the large loss of octane number. Moreover, in the process of solvent extraction, the use of additives has a certain promotion effect on solvent extraction, and it can be further inferred that when the solvent is used in a long-term cycle, especially when the solvent is decomposed and the impurity content increases, the auxiliary agent will affect the solvent. The effect of extracting sulfide is more favorable. In particular, with the etherification reaction process, the octane number of the gasoline product of the present invention can be increased, the sulfur content can be further reduced, and the olefins can also be greatly reduced, which is beneficial to meet the requirements of the future National VI gasoline standard.

The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details of the above-mentioned embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner unless they are inconsistent. In order to avoid unnecessary repetition, the present invention provides The combination method will not be specified otherwise.

In addition, the various embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the spirit of the present invention, they should also be regarded as the contents disclosed in the present invention.

Claims (40)

1. A method for deep desulfurization of gasoline, comprising: (1) Fractionation of gasoline feedstock at a cutting point temperature of 70~140°C to obtain light and heavy fractions; (2) in the presence of an oxidative deodorization catalyst, contacting the light fraction with an oxidant to carry out an oxidative deodorization reaction to obtain a light fraction after oxidative deodorization; (3) contacting the oxidatively deodorized light fraction with an extraction solvent to perform solvent extraction by distillation, obtaining a sulfur-containing solvent and a light fraction after solvent extraction, and then combining the sulfur-containing solvent with the solvent-containing light fraction by vacuum distillation; The sulfide is separated to obtain the sulfur-containing material after solvent extraction and the recovery solvent from which the sulfide has been removed, and in the solvent extraction process, the weight ratio of the extraction solvent to the light fraction after the oxidative deodorization is (0.5 ~20): 1; the solvent extraction is carried out in an extractive distillation column, and the conditions in the extractive distillation column include: the pressure at the top of the column is 100kPa ~ 500kPa; the temperature at the top of the column is 65 ~ 180 ℃; the temperature at the bottom of the column The temperature is 80-260°C; the extraction solvent contains a main extraction solvent and 0.1-20% by weight of auxiliary agents, and the main extraction solvent is selected from tetraethylene glycol, pentaethylene glycol, furfural, furfuryl alcohol, dimethyl glycol At least one of formamide, triethylene glycol methyl ether, acetonitrile and a solvent with a boiling point of 175-320°C; the auxiliary agent is miscible with the main extraction solvent and its boiling point or dry point is not higher than the At least one substance and/or water among alcohols, ketones, organic acids and organic nitrides at the boiling point or dry point of the main extraction solvent, and the organic nitrides are among amines, ureas and alcoholamines at least one of; The conditions for separating the sulfur-containing solvent from the sulfide contained therein by vacuum distillation include: the top pressure of the solvent recovery tower is 10kPa～100kPa, the top temperature is 50～100℃, and the bottom temperature is 100℃～250℃ ℃, the weight ratio of the stripping steam to the sulfur-containing solvent is (0.01-5.0): 1; (4) contacting the heavy fraction with a hydrodesulfurization catalyst to carry out a selective hydrodesulfurization reaction to obtain a heavy fraction after hydrogenation; (5) mixing the heavy fraction after the hydrogenation of step (4) with the light fraction after the solvent extraction of step (3) to obtain a gasoline product; The method further includes: performing water injection purification treatment on at least a part of the recovered solvent in a solvent regeneration tower to regenerate; the regeneration conditions in the solvent regeneration tower include: the pressure at the top of the tower is 1kPa-10kPa, and the temperature at the top of the tower is 90-110 °C, the column bottom temperature is 120 °C to 200 °C, and the weight ratio of the injected water to the recovered solvent is (0.1 to 10):1. 2 . The method according to claim 1 , wherein the method further comprises: before mixing with the hydrogenated heavy fraction of step (4), first extracting the solvent obtained in step (3) to light The fractions are etherified to obtain etherified light fractions; and then the etherified light fractions are mixed with the hydrogenated heavy fractions in step (4) to obtain the gasoline product. 3. The method according to claim 2, wherein the etherification reaction is carried out by contacting the solvent-extracted light fraction with a lower alcohol having a carbon number of not more than 6. 4. method according to claim 3, wherein, described low-carbon alcohol is at least one in methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-pentanol and cyclohexanol . 5 . The method according to claim 3 , wherein the conditions for the etherification reaction include: the molar ratio of the lower alcohol to the olefin in the light fraction after extraction by the solvent is (0.5-3):1 , the contact temperature is 20 ~ 100 ℃, and the pressure is 0.3 MPa ~ 2.0 MPa. 6 . The method according to claim 5 , wherein the conditions for the etherification reaction include: the molar ratio of the lower alcohol to the olefin in the light fraction after the solvent extraction is (1.0-1.2): 1 . 7. The method of claim 2, wherein the etherification reaction is carried out in the presence of a strongly acidic ion exchange resin as an etherification catalyst. 8. The method according to any one of claims 2-7, wherein the method further comprises: before carrying out the etherification reaction, performing adsorption pretreatment and/or performing adsorption pretreatment on the light fraction after the solvent extraction Selective hydrotreating. 9. The method of claim 8, wherein the selective hydrotreating pretreatment is performed in the presence of a transition metal supported catalyst comprising a support and an active metal supported on the support component, the carrier is selected from at least one of alumina, silica, aluminosilicate, titanium oxide, zeolite and activated carbon, and the metal active component is selected from nickel, cobalt, molybdenum, platinum and palladium at least one. 10 . The method according to claim 9 , wherein the carrier in the transition metal supported catalyst is alumina, and the supported metal active component in terms of oxide is 0.05 to 15 wt %. 11 . 11 . The method according to claim 9 , wherein the conditions for the selective hydrogenation pretreatment include: a hydrogen partial pressure of 0.1 MPa to 2.0 MPa, a temperature of room temperature to 250° C., and a liquid hourly volume space velocity of 1.0 h. 12 . ^-1 to 10.0h ^-1 , the volume ratio of hydrogen to oil is 1 to 100. 12. The method according to any one of claims 1-7, wherein the method further comprises: selectively hydrodesulfurizing the sulfur-containing material after solvent extraction in step (3) together with the heavy fraction response; or The sulfur-containing material after solvent extraction in step (3) is introduced into a catalytic cracking unit for catalytic cracking reaction to obtain at least part of the gasoline feedstock used in step (1). 13. The method according to any one of claims 1-7, wherein, in the solvent extraction process, the weight ratio of the extraction solvent to the light ends after oxidative deodorization is (1 to 5) :1. 14. The method according to any one of claims 1-7, wherein the conditions in the extractive distillation column include: the pressure at the top of the column is 110kPa-300kPa; and the temperature at the bottom of the column is 140-200°C. 15. The method according to any one of claims 1-7, wherein the boiling point of the main extraction solvent is 175-250°C. 16. The method according to any one of claims 1-7, wherein the main extraction solvent is selected from the group consisting of 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-formylmorpholine, triethylene glycol, tetraethylene glycol, pentaethylene glycol, triethylene glycol methyl ether, ethylene carbonate, propylene carbonate, propylene carbonate At least one of ester, nitrobenzene, polyethylene glycol with a relative molecular mass between 200 and 400, and polyethylene glycol methyl ether with a relative molecular mass between 200 and 400. 17. The method 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, in the auxiliary agent contained in the extraction solvent, the number of carbon atoms of the alcohols, ketones, organic acids and organic nitrides are not greater than 6. 19. The method according to any one of claims 1-7, wherein, in the extraction solvent, the content of the auxiliary agent is 0.5-15% by weight. 20. The method according to any one of claims 1-7, wherein the auxiliary agent is selected from the group consisting of water, methanol, ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, isobutyric acid, oxalic acid , malonic acid, succinic acid, urea, ethylenediamine, monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, At least one of diethanolamine, N-methyldiethanolamine, triethanolamine, n-propanolamine, isopropanolamine and diethylene glycolamine. 21. The method according to claim 20, wherein the auxiliary agent is selected from the group consisting of water, methanol, acetone, methyl ethyl ketone, isobutyric acid, oxalic acid, malonic acid, succinic acid, ethylenediamine, monoethanolamine, At least one of N-methylmonoethanolamine, isopropanolamine and diethylene glycolamine. 22. The method according to any one of claims 1-7, wherein the auxiliary agent is a mixture containing water, and the content of water in the extraction solvent is 0.1 to 5% by weight. 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 method according to any one of claims 1-7, wherein the conditions for separating the sulfur-containing solvent from the sulfur compounds contained therein by distillation under reduced pressure include: a column bottom temperature of 120-200°C. 25. The method according to any one of claims 1-7, wherein the regeneration conditions in the solvent regeneration tower include: the temperature at the top of the tower is 96-105°C, the temperature at the bottom of the tower is 150°C-200°C, and the injection The weight ratio of the water to the recovered solvent is (0.5-5):1. 26. The method of any one of claims 1-7, wherein the recovered solvent used for regeneration accounts for 1-10 wt% of the total recovered solvent. 27. The method of claim 26, wherein the recovered solvent used for regeneration accounts for 1-5 wt% of the total recovered solvent. 28. The method of any one of claims 1-7, wherein the selective hydrodesulfurization reaction is carried out in a first reaction zone and a second reaction zone connected in sequence, the first reaction zone and The second reaction zone is loaded with a first hydrodesulfurization catalyst and a second hydrodesulfurization catalyst, and the first hydrodesulfurization catalyst and the second hydrodesulfurization catalyst independently contain alumina support and/or silica-alumina A carrier and a hydrogenation active metal component supported on the carrier, the hydrogenation active metal component being a VIB group non-precious metal element selected from molybdenum and/or tungsten and/or an VIII selected from nickel and/or cobalt Group of non-precious metal elements. 29. The method 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 macropores Zeolite and/or medium pore zeolite. 30. The method according to claim 28, wherein, based on the total amount of the hydrodesulfurization catalyst, the content of the VIB group non-precious metal element in terms of oxides is 2-25 wt%, and the VIII group non-noble metal element is 2-25 wt% The content of the non-precious metal element in terms of oxide is 0.2 to 6% by weight. 31. The method according to claim 28, wherein the reaction conditions of the first reaction zone and the second reaction zone independently comprise: a hydrogen partial pressure of 0.1 MPa to 4.0 MPa, and a reaction temperature of 200° C. to 440° C. , the liquid hourly volume space velocity is 1.0h ^-1 ～ 10.0h ^-1 , and the volume ratio of hydrogen to oil is 200～1000. 32. The method according to claim 31, wherein the reaction conditions of the first reaction zone and the second reaction zone independently comprise: a hydrogen partial pressure of 1.0 MPa to 3.2 MPa, and a reaction temperature of 200°C to 300°C , the liquid hour volume space velocity is 2.0h ^-1 ~ 6.0h ^-1 , and the 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 according to claim 33, wherein the conditions for the oxidative deodorization reaction include: the reaction temperature is 0～300°C; the reaction pressure is 0.01MPa～7.0MPa; the liquid hourly volume space velocity is 0.05～10h ⁻¹ . 35. The method according to claim 34, wherein the conditions for the oxidative deodorization reaction include: the reaction temperature is from room temperature to 200°C; the reaction pressure is from 0.1 ^MPa to 2.0 MPa; 5.0h ^-1 . 36. The method according to claim 1, wherein the oxidative deodorization catalyst is a supported metal phthalocyanine catalyst, and the supported metal phthalocyanine catalyst contains a carrier and a metal phthalocyanine supported on the carrier, and the supported metal phthalocyanine catalyst The carrier is a porous material, and the loading amount of the metal phthalocyanine is 0.05 to 10% by weight. 37. The method of claim 36, wherein the supported amount of the metal phthalocyanine is 0.1 to 5 wt%. 38. The method according to claim 1, wherein the cut points of the light ends and the heavy ends are 80-120°C. 39. The method according to claim 38, wherein, based on the gasoline feedstock, the yield of the light ends is 40-60 wt%, and the yield of the heavy ends is 40-60 wt%; The gasoline raw material is selected from at least one of catalytically cracked gasoline, catalytically cracked gasoline, straight-run gasoline, coker gasoline, pyrolysis gasoline and thermally cracked gasoline. 40. The method according to any one of claims 1-7, wherein, in step (5), the sulfur content of the obtained gasoline product is ≯ 10 μg/g.

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