CN108018076A

CN108018076A - The method of deep desulfurization of gasoline and the equipment for deep desulfurization of gasoline

Info

Publication number: CN108018076A
Application number: CN201610964557.6A
Authority: CN
Inventors: 潘光成; 常春艳; 李涛; 唐文成; 习远兵; 赵丽萍; 田龙胜; 褚阳; 李明丰; 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: 2018-05-11
Anticipated expiration: 2036-10-28
Also published as: CN108018076B

Abstract

The present invention relates to the field of refinement of hydrocarbon material, discloses a kind of method of deep desulfurization of gasoline and the equipment for deep desulfurization of gasoline, and this method includes：(1) gasoline stocks are fractionated；(2) light fraction is contacted to carry out solvent extraction with extraction solvent, is then separated sulfur-bearing solvent with the sulfide wherein contained by distilling；(3) light fraction after solvent extraction is contacted with lye to carry out caustic extraction or contact light fraction after solvent extraction with adsorbent；(4) heavy distillat is contacted with making choice property hydrodesulfurization reaction with Hydrobon catalyst, heavy distillat after being hydrogenated with；(5) mixed by heavy distillat after hydrogenation with light fraction after caustic extraction or with light fraction after absorption to obtain gasoline products.The gasoline products of more low-sulfur on the premise of the greater loss of octane number is avoided, can be obtained by the method for the foregoing offer of the present invention.

Description

The method of deep desulfurization of gasoline and the equipment for deep desulfurization of gasoline

Technical field

The present invention relates to the field of refinement of hydrocarbon material, and in particular, to the method and one kind of a kind of deep desulfurization of gasoline For the equipment of deep desulfurization of gasoline, combined more particularly, to a kind of sour gasoline by being hydrogenated with mode with non-hydrogenation mode The deep desulfuration technique formed.

Background technology

It is well known that the discharge of poisonous and harmful substances drastically influence air quality in vehicle exhaust, for this reason, the world is each State is all to defining increasingly stringenter standard as the oil quality of engine fuel.China is in 1 day January in 2013 complete No. IV discharge standard is carried out in the range of state, and carries out No. V discharge standard in big cities such as Beijing, Shanghai.No. IV, No. V row The standard of putting respectively provides sulfur content in motor petrol and is not more than 50 μ g/g and 10 μ g/g.

Sulphur in gasoline mostlys come from catalytically cracked gasoline, develops as oil product processes raw material to heaviness direction, will The sulfur content of catalytically cracked gasoline is caused further to increase.Therefore, the sulfur content for reducing catalytically cracked gasoline is to reduce finished product vapour The key point of oily sulfur content.

Sulphur in gasoline mainly includes thio-alcohol, thioether class, (including thiophene and thiophene derive for disulfide class and thiophene-based Thing) etc..As in the gasoline standard of fuel, its mercaptan sulfur content and total sulfur content have been prescribed highest limit value.When mercaptan sulfur contains Measure exceeded or total sulfur content it is exceeded when must carry out removal of mercaptans or desulfuration purification to gasoline.

Since the catalytically cracked gasoline as motor petrol pond blend component is rich in alkene, using conventional hydro mode it is easy because Cause loss of octane number larger for the saturation of alkene.In order to avoid the greater loss of octane number in process, people are usual Desulfuration purification is carried out to catalytically cracked gasoline by the way of segment processing.

US3957625 reports a kind of method of gasoline desulfurization.The method is that gasoline is cut into light, weight two parts, The sulfur content in gasoline is reduced by way of to heavy naphtha making choice property hydrotreating.And US6610197 reports A kind of method of gasoline desulfurization in road, this method are that gasoline is cut into light, weight two parts, and light fraction is carried out at non-hydrogenation Reason, hydrotreating is carried out to heavy distillat, and the sulfur content in gasoline is reduced with this.

US6623627 reports a kind of production method of low-sulphur oil, and this method is that gasoline is cut into basic, normal, high boiling Point three parts cut, wherein the low boiler cut containing mercaptan contacts selectively removing mercaptan with lye, the mid-boiling point containing thiophene evaporates Point desulfurization is carried out by extracting, the extract containing thiophene of intermediate boiling fraction carries out desulfurization with high boiling fraction in hydrodesulfurizationzone zone Reaction, then will respectively handle after it is light, in, heavy distillat be mixed to get sulfur content reduction gasoline products.The low boiling point evaporates The mode for being contacted with lye and being to take caustic extraction is divided to carry out, the lye carries out oxidation regeneration after mercaptan is extracted, and passes through The mode of sedimentation is isolated disulphide Posterior circle caused by oxidizing process and is used.But disclosure does not contain the prior art The solvent extraction method of the intermediate boiling fraction of thiophene.

CN102851069A reports a kind of method of gasoline desulfurization, and this method includes gasoline cutting fractionation boiling range is opposite High heavy distillat and the relatively low light fraction of boiling range；It is under the conditions of selective hydrodesulfurization, heavy distillat and hydrogen and hydrogenation is de- Sulfur catalyst contacts the hydrodesulfurization of making choice property, obtains the heavy distillat after desulfurization；Light fraction is contacted with lye and is gently evaporated Divide desulfurization, by the weight after the obtained lye for absorbing sulfide and oxidant and oxidation catalyst and a part of desulfurization Cut contact is carried out at the same time alkali liquid regeneration and lye desulfurization so that the salt of the sulfide in lye is oxidized to disulphide, at the same time Make the disulphide in lye extract the desulfurization after heavy distillat in, be then separated, and tail gas is discharged；Will To at least a portion described in absorb the heavy distillat of disulphide and come back for the selective hydrodesulfurization；By the desulfurization The light fraction after heavy distillat and desulfurization afterwards is mixed to get product.

CN103555359A discloses a kind of process for deep desulphurization of catalytically cracked gasoline, and this method is also to be taken out by solvent The mode carried removes the sulfide in gasoline fraction.Its solvent extraction part is using liquid-liquid extraction desulfurization mode.

CN103740405A discloses a kind of alkali cleaning-extraction-hydrogenation combination technique for producing low-sulphur oil, the technique be by Gasoline is cut into light, heavy distillat, and light fraction carries out abstraction desulfurization again after alkali refining, and by the sulfur component extracted and again Cut, which mixes, carries out selective hydrogenation, and the heavy distillat after light fraction and selective hydrogenation after abstraction desulfurization is mixed into low-sulfur vapour Oil product.The alkali refining is that the mode for taking simple alkali cleaning carries out, and it is serious necessarily to consume alkali.Its abstraction desulfurization mode uses It is liquid-liquid extracting mode.

In above-mentioned disclosed sulfur method or technique, the purpose of alkali process is in the average molecular in gasoline fraction is removed The less mercaptan of quality, such as carbon number are not more than 4 mercaptan, and the purpose of solvent extraction is in the non-mercaptan in gasoline fraction is removed The sulfide of class, mainly thiophene compound.Increase when by alkali process and the gasoline fraction mass fraction that solvent is handled, accordingly The mass fraction for the gasoline fraction that ground passes through hydrotreating will reduce, then loss of octane number is undoubtedly as caused by hydrotreating Opposite it will reduce.However, the conventional usual desulfuration efficiency of liquid-liquid solvent extraction is relatively low, and the hydrocarbon of the unsulfided absorbed Class is more, follow-up to need to wash separation, and the impurity that the sulfide containing material separated carries is also more, is unfavorable for being sent into hydrogenation dress Put and handled, the solvent after especially recycling causes solvent to extract sulfide when recycling often because regeneration is not thorough Ability declines.

In order to obtain the gasoline products of more low-sulfur, and avoid the greater loss of octane number, it is necessary to provide a kind of new work The shortcomings that process is to overcome the foregoing prior art.

The content of the invention

The defects of the purpose of the present invention is overcoming the prior art, on the premise of the greater loss of octane number is avoided, there is provided A kind of method and apparatus for the method for the new deep desulfurization of gasoline for the gasoline products that can obtain more low-sulfur.

It was found by the inventors of the present invention that the mercaptan of small molecule is difficult to be extracted completely by extraction solvent, and it was found that extracting is steamed Evaporate, in Distex process extraction solvent pair some higher to the removal efficiency of sulfide compared to conventional liquid-liquid extracting The absorption of alkene is also less than conventional liquid-liquid extracting, is so on the one hand conducive to more retain alkene, reduces alkene Hydrocarbon extracted with sulfide after in follow-up (being incorporated in heavy distillat) hydrotreating caused by loss of octane number, on the other hand take out Less alkene is dissolved in extraction solvent, it is possible to reduce the adverse effect that alkene recycles solvent because oxidation polymerization etc. occurs, Avoid extraction solvent because of the accumulation of objectionable impurities frequent regeneration.If gasoline fraction is first carried out by the way of solvent extraction Handle, the thiophene-type sulfide in gasoline fraction can remove totally, but be likely to have the thio-alcohol vulcanization of some non-thiophene-baseds Thing cannot remove, this just needs further subsequent treatment.In the present invention, the mode of this subsequent treatment is industrial easy The caustic extraction or adsorption treatment of realization.The present inventor provides the following gasoline deep of the present invention based on foregoing research The method of desulfurization.

To achieve these goals, in a first aspect, the present invention provides a kind of method of deep desulfurization of gasoline, including：

(1) gasoline stocks are fractionated to obtain light fraction and heavy distillat at a temperature of 70~140 DEG C of cut point；

(2) light fraction is contacted with extraction solvent to carry out solvent extraction by distilling, obtains sulfur-bearing solvent and molten Light fraction after agent extracting, is then separated the sulfur-bearing solvent to obtain solvent with the sulfide wherein contained by being evaporated under reduced pressure Sulfide containing material and the recycling design for being stripped of sulfide after extracting；

(3) removal of mercaptans handle, the removal of mercaptans processing in the following ways 1 or mode 2 carry out,

Mode 1 includes：Light fraction after the solvent extraction is contacted to carry out caustic extraction with lye, obtains sulfur-bearing lye With light fraction after caustic extraction, the sulfur-bearing lye is then subjected to oxidation processes with the sulfur-bearing lye after aoxidize, and general Sulfur-bearing lye after the oxidation is contacted with varsol proposes processing to carry out back suction, obtains sulfide containing material after caustic extraction and can The regeneration lye of recycling；

Mode 2 includes：Light fraction after the solvent extraction is contacted with adsorbent, light fraction after being adsorbed；

(4) heavy distillat is contacted with making choice property hydrodesulfurization reaction with Hydrobon catalyst, is hydrogenated with Heavy distillat afterwards；

(5) the removal of mercaptans light fraction that step (3) obtains is mixed to obtain vapour with heavy distillat after the hydrogenation of step (4) Oil product, the removal of mercaptans light fraction are light fraction or the acquisition of the mode 2 after the caustic extraction that the mode 1 obtains Light fraction after absorption.

Second aspect, the present invention provide a kind of equipment for deep desulfurization of gasoline, including：

Fractionating system, gasoline fraction are fractionated by the fractionating system to obtain light fraction and heavy distillat；

Solvent extraction system, including solvent extraction distillation unit and solvent recovery unit, the solvent extraction distillation unit For the light fraction from fractionating system to be carried out solvent extraction, light fraction after sulfur-bearing solvent and solvent extraction is obtained；It is described molten Agent recovery unit be used to the sulfide wherein contained separating the sulfur-bearing solvent with obtain after solvent extraction sulfide containing material and It is stripped of the recycling design of sulfide；

Light fraction desulphurization system, the light fraction desulphurization system are caustic extraction system or adsorption system, the caustic extraction system System includes mercaptan extraction unit, alkali liquor oxidized unit and the anti-extraction unit of lye, and the mercaptan extraction unit is used for self-dissolving in future Light fraction is contacted with lye to carry out caustic extraction after the solvent extraction of agent extraction system, is obtained light fraction after caustic extraction and is contained Sulphur lye, the alkali liquor oxidized unit are used to the sulfur-bearing lye carrying out oxidation processes, the sulfur-bearing lye after being aoxidized；With And the anti-extraction unit of lye is used for after the sulfur-bearing lye progress back suction after the oxidation is carried processing to obtain caustic extraction Sulfide containing material and the regeneration lye that can be recycled；And the adsorption system is used for the solvent pumping of solvent extraction system in future Propose rear light fraction and contacted with the adsorbent contained in the adsorption system with light fraction after being adsorbed；

Selective hydrogenation system, the heavy distillat from fractionating system by pipeline be introduced in the selection hydrogenation system into Row selective hydrodesulfurization is reacted to give heavy distillat after hydrogenation；

Heavy distillat is mixed with removal of mercaptans light fraction after the hydrogenation is incorporated as gasoline products and is drawn by pipeline, the desulfurization Alcohol light fraction is light fraction after light fraction after caustic extraction or the absorption.

The present invention avoids the greater loss of octane number to obtain the gasoline products of more low-sulfur, is using hydrogenation mode While flexibly use such as adsorbent absorption, caustic extraction, the non-hydrogenation mode of solvent extraction so that by foregoing offer of the invention Method can on the premise of the greater loss of octane number is avoided, obtain more low-sulfur gasoline products.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Brief description of the drawings

Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, and attached drawing is merely representative of preferable flow chart, and does not provide related container, heating Device, cooler, pump, compressor reducer, mixer, valve, the details such as control device of technical process, but do not form the limit to the present invention System.In the accompanying drawings：

Fig. 1 is a kind of deep desulfurization of gasoline device structure schematic diagram of preferred embodiment of the present invention.

Fig. 2 is the deep desulfurization of gasoline device structure schematic diagram of another preferred embodiment of the present invention.

Description of reference numerals

1st, gasoline stocks 2, fractionating system

3rd, heavy distillat 4, light fraction

5th, light fraction after solvent extraction system 6, solvent extraction

7th, sulfide containing material 81, caustic extraction system after solvent extraction

82nd, light fraction after adsorption system 9, caustic extraction

91st, sulfide containing material after light fraction 10, caustic extraction after adsorbing

11st, light fraction after mixing sulfide containing material 12, back suction drawings caustic extraction

13rd, light fraction after etherification system 14, etherificate

15th, heavy distillat after selective hydrogenation system 16, hydrogenation

Embodiment

The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.

In a first aspect, the present invention provides a kind of method of deep desulfurization of gasoline, including：

The light fraction is the relatively light cut of boiling range, and the double distilled is divided into the relatively heavy cut of boiling range.The institute of the present invention The most of mercaptan and alkene concentrated in light fraction in gasoline stocks are stated, the major part in gasoline stocks has been concentrated in heavy distillat The sulfide of other relatively high boiling predominantly thiophene-baseds.

In the step (3) of the present invention, caustic extraction or adsorbent mode can be used to take out the solvent Propose rear light fraction and carry out desulfurization.

Solvent extraction under preferable case presented below in relation to the present invention：

The solvent extraction causes the sulfide based on thiophene in light fraction is transferred in extraction solvent to form sulfur-bearing Solvent.

Preferably, the solvent extraction carries out in extraction distillation tower, and the light fraction obtained after fractionation is from extraction distillation tower Middle part enter tower in, extraction solvent from the top of extraction distillation tower enter tower in, under the selectively acting of solvent, gently Relatively high boiling thiophene in cut enters the bottom of towe of extraction distillation tower with thio-ether type compounds with extraction solvent.Extractive distillation The low-sulfur light fraction part that column overhead steams is circulated in overhead reflux, and a part is outer to be lined up as light fraction after solvent extraction.Take out The sulfur-rich solvent part for putting forward destilling tower bottom of towe is circulated in bottom of towe, and draining into solvent recovery unit outside a part is handled.

The extraction solvent and the weight ratio of the light fraction after fractionation are (0.5~20)：1, more preferably (1~5)： 1.Inventor has found, in liquid-liquid extracting mode, sulfur-bearing solvent absorbs in addition to the sulfide in light fraction is absorbed toward contact Wherein much more compared with sulfide other components, so that the solvent recovering system to distillation mode brings problems, as can Residual component is more in solvent after consumption increase, recycling, returns to solvent extraction system and is easy to cause the quick of solvent extraction ability Decline.And in the solvent extraction distillation desulfurization method of the present invention, the treating material component that extraction solvent absorbs is less, and recycling is molten Agent extracting ability can effectively be recovered.

Preferably, the solvent extraction carries out in extraction distillation tower, and the condition in the extraction distillation tower includes：Tower top Pressure is 100kPa~500kPa, is preferably 110kPa~300kPa；Tower top temperature is 50~180 DEG C；Column bottom temperature for 80~ 260 DEG C, be preferably 140~200 DEG C.

Preferably, the μ g/g of the sulfur content in light fraction after the solvent extraction that is obtained after the solvent extraction ≯ 10 are passed through.

Preferably, main extraction solvent is contained in the extraction solvent, the boiling point of the main extraction solvent is 175~320 DEG C, More preferably boiling point is 175~250 DEG C.

Preferably, the main extraction solvent is selected from sulfolane, 3- methyl sulfolanes, 2,4- dimethylsulfolanes, 3- ethyls Sulfolane, Methylethyl sulfone, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dibutyl sulfone, dimethyl sulfoxide (DMSO), furfural, furfuryl alcohol, α- Pyrrolidones, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidones, N- propyl group -2-Pyrrolidone, N- formyl-morpholines, Dimethylformamide, triethylene glycol, tetraethylene glycol, five glycol, triethylene glycol methyl ether, tetraethylene glycol methyl ether, ethylene carbonate, propylene carbonate The polyethylene glycol and average molecular matter of ester, propylene carbonate, acetonitrile, nitrobenzene, relative molecular mass between 200~400 Measure at least one of methoxypolyethylene glycol between 200~400；It is highly preferred that the main extraction solvent be selected from sulfolane, At least one of N- formyl-morpholines, n-methyl-2-pyrrolidone, tetraethylene glycol and five glycol.

In solvent extraction destilling tower, existing gas phase, and have liquid phase, the liquid phase is single liquid phase, i.e., in liquid phase section, The solvent of liquid phase and the light fraction of liquid phase are in dissolved state, and the sulfide be so conducive in light fraction is transferred to extraction solvent In, more liquid phase states, are just unfavorable for the extracting of sulfide once being formed.In order to improve absorption energy of the extraction solvent to sulfide Power, and contribute to the liquid phase region of extraction distillation tower to keep single liquid phase, it is preferable that further contain in the extraction solvent There is an auxiliary agent, the auxiliary agent is can dissolve each other and its boiling point or do not higher than the main extraction solvent with the main extraction solvent At least one of boiling point or the alcohols done, ketone, organic acid and organic nitrogen compound material and/or water, the organic nitrogen Compound is at least one of amine, ureas and alcamine compound.

Preferably, the auxiliary agent is can dissolve each other and its boiling point or do not higher than the main pumping with the main extraction solvent The boiling point of extraction solvent or alcohols of the carbon number no more than 6 done, ketone of the carbon number no more than 6, carbon number are little In 6 at least one of organic nitrogen compound material and/or the water of organic acid and carbon number no more than 6, the organic nitrogen Compound is at least one of amine, ureas and alcamines.

Preferably, alcohols of the carbon number no more than 6 is methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, tertiary fourth At least one of alcohol, n-amyl alcohol and cyclohexanol.

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

Preferably, organic acid of the carbon number no more than 6 is in isobutyric acid, ethanedioic acid, malonic acid and succinic acid At least one.

Preferably, organic nitrogen compound of the carbon number no more than 6 is selected from urea, ethylenediamine, monoethanolamine, N- methyl Monoethanolamine, N- ethyls monoethanolamine, N, N- dimethylethanolamines, N, N- diethyl ethylene diamines, diethanol amine, N- methyl diethyls At least one of hydramine, triethanolamine, n-propanolamine, isopropanolamine and diglycolamine.

It is highly preferred that contain water, methanol, ethanol, normal propyl alcohol, isopropanol, acetone, methyl ethyl ketone, isobutyric acid, second two in described Acid, malonic acid, succinic acid, urea, ethylenediamine, monoethanolamine, 2-Methylaminoethanol, N- ethyls monoethanolamine, N, N- diformazans Ethylethanolamine, N, N- diethyl ethylene diamines, diethanol amine, N methyldiethanol amine, triethanolamine, n-propanolamine, isopropanolamine At least one of with diglycolamine.It is particularly preferred that the auxiliary agent is selected from water, methanol, acetone, methyl ethyl ketone, isobutyric acid, second two At least one in acid, malonic acid, succinic acid, ethylenediamine, monoethanolamine, 2-Methylaminoethanol, isopropanolamine and diglycolamine Kind.

Preferably, in the extraction solvent, the content of the auxiliary agent is 0.1~20 weight %, more preferably 0.5~15 Weight %；It is particularly preferred that the content of the auxiliary agent is 1~10 weight %.

Preferably, the auxiliary agent is the mixture containing water.However, formation influence of the water on multiphase is very big, once solvent When middle water content is larger, tend to form multiphase state in extraction distillation tower.Therefore, when the auxiliary agent is mixed containing water During compound, preferably content of the water in the extraction solvent is 0.1~5 weight %, more preferably 0.1~3 weight %.

Preferably, defoamer is contained in the extraction solvent, the defoamer is selected from silicone compounds, alkylsulfonate Compound, polyether compound, polyethylene glycols compound, polyesters compound, amides compound and aliphatic alcohols chemical combination At least one of thing.

It was found by the inventors of the present invention that when the extraction solvent containing auxiliary agent is used in solvent extraction distillation process, can The effective rate of utilization of extraction solvent is improved, reduces the solvent reclamation frequency, so as to cause the relative reduction and running cost of energy consumption It is opposite to reduce.

Solvent recovery under preferable case presented below in relation to the present invention：

Sulfur-bearing solvent rich in sulfide needs to recycle after removing absorbed sulfide, removes sulfide Mode is known as solvent recovery.The solvent recovery is carried out by the way of distillation, will be from the sulfur-bearing during solvent extraction Solvent steams sulfide containing material under heating conditions, which includes the aromatic hydrocarbons in light fraction, thiophene, thioether class Compound, the sulfide containing material are lined up as sulfide containing material after solvent extraction outside.Being stripped of the solvent after sulfide becomes recycling design, And return to the recycling of solvent extraction distillation process.

Preferably, the solvent recovery is carried out by the way of vacuum distillation, by being evaporated under reduced pressure the sulfur-bearing solvent Condition separated with the sulfide wherein contained includes：The tower top pressure of solvent recovery tower is 10kPa~100kPa, tower top temperature For 50~100 DEG C, column bottom temperature is 100 DEG C~250 DEG C, and more preferably column bottom temperature is 120~200 DEG C, stripped vapor with it is described The weight ratio of sulfur-bearing solvent is (0.01~5.0)：1.

Sulfur-bearing hydrocarbon material is stripped of in recycling design, but can occur such as to aoxidize in operation process, decompose side reaction, so that Some soluble higher-boiling compounds such as impurity such as stable salts, organic polymer, deposit is formed, these materials are in a solvent In the presence of and accumulate, the solvability of extraction solvent can be undoubtedly reduced, so as to reduce the efficiency of gasoline extraction desulfurization, it is therefore desirable to right Solvent carries out regeneration treatment, improves the purity of solvent.

Preferably, this method further comprises：At least partly described recycling design is subjected to water filling in solvent regeneration tower Purification processes are to regenerate.

Solvent reclamation under preferable case presented below in relation to the present invention：

The water filling purification processes can be realized by carrying out water filling vacuum distillation to solvent, relatively light in recycling design The remaining hydrocarbon material azeotrope with water of matter and discharged from tower top, relatively heavy higher-boiling compound impurity is with residue in recycling design Form is discharged from solvent regeneration tower bottom of towe, and the solvent after purification is discharged on the downside of solvent regeneration tower, becomes regenerated solvent. Preferably, the water in water filling purification processes comes from solvent extraction distillation process and the condensed water collected by solvent recovery process. Regenerated solvent, which can directly return to solvent recovery tower or the recycling design mixing Posterior circle directly with solvent recovery tower outflow, to be made With.

Preferably, the regeneration condition in the solvent regeneration tower includes：Tower top pressure is 1kPa~10kPa, tower top temperature For 90~110 DEG C, preferably tower top temperature is 96~105 DEG C, and column bottom temperature is 120 DEG C~200 DEG C, and preferably column bottom temperature is 150 DEG C~200 DEG C, the water of injection and the weight ratio of the recycling design are (0.1~10)：1, preferred weight ratio is (0.5~5)：1.

Preferably, 1~10 weight % of all recycling designs is accounted for for carrying out regenerated recycling design, is more preferably accounted for All 1~5 weight % of the recycling design.

The present invention removal of mercaptans processing can by the caustic extraction of employing mode 1 or in a manner of 2 adsorbent suction type carry out.

The caustic extraction of the present invention includes three consecutive basic processes, i.e.,：Mercaptan extracting, sulfur-bearing are alkali liquor oxidized Carried with lye back suction.

Mercaptan extraction steps under preferable case presented below in relation to the present invention：

Contacted containing mercaptan with light fraction after the solvent extraction of alkene with substantially free of disulphide with the lye of oxygen, it is molten Mercaptan after agent extracting in light fraction, which is absorbed into lye, generates mercaptides, after removing mercaptan and the solvent extraction of sulfur content reduction Light fraction is flowed out after being separated with extracting lye, becomes light fraction after the caustic extraction.Light fraction is basic after the caustic extraction On no longer contain mercaptan, and sulfur content accordingly reduces.

Preferably, in the Thiolex process, contact of the light fraction with lye is preferably with inverse after the solvent extraction Stream mode carries out, and can also use known various modes, equipment or the container for being conducive to immiscible two kinds of fluids contact Carry out, such as contacted in manner of cocurrent flow, the equipment or container of the contact can be static mixers, or be equipped with Contact the vertical column of device, such as the contact device such as plate column, packed tower, fiber-film contact equipped with stainless steel wire fibre bundle For making to produce closely contact between the two of injection kinds of fluids.

Lye in the mercaptan extracting includes any of alkalescence for having and mercaptan ability being extracted from gasoline stocks Reagent.Preferably, the lye in the caustic extraction is the aqueous solution of ammonium hydroxide and/or alkali metal hydroxide, such as hydroxide Sodium, potassium hydroxide, the aqueous solution of lithium hydroxide.And the concentration of the lye is 1~50 weight %, more preferably 5~25 weights Measure %.If desired, the aqueous solutions of alkaline earth metal hydroxide such as calcium hydroxide, barium hydroxide can also be used and had The aqueous solution of machine quaternary ammonium base.

Preferably, the mercaptan extraction conditions include：Temperature is 5~100 DEG C, is preferably 15~65 DEG C；Pressure is 0.1MPa~2.0MPa, the dosage volume ratio of light fraction is (1~50) after the solvent extraction that the lye is contacted with it： 100, be preferably (5~40)：100.

Oxidation treatment step under preferable case presented below in relation to the present invention：

The sulfur-bearing lye carries out oxidation processes, so that the mercaptides in sulfur-bearing lye is oxidized to two sulphur after peroxidating Compound.The oxidant used in oxidizing process is preferably the oxygen in air.The air that the alkali liquor oxidized process of sulfur-bearing is injected Air is preferably purified, air capacity, which is more than or equal to, makes mercaptan salt in sulfur-bearing lye be oxidized to the chemistry meter needed for disulphide 2~4 times of calculation amount, usually stoichiometric amount.

Preferably, the condition of the oxidation processes includes：Temperature is 5~100 DEG C, is preferably 15~65 DEG C, and pressure is 0.1MPa~2.0MPa, is preferably 0.1MPa~0.8MPa, and the pressure during sulfur-bearing is alkali liquor oxidized is generally below the lye The pressure of extractive process.

Preferably, the oxidation processes carry out in the presence of metal phthalocyanine fixed bed of oxidation catalyst.Preferably, in metal In phthalocyanine fixed bed of oxidation catalyst, on the basis of the metal phthalocyanine fixed bed of oxidation catalyst, metal phthalocyanine compound Load capacity is 0.01~10 weight %, is preferably 0.05~3 weight %.

Preferably, the metal phthalocyanine is selected from magnesium phthalocyanine, titanium phthalocyanines, hafnium phthalocyanine, vanadyl phthalocyanine, tantalum phthalocyanine, molybdenum phthalocyanine, manganese phthalein At least one of cyanines, iron-phthalocyanine, cobalt phthalocyanine, platinum phthalocyanine, palladium phthalocyanine, copper phthalocyanine, silver-colored phthalocyanine, ZnPc and tin phthalocyanine；It is more excellent It is cobalt phthalocyanine and/or vanadyl phthalocyanine to select the metal phthalocyanine.

Preferably, the metal phthalocyanine be selected from metal phthalocyanine sulfonated bodies, carboxylate and quaternary ammonium compound,Class compound Deng, be preferably cobalt phthalocyanine sulfonated bodies, include single sulfonated bodies (single sulfonated phthalocyanine cobalt), the double sulfonated bodies of cobalt phthalocyanine of cobalt phthalocyanine Three sulfonated bodies (three sulfonated phthalocyanine cobalts) of (double sulfonated phthalocyanine cobalts), cobalt phthalocyanine, four sulfonated bodies (four sulfonated phthalocyanine cobalts) of cobalt phthalocyanine At least one of.

Back suction under preferable case presented below in relation to the present invention proposes processing：

Contain disulphide in lye after oxidation, it is necessary to disulphide removing could be recycled, remove curing The mode of thing is that back suction proposes processing, and sulfur-bearing lye that will be after the oxidation containing disulphide is contacted with varsol, two sulphur Compound is transferred in varsol and is separated with lye, and the regeneration lye that back suction obtains after carrying returns to be circulated in Thiolex process Use.Before back suction proposes processing, the lye after oxidation and unnecessary air tail gas separation can be made by way of sedimentation, so The varsol contact afterwards, absorbing the circulation of the sulfur-bearing lye after the varsol of disulphide can continue and aoxidize makes With, and intermittently or serially line up outside as sulfide containing material after caustic extraction.Preferably, the body of the varsol and lye after oxidation Product ratio is (0.1~10)：1, intermittently or serially outer it can arrange the varsol for absorbing sulfide.Back suction carry during pressure Generally below alkali liquor oxidized pressure.

Preferably, the varsol that the back suction is carried in processing is selected from heavy distillat, solvent pumping after the hydrogenation Propose light fraction and gasoline production after light fraction, the etherificate after light fraction, the absorption after rear light fraction, the caustic extraction At least one of product.

Adsorbent adsorption step under preferable case presented below in relation to the present invention：

The adsorbent adsorption step is realized by the way that light fraction after the solvent extraction is contacted with adsorbent, so as to obtain Light fraction after to absorption.It is adsorbed by adsorbent by the sulfide in light fraction after adsorbent adsorption step solvent extraction de- Remove.

As long as there are the various materials of adsorption capacity can serve as the adsorbent in the present invention to sulfide to use, preferably To porous material of the sulfide with physical suction-operated and to transition gold of the sulfide with chemically suction-operated The adsorbent for belonging to material as the present invention uses, and preferred adsorbent uses in solid form.

Used adsorbent can be physical adsorbent and/or chemically adsorbent.

The physical adsorbent is preferably comprised in silica, aluminium oxide, zeolite, clay and activated carbon at least A kind of porous material.

The chemically adsorbent preferably comprises the metal containing transition metal, metal oxide or metal ion Compound, the transition metal are selected from least one of ferro element, cobalt element, nickel element, copper and Zn-ef ficiency.It is excellent Selection of land, also containing being helped selected from least one of alkali metal and alkali earth metal adsorbent in the chemically adsorbent Agent.

Preferably, light fraction includes with the condition that the adsorbent contacts after the solvent extraction：Temperature is 10~300 ℃；Pressure is 0.1~2MPa, and liquid hourly space velocity (LHSV) is 0.1~1h^-1.It is highly preferred that the temperature of the contact is 15~200 DEG C.

The present invention has no particular limits the preparation method of the adsorbent, also no special to the shape of the adsorbent Other limitation.

Preferably, the μ g/ of sulfur content after the absorption obtained after the adsorbent adsorption step in light fraction ≯ 10 g。

Preferably, method of the invention further comprises：Before being mixed with heavy distillat after the hydrogenation of step (4), The removal of mercaptans light fraction that first step (3) is obtained carries out etherification reaction, light fraction after being etherified；Then again by the ether Light fraction is mixed to obtain the gasoline products with heavy distillat after the hydrogenation of step (4) after change.

The etherification reaction of the present invention, which makes it possible to obtain olefin(e) centent, to be reduced and light fraction after the increased etherificate of octane number.

Etherification reaction under preferable case presented below in relation to the present invention：

Preferably, the etherification reaction is by the way that the removal of mercaptans light fraction and low-carbon alcohols of the carbon number no more than 6 are connect Touch and carry out.

Preferably, the low-carbon alcohols for etherification reaction are methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, tertiary fourth At least one of alcohol, n-amyl alcohol and cyclohexanol；Particularly preferably methanol.

Preferably, the condition of the etherification reaction includes：The low-carbon alcohols and the alkene in the removal of mercaptans light fraction Molar ratio is (0.5~3)：1, be preferably (1.0~1.2)：1, the temperature of contact is 20~100 DEG C, pressure for 0.3MPa~ 1.0MPa。

Preferably, the etherification reaction carries out in the presence of the catalyst for etherification as strong-acid ion exchange resin.Institute It for example can be sulfonic acid ion exchange resin to state strong-acid ion exchange resin.

In the case of more preferably, the condition that the removal of mercaptans light fraction is contacted with low-carbon alcohols causes after being etherified in light fraction Olefin removal rate ≮ 35%.

Preferably, method of the invention further comprises：It is first that the removal of mercaptans is light before the etherification reaction is carried out Cut carries out absorption pretreatment and/or making choice property weighted BMO spaces.

Especially, the absorption pretreatment carried out before etherification reaction and/or making choice property weighted BMO spaces be in order to Alkadienes and basic nitrogen compound that may be present in cut are removed, to prevent alkadienes that may be present and alkalescence in cut Nitride causes catalyst for etherification to inactivate.The adsorbent used in absorption pretreatment is not necessarily gently evaporated with foregoing in order to remove Sulphur compound (removal of mercaptans processing in) in point and the adsorbent that uses is identical.Those skilled in the art can carry according to the present invention The purpose of alkadienes and basic nitrogen compound that may be present and the present invention provide in the desulfurization purpose and removing cut of confession Adsorbent and carry out desulfurization operations or etherificate before absorption pretreatment operation.Under preferable case, make in the absorption pretreatment Adsorbent is acid porous molecular sieve material, and the absorption pretreatment can carry out at normal temperatures and pressures.Also, In the case of being not particularly illustrated, the adsorbent being mentioned above is for the sulfide in light fraction after solvent extraction to be removed With the adsorbent used during light fraction after being adsorbed.

In the present invention, light fraction is after solvent extraction and caustic extraction, or after solvent extraction and adsorbent absorption, Most sulfide are removed, and selective hydrogenation pretreatment can carry out under conditions of more relaxing, such as can use Easily by the high activity noble metal catalyst of sulfur poisoning under relatively low temperature, relatively low pressure, relatively low hydrogen to oil volume ratio into Row is so as to effectively avoid the loss of the octane number caused by the hydrogenation of monoolefine.

Preferably, the selective hydrogenation pretreatment carries out in the presence of transition metal loaded catalyst.Make choice Property selective hydrogenation pretreatment catalyst used in weighted BMO spaces can be can be by diene under certain reaction condition Hydrocarbon saturation and avoid the hydrogenation or Hydro-catalyst of monoolefine saturation, the selective hydrogenation pretreatment catalyst include transition gold Belong to loaded catalyst, can be non-noble metal supported catalyst, or noble metal carrier catalyst, or this The combination of two class catalyst.The transition metal loaded catalyst includes the metal active of carrier and load on the carrier Component, the carrier is selected from least one of aluminium oxide, silica, alumino-silicate, titanium oxide, zeolite and activated carbon, described Metal active constituent is selected from least one of nickel, cobalt, molybdenum, platinum and palladium.

According to a kind of preferred embodiment, the carrier in the transition metal loaded catalyst is aluminium oxide, Metal active constituent is using the load capacity that oxide is counted as 0.05~15 weight %.

Preferably, the condition of the selective hydrogenation pretreatment includes：Hydrogen dividing potential drop is 0.1MPa~2.0MPa, and temperature is room Temperature~250 DEG C, volume space velocity is 1.0h during liquid^-1~10.0h^-1, hydrogen to oil volume ratio is 1~100.

A kind of preferred embodiment according to the present invention, method of the invention further comprise：By in step (2) Solvent extraction after after caustic extraction in sulfide containing material and/or step (3) sulfide containing material selected together with the heavy distillat Selecting property hydrodesulfurization reaction.

A kind of preferred embodiment according to the present invention, method of the invention further comprise：By in step (2) Solvent extraction after after caustic extraction in sulfide containing material and/or step (3) sulfide containing material be introduced into catalytic cracking unit and carry out Catalytic cracking reaction is to obtain at least part gasoline stocks for step (1).

Selective hydrodesulfurization reaction under preferable case presented below in relation to the present invention：

Preferably, selective hydrodesulfurization reaction in sequentially connected first reaction zone and second reaction zone into OK, the first Hydrobon catalyst is loaded respectively in first reaction zone and the second reaction zone and the second hydrodesulfurization is urged Agent, first Hydrobon catalyst and the second Hydrobon catalyst independently of one another containing alumina support and/or The hydrogenation active metal component of silica-alumina supports and load on the carrier, the hydrogenation active metal component are selected from molybdenum And/or group vib non-noble metal j element and/or the VIII group non-noble metal j element selected from nickel and/or cobalt of tungsten.

Preferably, first Hydrobon catalyst and the second Hydrobon catalyst independently of one another containing molybdenum and/ Or tungsten, nickel and/or cobalt, alumina host and large pore zeolite and/or mesopore zeolite.

Preferably, on the basis of the total amount of the Hydrobon catalyst, the group vib non-noble metal j element is with oxide The content of meter is 2~25 weight %, and the VIII group non-noble metal j element is using the content that oxide is counted as 0.2~6 weight %.Should " Hydrobon catalyst " at place is the first Hydrobon catalyst or the second Hydrobon catalyst.

Preferably, first Hydrobon catalyst is desulphurizing activated de- less than second Hydrobon catalyst Sulphur activity.The present invention's is desulphurizing activated with " when handling identical raw material, the Hydrobon catalyst of unit volume is reaching identical Desulfurization effect under reaction temperature (T) " represent, T is bigger to represent that activity is lower.

Preferably, first reaction zone and the reaction condition of second reaction zone include independently of one another：Hydrogen dividing potential drop is 0.1MPa~4.0MPa, reaction temperature are 200 DEG C~440 DEG C, and volume space velocity is 1.0h during liquid^-1~10.0h^-1, hydrogen to oil volume ratio For 200~1000.It is highly preferred that first reaction zone and the reaction condition of second reaction zone include independently of one another：Hydrogen point Press as 1.0MPa~3.2MPa, reaction temperature is 200 DEG C~300 DEG C, and volume space velocity is 2.0h during liquid^-1~6.0h^-1, hydrogen oil body Product is than being 200~600.

Preferably, sulfur content ≯ 10 in heavy distillat after the hydrogenation that the condition of the selective hydrodesulfurization reaction causes μg/g。

Preferably, the cut point of the light fraction and heavy distillat is 80~120 DEG C.

Preferably, the lower limit for doing the boiling range temperature range not higher than extraction solvent of the light fraction.

Preferably, on the basis of the gasoline stocks, the yield of the light fraction is 40~60 weight %, the heavy distillat Yield be 40~60 weight %.

Preferably, the gasoline stocks are selected from catalytically cracked gasoline, catalytic cracking gasoline, direct steaming gasoline, coker gasoline, split Solve at least one of gasoline and pressure gasoline.

Preferably, in step (5), the μ g/g of the sulfur content of gained gasoline products ≯ 10.Especially, step of the invention (5) product that gasoline products are obtained by mixing for heavy distillat after hydrogenation with light fraction after light fraction after caustic extraction or absorption, Or the product being obtained by mixing for heavy distillat after hydrogenation with light fraction after etherificate.

Second aspect, the present invention provides a kind of equipment for deep desulfurization of gasoline, including：

Preferably, which further comprises etherification system, and the removal of mercaptans light fraction from light fraction desulphurization system is first led to Cross pipeline and be introduced in the etherification system and carry out etherification reaction with light fraction after being etherified；Then again by this be etherified after light fraction Mixed with heavy distillat after the hydrogenation to be drawn as gasoline products by pipeline.

According to a kind of preferred embodiment, which further comprises sulfide containing material after the caustic extraction And/or sulfide containing material is introduced to the pipeline in selective hydrogenation system after the solvent extraction.

According to another preferred embodiment, which further comprises cracking system, is taken out from the solvent Sulfide containing material passes through after carrying sulfide containing material after the solvent extraction of system and/or the caustic extraction from the light fraction desulphurization system Pipeline, which is introduced in the cracking system, carries out catalytic cracking reaction, and the product in the cracking system is introduced to institute by pipeline State in fractionating system.

Preferably, the solvent extraction system further comprises solvent regeneration unit, which is used in the future Be introduced to from the recycling design of the solvent recovery unit in the solvent regeneration unit by pipeline carry out water filling purification processes with Regeneration.

Preferably, the selective hydrogenation system includes sequentially connected first reaction zone and second reaction zone to carry out institute State selective hydrodesulfurization reaction.

According to a kind of preferred embodiment, the equipment for deep desulfurization of gasoline of the invention has Fig. 1 Shown structure diagram, the light fraction desulphurization system of the embodiment is caustic extraction system, specifically：

Gasoline stocks 1 enter fractionating system 2 by pipeline, fractionate out heavy distillat 3 and light fraction 4.The heavy distillat 3 is through pipe Line flows out, and is mixed into selective hydrogenation system 15 with hydrogen, through the first reaction zone in relatively low the first active hydrogenation Making choice property hydrogenation reaction under desulphurization catalyst effect, subsequently into second reaction zone in of a relatively high the second active hydrogenation Making choice property hydrogenation reaction under desulphurization catalyst effect, flows out and heavy distillat 16 after being hydrogenated with from pipeline.From fractionation train The light fraction 4 of system 2 enters in solvent extraction system 5 through pipeline to be contacted with extraction solvent, remaining sulfide transfer in light fraction Into extraction solvent, light fraction 6 and sulfur-bearing solvent after solvent extraction are obtained.The sulfur-bearing solvent for absorbing sulfide is returned into solvent Receive unit and carry out solvent recovery, the sulfide absorbed separates under conditions of distillation with extraction solvent, after obtaining solvent extraction Sulfide containing material 7, sulfide containing material 7 is mixed with sulfide containing material after caustic extraction 10 after the solvent extraction, forms mixing sulfide containing material 11, The mixing sulfide containing material 11 enters in selective hydrogenation system 15 together with heavy distillat 3, or is incorporated in cracking system and is split Change reaction, a part of gasoline stocks 1 of the gasoline fraction obtained after cracking as the present invention.A part of recycling design flows at the same time Solvent regeneration unit is contacted with water, carries out purification regeneration, the hydro carbons (azeotrope with water) absorbed in solvent, the heavy rich in impurity Raffinate is separated with regenerated solvent, and regenerated solvent is incorporated in recycling design, is continued to contact with the light fraction obtained after fractionation and is circulated Use.

Light fraction 6 enters in caustic extraction system 81 and is contacted with lye after solvent extraction, after solvent extraction in light fraction Mercaptan is transferred in lye, obtains light fraction 9 after caustic extraction, and leaves caustic extraction system 81 through pipeline, and absorbs sulphur The oxidation by air under fixed bed of oxidation catalyst effect of the sulfur-bearing lye of alcohol, the mercaptan absorbed are oxidized to disulphide, Lye after oxidation isolates unnecessary air, and contacts with back suction extraction solvent to carry out anti-extraction procedure, two sulphur in lye Compound is transferred in back suction extraction solvent and is separated with lye, obtains sulfide containing material 10 and regeneration lye after caustic extraction, the lye Sulfide containing material 10 leaves caustic extraction system 81 through pipeline after extracting, and back suction is stripped of disulphide and there is no sky after carrying The regeneration lye of gas continues to contact and recycle with light fraction after solvent extraction.The back suction extraction solvent is to carry out self-selectively to add Hydrogen system 15 and the light fraction 9 after heavy distillat 16, the caustic extraction from caustic extraction system 81, anti-after the hydrogenation of pipeline outflow Light fraction 12 or from final low-sulphur oil product after extracting caustic extraction, wherein, it is light after the back suction drawings caustic extraction Cut 12 is light fraction after a part of caustic extraction from caustic extraction system 81.

It is preferred that in the case of, alkali liquor oxidized unit and the anti-extraction unit of lye can be merged into an oxidation sweetening unit Operated, as long as lye can be realized in for example upright tower or in the upright tower of the sleeping tank of bottom of towe connection in a system Oxidation and with the separation of air, sulfide containing material, be then stripped of the regeneration lye of sulfide and air in caustic extraction Recycled in system 81.

Under preferable case, after caustic extraction light fraction 9 through pipeline enter etherification system 13 in.

Light fraction 9 preferably first carries out pre-hydrotreating after into the caustic extraction in etherification system 13, and after treatment with Low-carbon alcohols contact, and make the alkene after caustic extraction in light fraction with low-carbon alcohols reaction generation ether, light fraction 14 after being etherified.

Heavy distillat 16 has been mixed into low-sulfur, low alkene and octane number with light fraction 14 after the etherificate after the hydrogenation Increased gasoline products；Or heavy distillat 16 is mixed into low-sulfur, low alkene with light fraction 9 after the caustic extraction after the hydrogenation Hydrocarbon and the less gasoline products of loss of octane number.

According to another preferred embodiment, the equipment for deep desulfurization of gasoline of the invention has figure Structure diagram shown in 2, the light fraction desulphurization system of the embodiment is adsorption system, specifically：

Gasoline stocks 1 enter fractionating system 2 by pipeline, fractionate out heavy distillat 3 and light fraction 4.The heavy distillat 3 is through pipe Line flows out, and is mixed into selective hydrogenation system 15 with hydrogen, through the first reaction zone in relatively low the first active hydrogenation Making choice property hydrogenation reaction under desulphurization catalyst effect, subsequently into second reaction zone in of a relatively high the second active hydrogenation Making choice property hydrogenation reaction under desulphurization catalyst effect, flows out and heavy distillat 16 after being hydrogenated with from pipeline.From fractionation train The light fraction 4 of system 2 enters in solvent extraction system 5 through pipeline to be contacted with extraction solvent, remaining sulfide transfer in light fraction Into extraction solvent, light fraction 6 and sulfur-bearing solvent after solvent extraction are obtained.The sulfur-bearing solvent for absorbing sulfide is returned into solvent Receive unit and carry out solvent recovery, the sulfide absorbed separates under conditions of distillation with extraction solvent, after obtaining solvent extraction Sulfide containing material 7, sulfide containing material 7 enters in selective hydrogenation system 15 together with heavy distillat 3 after the solvent extraction, or is incorporated to and splits Cracking reaction, a part of gasoline stocks 1 of the gasoline fraction obtained after cracking as the present invention are carried out in change system.One at the same time Point recycling design flows into solvent regeneration unit and is contacted with water, carries out purification regeneration, hydro carbons (azeotrope with water) absorbed in solvent, Heavy residue rich in impurity is separated with regenerated solvent, and regenerated solvent is incorporated in recycling design, continue be fractionated after obtain it is light Cut is contacted and recycled.

Light fraction 6 flows into adsorption system 82 from pipeline after the solvent extraction, contacts with adsorbent, is gently evaporated after solvent extraction Remaining trace sulfide in 6 is divided to be adsorbed by adsorbent, light fraction 91 after being adsorbed.

Under preferable case, after the absorption light fraction 91 through pipeline enter etherification system 13 in.

Light fraction 91 preferably first carries out pre-hydrotreating after into the absorption in etherification system 13, and after treatment with low-carbon Alcohol contacts, and makes the alkene after absorption in light fraction with low-carbon alcohols reaction generation ether, light fraction 14 after being etherified.

Heavy distillat 16 has been mixed into low-sulfur, low alkene and octane number with light fraction 14 after the etherificate after the hydrogenation Increased gasoline products；Or heavy distillat 16 is mixed into low-sulfur, low alkene with light fraction 91 after the absorption after the hydrogenation And the gasoline products that loss of octane number is less.

Deep desulfurization of gasoline technique provided by the invention has the advantages that in detail below：

Solvent pumping is respectively adopted present invention employs the mode to sour gasoline segment processing, and to the gasoline of each fraction section Carry, caustic extraction or adsorbent adsorb, the processing mode of selective hydrogenation.

The present invention configures caustic extraction after solvent extraction, non-in light fraction due to the raising of solvent extraction efficiency Mercaptan sulfur compounds and part mercaptan are removed by solvent extraction, and remaining Biogenic thiols can be very convenient by caustic extraction mode Ground removes, and the severity of caustic extraction operation can reduce.

In order to effectively reduce the sulfur content of gasoline fraction, present invention employs have notable selective absorbing to sulfide Extraction solvent, and the mode for employing extractive distillation extracts the sulfide in removing gasoline fraction and the mode of vacuum distillation Recycle extraction solvent, the light fraction after solvent extraction separates complete (not carrying secretly mutually substantially) with extraction solvent, it is not necessary to after Extraction solvent can also separate well with the sulfide and sulfide containing material absorbed when continuing processing, and recycling, after recycling A solvent part carries out regeneration treatment, overcomes Conventional solvents and regenerates halfway shortcoming, not only passes through the azeotropism with water The remaining hydrocarbon material dissolved in solvent is isolated, but also the impurity such as the higher boiling polymer accumulated in solvent, deposit are taken off Remove, refining effect is notable during solvent reclamation so that the solvent after recycling with a part of regenerated solvent mixing Posterior circle pumping The ability of carrying is effectively restored.

Due to the raising of desulfuration efficiency, the doing for light fraction in the present invention can suitably raise, and can so increase vapour The yield of light fraction when oil evaporates and reduce the yield of heavy distillat, heavy distillat enter hydrogenation system treating capacity reduce therewith, because Loss of octane number just can be reduced effectively caused by the hydrogenation of heavy distillat.

Simultaneously as solvent extraction is prepared before caustic extraction, caustic extraction flow can even simplify, such as reduce The usage amount of lye back suction drawings back suction extraction solvent, or oxidation step and back suction put forward into step group be merged into the oxidation of a step and take off Sulphur step operation (is completed (to contain two with sulfide containing material after air, caustic extraction while realizing alkali liquor oxidized in oxidation step The back suction extraction solvent phase of sulfide) separation, and the lye after separating returns to caustic extraction mercaptan step), light fraction lye is taken out Only need to be by the relatively low Mercaptan removal of boiling point, as the disulphide changed into by mercaptan whether completely from light when carrying Separated in cut, have no effect on the effect of follow-up solvent extraction.Because under solvent extraction distillation condition, remove Remaining sulfide is mainly thiophene in the light fraction of mercaptan, can be easy to be enriched to extraction tower bottom by extraction solvent absorption, and Disulphide contained by it boiling point that (is transformed by low-boiling mercaptan) is higher, although not necessarily by extraction solvent well Absorb, but under column plate effect, due to boiling-point difference, it is easy to separated with the hydrocarbon component of light fraction, and be enriched to extraction tower bottom.Very Substantially, such optimize enables to the salkali waste discharge number of caustic extraction system to be reduced with quantity.And if using liquid- Thiophenes are had the solvent compared with high selectivity absorption efficiency by the mode that liquid solvent extraction is distilled to recover with positive pressure solvent Effect in terms of thioether class sulphur is absorbed is usual and bad, it is difficult to deep desulfuration, and due to entrainment mutually, the gasoline after extracting Cut often also needs to subsequent treatment, such as washes, and the solvent after extracting recycles logical because the material absorbed relatively more Often it is difficult to the effective use for thoroughly, being unfavorable for solvent.

In the present invention, either caustic extraction or solvent extraction, can all produce the material rich in sulphur.In bar of the present invention Under part, these materials rich in sulphur can together with heavy distillat making choice property hydrodesulfurization reaction, and to hydrogenation system Very little is influenced, the greater loss of octane number will not be caused.It is also possible to these materials rich in sulphur are incorporated to catalytic cracking Riser carries out cracking reaction, in operation also advantageously.

Another remarkable advantage of desulfurization process of gasoline provided by the invention is：Selective hydrodesulfurization system of the present invention Employ two kinds of hydrogenation catalysts to be engaged, carrying out catalytic hydrogenation with the second hydroconversion reaction zone in the first hydroconversion reaction zone respectively takes off Reaction of Salmon-Saxl, can stably obtain the gasoline products that sulfur content is not more than 10 μ g/g, and loss of octane number is smaller.

In order to reduce the loss of octane number, the present invention preferably configures after caustic extraction step or adsorbent adsorption step Etherification step, makes the alkene in light fraction generate high-octane ether compound with low-carbon alcohols reaction.Since solvent extraction takes off Except most of sulfide and other heteroatomic compounds in light fraction so that the pretreatment before being etherified can be in mitigation Under the conditions of carry out, advantageously reduce running cost.

In the method for the present invention by using extractive distillation coordinate other process means compared to it is existing containing conventional liquid- The liquid of the obtained gasoline products of technique of liquid extracting is received will height.Moreover, easily go out in liquid-liquid extractive process of the prior art Existing oil carries agent, agent carries the situation of oil, it is necessary to further the mode such as washing is handled, and be easy to cause liquid and receives loss.

To sum up, the present invention deep desulfuration technique no matter on desulfurization effect, reduce loss of octane number in terms of, still In terms of the feasibility of device operation is with stability and environmental protection effect, all more advanced, this is that the prior art cannot compare 's.

Below will the present invention will be described in detail by example.In following instance, in case of no particular description, The various raw materials used are all from commercially available.

One kind in catalyst for selectively hydrodesulfurizing used below is by Sinopec Group The catalyst for the product designation RSDS-11 that catalyst branch company Chang Ling catalyst plant provides.

Another composition of catalyst for selectively hydrodesulfurizing Cat1：The content of cobalt oxide is 4.3 weight %, molybdenum oxide Content is 12.4 weight %, and surplus is alumina support.

The composition of selective hydrogenation pretreatment catalyst Cat2 used below is：The Pd of 0.5 weight %, surplus Al₂O₃ Carrier.

Metal phthalocyanine fixed bed of oxidation catalyst used below is had greatly Fine Chemical Works offer, trade names by Guangzhou For ARC-01.

The adsorbent used below in removal of mercaptans processing is had greatly Fine Chemical Works offer, product designation SSA- by Guangzhou 01。

Lye used below is the sodium hydrate aqueous solution that concentration is 25 weight %.

Embodiment 1

The present embodiment carries out deep desulfuration processing using the equipment shown in Fig. 1 to the gasoline stocks A in table 1.

Gasoline stocks A is fractionated to obtain light fraction and yield of the yield as 50 weight % at a temperature of 95 DEG C of cut point For the heavy distillat of 50 weight %.

In solvent extraction system, in solvent extraction destilling tower to fractionation after light fraction carry out solvent extraction distillation, obtain Light fraction and sulfur-bearing solvent after to solvent extraction, sulfur-bearing solvent are 5 weight % of light fraction total amount.Then existed by vacuum distillation The sulfur-bearing solvent separated with the sulfide wherein contained in solvent recovery tower to obtain after solvent extraction sulfide containing material and de- Except the recycling design of sulfide：

In solvent extraction destilling tower：Extraction solvent and the feed weight of light fraction ratio are 3：1, column bottom temperature is 170 DEG C, Tower top temperature is 80 DEG C, tower top pressure 180kPa, and the main extraction solvent in extraction solvent is N- formyl-morpholines, and auxiliary agent is water And methanol, and the 5 weight % that auxiliary agent content is extraction solvent, content of the water in extraction solvent is 1 weight %.

In solvent recovery tower：Column bottom temperature is 180 DEG C, and tower top temperature is 80 DEG C, tower top pressure 40kPa, and stripping steams The dosage weight ratio of vapour and the sulfur-bearing solvent is 0.2：1.

In solvent regeneration tower：For the 3 weight % that regenerated recycling design is whole recycling designs, column bottom temperature is 180 DEG C, tower top temperature is 100 DEG C, tower top pressure 10kPa, and raffinate is discharged from bottom of towe, after regenerated solvent is mixed with recycling design Recycle, the water stripping used comes from the condensed water that solvent extraction destilling tower is collected with solvent recovery tower.After solvent extraction The μ g/g of non-mercaptan sulfur content in light fraction ≯ 5.

In caustic extraction system, volume ratio when light fraction is contacted with lye after solvent extraction is 8：2, temperature 25 DEG C, pressure 0.6MPa, obtains light fraction and sulfur-bearing lye after caustic extraction；The sulfur-bearing lye for absorbing mercaptan is urged in ARC-01 Agent effect is lower to carry out oxidation processes, and the injection rate of air is 2.4 times of theoretical amount in oxidizing process, and pressure during oxidation is 0.5MPa, temperature are 40 DEG C；Sulfur-bearing lye after oxidation by volume 1：10 after the hydrogenation from selective hydrogenation system with weighing Cut mixing carries the disulphide in the sulfur-bearing lye after removing oxidation with back suction, obtains regeneration lye and caustic extraction sulfur-bearing thing Material, regeneration lye recycle；The caustic extraction sulfide containing material is continuously discharged.

To making choice property of light fraction weighted BMO spaces and etherification process after caustic extraction, selective hydrogenation pretreatment condition For：Using selective hydrogenation pretreatment catalyst Cat2, reaction temperature is 80 DEG C, reaction pressure 1.0MPa, and volume is empty during liquid Speed is 4.0h^-1, hydrogen to oil volume ratio 1.Etherification reaction is carried out by the way that light fraction after the caustic extraction is contacted with methanol, etherificate Condition is：Using sulfonic acid ion exchange resin as catalyst for etherification, methanol and the alkene in light fraction after the caustic extraction The molar ratio of hydrocarbon is 1.02：1, liquid hourly space velocity (LHSV) 2.0h^-1, reaction temperature is 70 DEG C, reaction pressure 1.0MPa, after obtaining etherificate Light fraction.

In the selective hydrogenation system for heavy distillat, by sulfur-bearing thing after sulfide containing material, solvent extraction after caustic extraction Material making choice property hydrodesulfurization reaction together with heavy distillat after fractionation, the condition of selective hydrodesulfurization reaction：Hydrogen dividing potential drop is 1.6MPa, the first reaction zone use RSDS-11 catalyst, and reaction temperature is 200 DEG C, and second reaction zone uses catalyst Cat1, Reaction temperature is 300 DEG C, and volume space velocity is 3.0h during liquid^-1, hydrogen to oil volume ratio 400.Weight after being hydrogenated with after selective hydrogenation Cut, sulfur content is 8 μ g/g in heavy distillat after hydrogenation.

Light fraction after caustic extraction and heavy distillat after hydrogenation are mixed into low-sulphur oil product B；Or will gently it be evaporated after etherificate Divide and be mixed into low-sulfur, low-alkene gasoline products C with heavy distillat after hydrogenation.

The property of gasoline products B and gasoline products C are shown in Table 1.

From table 1 it follows that the desulfurization degree of gasoline products B is up to 98.7%, product sulfur content is only 8 μ g/g, is met No. V discharge standard gasoline products sulfur content of country is not more than the requirement of 10 μ g/g, and alkene saturation factor is 12.0%, RON penalty values For 1.1 units.

From table 1 it follows that the desulfurization degree of gasoline products C is up to 98.8%, product sulfur content is only 7 μ g/g, is met No. V discharge standard gasoline products sulfur content of country is not more than the requirement of 10 μ g/g, and olefin removal rate is 42.0%, RON increases 0.8 unit.

It can thus be seen that the group technology of the present invention has good desulfurization effect and reduces the effect of loss of octane number Fruit, if without the etherification process of light fraction, alkene saturation factor is few, and loss of octane number is also small, and passes through light fraction etherification process Afterwards, olefin(e) centent can be significantly reduced, and makes octane number effectively recover even to increase.

Also, in the present embodiment, due to having used the extraction solvent containing auxiliary agent in extractive distillation so that extracting is molten The effective rate of utilization of agent significantly improves, the solvent reclamation frequency reduce, and cause energy consumption relative reduction and running cost it is opposite Reduce.

Table 1

Comparative example 1

This comparative example, which uses, to be first fractionated gasoline stocks to obtain light fraction and heavy distillat, then carries out light fraction Caustic extraction, and heavy distillat is subjected to hydrodesulfurization, this comparative example is carried out using parameter similar to Example 1, this contrast The gasoline stocks of example are the feedstock oil A in table 1, unlike：

The cut point of gasoline stocks in embodiment 1 is defined to 65 DEG C, it is that the light of 30 weight % evaporates that yield is obtained after fractionation Divide the yield for the heavy distillat of 70 weight % with yield；

Light fraction is handled using caustic extraction mode, and caustic extraction condition is as follows：When light fraction is contacted with lye Volume ratio is 8：2, temperature is 25 DEG C, and pressure 0.6MPa, obtains light fraction after caustic extraction；Absorb the sulfur-bearing lye of mercaptan Aoxidized under the metal phthalocyanine catalyst effect being suspended in lye, metal phthalocyanine (sulfonated phthalocyanine cobalt, commercially available product) is in alkali Addition in liquid is 500 μ g/g, and the injection rate of air is 2.4 times of theoretical amount in oxidizing process, and pressure during oxidation is 0.5MPa, temperature are 40 DEG C；Sulfur-bearing lye after oxidation by volume 1：10 after the hydrogenation from selective hydrogenation system with weighing Cut mixing carries the disulphide in the sulfur-bearing lye after removing oxidation with back suction, obtains regeneration lye and caustic extraction sulfur-bearing thing Material, regeneration lye recycle；The caustic extraction sulfide containing material is continuously discharged.

This comparative example only with by after fractionation light fraction carry out caustic extraction and without solvent extraction, and will fractionation Heavy distillat making choice property hydrogenation reaction afterwards；This comparative example does not carry out solvent extraction and etherification process to light fraction.

For a kind of hydrogenation catalyst RSDS-11, hydrogenation temperature 320 are used only in the selective hydrogenation system of heavy distillat ℃。

Light fraction μ g/g of sulfur content ≯ 10 after caustic extraction, and sulfur content is 9 μ g/g after heavy fractioning hydrogenation.

Light fraction after caustic extraction and heavy distillat after hydrogenation are mixed into low-sulphur oil product D by this comparative example, as a result such as table 2 Shown in.

From table 2 it can be seen that the gasoline products D of the μ g/g of sulfur content ≯ 10 in order to obtain, with obtaining gasoline production in embodiment 1 The group technology of product B is compared, and the alkene saturation factor of the group technology of comparative example 1 is up to 41.0%, and octane number RON losses are up to 3.8 units.

Table 2

Oil product title	Raw material A	Light fraction after fractionation	Heavy distillat after fractionation	Gasoline products D
					Density (20 DEG C)/(g/cm³)	0.7302	0.6650	0.7512	0.7254
Sulfur content/(μ g/g)	600	107	811	9
					Mercaptan sulfur content/(μ g/g)	60	98	37	4
Olefin(e) centent/volume %	30.0	41.5	25.0	17.7
					RON	92.0	-	-	88.2
Desulfurization degree/%	-	-	-	98.5
					Alkene saturation/removal efficiency/%	-	-	-	41.0
△RON	-	-	-	-3.8

Embodiment 2

The present embodiment carries out deep desulfuration processing using the equipment shown in Fig. 2 to gasoline stocks E.

Gasoline stocks E is fractionated to obtain light fraction and receipts of the yield as 60 weight % at a temperature of 120 DEG C of cut point Rate is the heavy distillat of 40 weight %.

In solvent extraction system, solvent extraction distillation is carried out to the light fraction after fractionation in solvent extraction destilling tower, Light fraction and sulfur-bearing solvent after solvent extraction are obtained, sulfur-bearing solvent is 7 weight % of light fraction total amount.Then by distilling molten The sulfur-bearing solvent is separated to obtain sulfide containing material and removing after solvent extraction with the sulfide wherein contained in agent recovery tower The recycling design of sulfide：

In solvent extraction destilling tower：Extraction solvent and the feed weight ratio of the light fraction after fractionation are 4：1, column bottom temperature For 150 DEG C, tower top temperature is 95 DEG C, tower top pressure 200kPa, and the main extraction solvent in extraction solvent is N- methyl -2- pyrroles Alkanone, auxiliary agent are acetone, and the 4.2 weight % that auxiliary agent content is extraction solvent.

In solvent recovery tower：Column bottom temperature is 200 DEG C, and tower top temperature is 90 DEG C, tower top pressure 40kPa, and stripping steams The dosage weight ratio of vapour and the sulfur-bearing solvent is 0.25：1.

In solvent regeneration tower：For the 5 weight % that regenerated recycling design is whole recycling designs, column bottom temperature is 170 DEG C, tower top temperature is 100 DEG C, tower top pressure 8kPa, and raffinate is discharged from bottom of towe, after regenerated solvent is mixed with recycling design Recycle, the water stripping used comes from the condensed water that solvent extraction destilling tower is collected with solvent recovery tower.After solvent extraction Thiophene sulphur content in light fraction is 3 μ g/g.

After for solvent extraction in the adsorption system of light fraction, sorbent used SSA-01.Adsorbing the temperature contacted is 140 DEG C, pressure 0.6MPa, liquid hourly space velocity (LHSV) 0.5h^-1.The μ g/g of the sulfur content of light fraction after absorption ≯ 1.

To making choice property of light fraction weighted BMO spaces and etherification process after absorption, selective hydrogenation pretreatment condition is： Using selective hydrogenation pretreatment catalyst Cat2, reaction temperature is 100 DEG C, reaction pressure 1.2MPa, volume space velocity during liquid For 5h^-1, hydrogen to oil volume ratio 5.Etherification reaction is carried out by the way that light fraction after the absorption is contacted with methanol, and etherification conditions are： Using sulfonic acid ion exchange resin as catalyst for etherification, the molar ratio of methanol and the alkene in light fraction after the absorption is 1.05：1, liquid hourly space velocity (LHSV) 2.0h^-1, reaction temperature is 80 DEG C, reaction pressure 1.0MPa, light fraction after being etherified.

In the selective hydrogenation system for heavy distillat, by sulfide containing material after solvent extraction together with heavy distillat after fractionation Making choice property hydrodesulfurization reaction, the condition of selective hydrodesulfurization reaction：Hydrogen dividing potential drop is 1.6MPa, and the first reaction zone uses RSDS-11 catalyst, reaction temperature are 220 DEG C, and second reaction zone use catalyst Cat1, and reaction temperature is 295 DEG C, body during liquid Product air speed is 3.0h^-1, hydrogen to oil volume ratio 400.Heavy distillat after being hydrogenated with after selective hydrogenation, sulphur contains in heavy distillat after hydrogenation Measure as 6 μ g/g.

Light fraction after absorption and heavy distillat after hydrogenation are mixed into low-sulphur oil product F；Or will etherificate after light fraction with Heavy distillat is mixed into low-sulfur, low-alkene gasoline product G after hydrogenation.

The property of gasoline products F and gasoline products G are shown in Table 3.

From table 3 it is observed that the desulfurization degree of gasoline products F is up to 99.0%, product sulfur content is only 3 μ g/g, is met No. V discharge standard gasoline products sulfur content of country is not more than the requirement of 10 μ g/g, and alkene saturation factor is 13.5%, RON penalty values For 0,5 unit.

From table 3 it is observed that the desulfurization degree of gasoline products G is up to 99.4%, product sulfur content is only 2 μ g/g, is met No. V discharge standard gasoline products sulfur content of country is not more than the requirement of 10 μ g/g, and olefin removal rate is 58.1%, RON increases 0.7 unit.

Table 3

Embodiment 3

The present embodiment is using feedstock oil E same as Example 2 and identical combination sulfur removal technology, identical technique ginseng Number carries out, unlike：

Do not contain auxiliary agent in the extraction solvent used during the solvent extraction of the present embodiment, remaining with embodiment 2 Identical, as a result the thiophene sulphur content after solvent extraction in light fraction is 5 μ g/g.

Heavy distillat after being hydrogenated with after selective hydrogenation, sulfur content is 6 μ g/g in heavy distillat after hydrogenation.

Light fraction after absorption and heavy distillat after hydrogenation are mixed into low-sulphur oil product H；Or will etherificate after light fraction with Heavy distillat is mixed into low-sulfur, low-alkene gasoline product I after hydrogenation.

The property of gasoline products H and gasoline products I are shown in Table 4.

As can be seen from Table 4, the desulfurization degree of gasoline products H is up to 99.0%, and product sulfur content is only 3 μ g/g, meets No. V discharge standard gasoline products sulfur content of country is not more than the requirement of 10 μ g/g, and alkene saturation factor is 13.5%, RON penalty values For 0.5 unit.

As can be seen from Table 4, the desulfurization degree of gasoline products I is up to 99.4%, and product sulfur content is only 2 μ g/g, meets No. V discharge standard gasoline products sulfur content of country is not more than the requirement of 10 μ g/g, and olefin removal rate is 58.1%, RON increases 0.7 unit.

The result of contrast the present embodiment and embodiment 2 can be seen that uses the pumping containing auxiliary agent during solvent extraction Extraction solvent, enables to the thiophene sulphur content after solvent extraction of the present invention more lower, but after follow-up adsorption treatment, The sulfur content of product can tend to be identical.

However, from the point of view of solvent extraction, in the present embodiment, since auxiliary agent is not used, in extractive distillation, take out The effective rate of utilization of extraction solvent can reduce, and the long period for being unfavorable for extracting carries out.

Table 4

It can be seen from the results above that method provided by the invention can be in the premise for the greater loss for avoiding octane number Under, the gasoline products of acquisition more low-sulfur.Also, during solvent extraction, the use of auxiliary agent has necessarily solvent extraction Facilitation, and can further deducing, when solvent is recycled for a long time, especially when solvent decomposes, impurity content Rise, auxiliary agent to the effect of solvent extraction sulfide advantageously.Especially, coordinate etherification reaction process, enable to this hair The octane number of bright gasoline products raises and sulfur content further reduces, while alkene is also greatly lowered, and is conducive to meet not Carry out the requirement of VI gasoline standard of state.

The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of method of deep desulfurization of gasoline, including：

(2) light fraction is contacted with extraction solvent to carry out solvent extraction by distilling, obtains sulfur-bearing solvent and solvent is taken out Rear light fraction is proposed, is then separated the sulfur-bearing solvent to obtain solvent extraction with the sulfide wherein contained by being evaporated under reduced pressure Sulfide containing material and the recycling design for being stripped of sulfide afterwards；

Mode 1 includes：Light fraction after the solvent extraction is contacted to carry out caustic extraction with lye, obtains sulfur-bearing lye and alkali Light fraction after liquid extracting, then carries out oxidation processes with the sulfur-bearing lye after being aoxidized by the sulfur-bearing lye, and by the oxygen Sulfur-bearing lye after change is contacted with varsol proposes processing to carry out back suction, obtains sulfide containing material after caustic extraction and can circulate The regeneration lye used；

(4) heavy distillat is contacted with Hydrobon catalyst with making choice property hydrodesulfurization reaction, weight after being hydrogenated with Cut；

(5) the removal of mercaptans light fraction that step (3) obtains is mixed with heavy distillat after the hydrogenation of step (4) to obtain gasoline production Product, the removal of mercaptans light fraction are the absorption of light fraction or the acquisition of the mode 2 after the caustic extraction of the mode 1 acquisition Light fraction afterwards.

2. according to the method described in claim 1, wherein, this method further comprises：With being weighed after the hydrogenation of step (4) Before cut mixing, the removal of mercaptans light fraction is first subjected to etherification reaction, light fraction after being etherified；Then again by the ether Light fraction is mixed to obtain the gasoline products with heavy distillat after the hydrogenation of step (4) after change.

3. according to the method described in claim 2, wherein, the etherification reaction is by by the removal of mercaptans light fraction and carbon atom Low-carbon alcohols of the number no more than 6 are contacted and carried out；Preferably,

The low-carbon alcohols be methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, n-amyl alcohol and cyclohexanol at least It is a kind of.

4. according to the method in claim 2 or 3, wherein, the condition of the etherification reaction includes：The low-carbon alcohols are former with carbon The molar ratio that subnumber is not more than the alkene in 6 is (0.5~3)：1, be preferably (1.0~1.2)：1, the temperature of contact for 20~ 100 DEG C, pressure is 0.3MPa~1.0MPa；Preferably,

The etherification reaction carries out in the presence of the strong-acid ion exchange resin as catalyst for etherification.

5. according to the method described in any one in claim 2-4, wherein, this method further comprises：Carrying out the ether Before changing reaction, the removal of mercaptans light fraction is first subjected to absorption pretreatment and/or making choice property weighted BMO spaces；It is preferred that Ground,

The selective hydrogenation pretreatment carries out in the presence of transition metal loaded catalyst, and the transition metal support type is urged Agent includes the metal active constituent of carrier and load on the carrier, and the carrier is selected from aluminium oxide, silica, aluminosilicate At least one of salt, titanium oxide, zeolite and activated carbon, the metal active constituent in nickel, cobalt, molybdenum, platinum and palladium extremely Few one kind；Preferably,

Carrier in the transition metal loaded catalyst is aluminium oxide, and load capacity of the metal active constituent in terms of oxide is 0.05~15 weight %；Preferably,

The condition of the selective hydrogenation pretreatment includes：Hydrogen dividing potential drop is 0.1MPa~2.0MPa, and temperature is room temperature~250 DEG C, Volume space velocity is 1.0h during liquid^-1~10.0h^-1, hydrogen to oil volume ratio is 1~100.

6. according to the method described in any one in claim 1-5, wherein, this method further comprises：By in step (2) Sulfide containing material makes choice together with the heavy distillat after caustic extraction after solvent extraction in sulfide containing material and/or step (3) Property hydrodesulfurization reaction；Or

Sulfide containing material after sulfide containing material after solvent extraction in step (2) and/or the caustic extraction in step (3) is introduced into catalysis Catalytic cracking reaction is carried out in cracking unit to obtain at least part gasoline stocks for step (1).

7. according to the method described in any one in claim 1-6, wherein, during the solvent extraction, the extracting Solvent and the weight ratio of the light fraction are (0.5~20)：1, be preferably (1~5)：1；Preferably,

The solvent extraction carries out in extraction distillation tower, and the condition in the extraction distillation tower includes：Tower top pressure is 100kPa~500kPa, is preferably 110kPa~300kPa；Tower top temperature is 50~180 DEG C；Column bottom temperature is 80~260 DEG C, Preferably 140~200 DEG C.

8. the method according to claim 1 or 7, wherein, main extraction solvent, the main extracting are contained in the extraction solvent The boiling point of solvent is 175~320 DEG C, and preferably boiling point is 175~250 DEG C；Preferably,

The main extraction solvent is selected from sulfolane, 3- methyl sulfolanes, 2,4- dimethylsulfolanes, 3- ethylsulfolanes, methyl Ethyl sulfone, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dibutyl sulfone, dimethyl sulfoxide (DMSO), furfural, furfuryl alcohol, alpha-pyrrolidone, N- N-methyl-2-2-pyrrolidone N, N- ethyl-2-pyrrolidones, N- propyl group -2-Pyrrolidone, N- formyl-morpholines, dimethyl formyl Amine, triethylene glycol, tetraethylene glycol, five glycol, triethylene glycol methyl ether, tetraethylene glycol methyl ether, ethylene carbonate, propene carbonate, isobutyl carbonate third The polyethylene glycol and relative molecular mass of enester, acetonitrile, nitrobenzene, relative molecular mass between 200~400 are 200~400 Between at least one of methoxypolyethylene glycol；Preferably,

The main extraction solvent is in sulfolane, N- formyl-morpholines, n-methyl-2-pyrrolidone, tetraethylene glycol and five glycol At least one.

9. according to the method described in any one in claim 1,7 and 8, wherein, further contain in the extraction solvent and help Agent, the auxiliary agent is can dissolve each other and its boiling point or do the boiling point not higher than the main extraction solvent with the main extraction solvent Or at least one of alcohols, ketone, organic acid and organic nitrogen compound done material and/or water, the organic nitrogen compound For at least one of amine, ureas and alcamines；Preferably,

The alcohols, ketone, the carbon number of organic acid and organic nitrogen compound are no more than 6；Preferably,

In the extraction solvent, the content of the auxiliary agent is 0.1~20 weight %, is preferably 0.5~15 weight %.

10. according to the method described in claim 9, wherein, the auxiliary agent is selected from water, methanol, ethanol, normal propyl alcohol, isopropanol, third Ketone, methyl ethyl ketone, isobutyric acid, ethanedioic acid, malonic acid, succinic acid, urea, ethylenediamine, monoethanolamine, 2-Methylaminoethanol, N- Ethyl monoethanolamine, N, N- dimethylethanolamines, N, N- diethyl ethylene diamines, diethanol amine, N methyldiethanol amine, three ethanol At least one of amine, n-propanolamine, isopropanolamine and diglycolamine；Preferably,

The auxiliary agent is selected from water, methanol, acetone, methyl ethyl ketone, isobutyric acid, ethanedioic acid, malonic acid, succinic acid, ethylenediamine, an ethanol At least one of amine, 2-Methylaminoethanol, isopropanolamine and diglycolamine；

Preferably, the auxiliary agent is the mixture containing water, and content of the water in the extraction solvent is 0.1~5 weight %, excellent Elect 0.1~3 weight % as.

11. according to the method described in any one in claim 1-10, wherein, by vacuum distillation by the sulfur-bearing solvent with The separated condition of sulfide wherein contained includes：The tower top pressure of solvent recovery tower is 10kPa~100kPa, and tower top temperature is 50~100 DEG C, column bottom temperature is 100 DEG C~250 DEG C, and preferably column bottom temperature is 120~200 DEG C, stripped vapor and the sulfur-bearing The weight ratio of solvent is (0.01~5.0)：1.

12. according to the method described in any one in claim 1-11, wherein, this method further comprises：Will be at least partly The recycling design carries out water filling purification processes to regenerate in solvent regeneration tower；Preferably,

Regeneration condition in the solvent regeneration tower includes：Tower top pressure is 1kPa~10kPa, and tower top temperature is 90~110 DEG C, It is preferred that tower top temperature is 96~105 DEG C, column bottom temperature is 120 DEG C~200 DEG C, and preferably column bottom temperature is 150 DEG C~200 DEG C, note The weight ratio of the water entered and the recycling design is (0.1~10)：1, preferred weight ratio is (0.5~5)：1；Preferably

1~10 weight % of all recycling designs is accounted for for carrying out regenerated recycling design, preferably accounts for all recycling 1~5 weight % of solvent.

13. according to the method described in any one in claim 1-12, wherein, the selective hydrodesulfurization reaction is successively Carried out in first reaction zone of connection and second reaction zone, load the in first reaction zone and the second reaction zone respectively One Hydrobon catalyst and the second Hydrobon catalyst, first Hydrobon catalyst and the second hydrodesulfurization catalytic Agent is independently of one another containing alumina support and/or silica-alumina supports and load hydrogenation active metals group on the carrier Point, the hydrogenation active metal component is for the group vib non-noble metal j element selected from molybdenum and/or tungsten and/or selected from nickel and/or cobalt VIII group non-noble metal j element；Preferably,

First Hydrobon catalyst and the second Hydrobon catalyst independently of one another containing molybdenum and/or tungsten, nickel and/or Cobalt, alumina host and large pore zeolite and/or mesopore zeolite；Preferably,

On the basis of the total amount of the Hydrobon catalyst, the group vib non-noble metal j element is using the content that oxide is counted as 2 ~25 weight %, the VIII group non-noble metal j element is using the content that oxide is counted as 0.2~6 weight %.

14. according to the method for claim 13, wherein, the reaction condition of first reaction zone and second reaction zone is each Independently include：Hydrogen dividing potential drop is 0.1MPa~4.0MPa, and reaction temperature is 200 DEG C~440 DEG C, and volume space velocity is 1.0h during liquid^-1 ~10.0h^-1, hydrogen to oil volume ratio is 200~1000；Preferably,

First reaction zone and the reaction condition of second reaction zone include independently of one another：Hydrogen dividing potential drop for 1.0MPa~ 3.2MPa, reaction temperature are 200 DEG C~300 DEG C, and volume space velocity is 2.0h during liquid^-1~6.0h^-1, hydrogen to oil volume ratio for 200~ 600。

15. according to the method described in claim 1, wherein, the lye in the caustic extraction is ammonium hydroxide and/or alkali metal hydrogen-oxygen The aqueous solution of compound, and the concentration of the lye is 1~50 weight %, is preferably 5~25 weight %；Preferably,

Adsorbent adsorbent for physical adsorbent and/or chemically；The physical adsorbent, which preferably comprises, to be selected from The porous material of at least one of silica, aluminium oxide, zeolite, clay and activated carbon；Wrapped in the chemically adsorbent Include absorption agent aid and metal, metal oxide or metal ion compound containing transition metal, the transition metal Element is selected from least one of ferro element, cobalt element, nickel element, copper and Zn-ef ficiency, and the absorption agent aid is selected from alkali At least one of metallic element and alkali earth metal；Preferably,

Light fraction includes with the condition that the adsorbent contacts after the solvent extraction：Temperature is 10~300 DEG C；Pressure is 0.1 ~2MPa, liquid hourly space velocity (LHSV) are 0.1~1h^-1。

16. according to the method described in claim 1, wherein, the cut point of the light fraction and heavy distillat is 80~120 DEG C；It is excellent Selection of land,

On the basis of the gasoline stocks, the yield of the light fraction is 40~60 weight %, and the yield of the heavy distillat is 40 ~60 weight %；Preferably,

The gasoline stocks are selected from catalytically cracked gasoline, catalytic cracking gasoline, direct steaming gasoline, coker gasoline, drippolene and heat At least one of cracking gasoline.

17. according to the method described in any one in claim 1-16, wherein, in step (5), the sulphur of gained gasoline products The μ g/g of content ≯ 10.

18. a kind of equipment for deep desulfurization of gasoline, including：

Fractionating system (2), gasoline fraction are fractionated to obtain light fraction and heavy distillat by the fractionating system (2)；

Solvent extraction system (5), including solvent extraction distillation unit and solvent recovery unit, the solvent extraction distillation unit are used Solvent extraction is carried out in the light fraction that will come from fractionating system (2), obtains light fraction after sulfur-bearing solvent and solvent extraction；It is described molten Agent recovery unit be used to the sulfide wherein contained separating the sulfur-bearing solvent with obtain after solvent extraction sulfide containing material and It is stripped of the recycling design of sulfide；

Light fraction desulphurization system, the light fraction desulphurization system are caustic extraction system (81) or adsorption system (82), which takes out Putting forward system (81) includes mercaptan extraction unit, alkali liquor oxidized unit and the anti-extraction unit of lye, and the mercaptan extraction unit is used for Light fraction is contacted with lye to carry out caustic extraction after the solvent extraction of solvent extraction system in future (5), obtains caustic extraction Light fraction and sulfur-bearing lye afterwards, the alkali liquor oxidized unit is used to the sulfur-bearing lye carrying out oxidation processes, after obtaining oxidation Sulfur-bearing lye；And the anti-extraction unit of lye is used to the sulfur-bearing lye progress back suction after the oxidation proposing processing to obtain Sulfide containing material and the regeneration lye that can be recycled after to caustic extraction；And the adsorption system (82) is used for solvent in future Light fraction is contacted with the adsorbent contained in the adsorption system gently to evaporate after being adsorbed after the solvent extraction of extraction system (5) Point；

Selective hydrogenation system (15), the heavy distillat from fractionating system (2) are introduced to the selection hydrogenation system by pipeline (15) making choice property hydrodesulfurization reaction is with heavy distillat after being hydrogenated with；

Heavy distillat is mixed with removal of mercaptans light fraction after the hydrogenation is incorporated as gasoline products and is drawn by pipeline, and the removal of mercaptans is light Cut is light fraction after light fraction after caustic extraction or the absorption；Preferably,

The equipment further comprises etherification system (13), and the removal of mercaptans light fraction from light fraction desulphurization system first passes through pipeline and draws Enter to etherification reaction is carried out in the etherification system (13) with light fraction after being etherified；Then again by this be etherified after light fraction and institute Heavy distillat mixing as gasoline products by pipeline to be drawn after stating hydrogenation；Preferably,

The solvent extraction system (5) further comprises solvent regeneration unit, which is used to come from described molten The recycling design of agent recovery unit is introduced in the solvent regeneration unit by pipeline carries out water filling purification processes to regenerate.