CN101275085B - Combined method for gasoline desulfurization - Google Patents
Combined method for gasoline desulfurization Download PDFInfo
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- CN101275085B CN101275085B CN2007100649820A CN200710064982A CN101275085B CN 101275085 B CN101275085 B CN 101275085B CN 2007100649820 A CN2007100649820 A CN 2007100649820A CN 200710064982 A CN200710064982 A CN 200710064982A CN 101275085 B CN101275085 B CN 101275085B
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Abstract
The present invention provides a combination method of gasoline desulfurization, including dividing gasoline into a light fraction and a heavy fraction, the heavy fraction is divided into a large fluid and a small fluid; the light fraction is processed with caustic extraction; the lye is regenerated under the impact of oxidant; the mixer of the regeneration lye and the disulphide is contacted with a small heavy fraction, the disulphide is extracted in the heavy fraction; the mixer of the small heavy fraction containing disulphide and the regeneration lye is mixed with the large heavy fraction after settlement separate, processing selective hydrodesulfurization reaction; the heavy fraction after desulphurized is mixed with the light fraction after desulphurized, the product is obtained by removing the new thiol in the hydrogenation course. The combination method of the invention uses small heavy fraction absorb disulphide produced by the light fraction lye extraction course, not using other hydrocarbon solvent, processing treatment without other hydrogenation unit, reducing the production cost; furthermore, the trace oxygen in the regeneration lye is also removed, improving the efficiency of lye extraction.
Description
Technical field
The present invention relates to a kind of method of gasoline desulfur, specifically, relate to the combined method that a kind of catalytically cracked gasoline carries out desulfurization through hydrogenation and non-hydrogenation mode.
Background technology
As everyone knows, the discharging of hazardous and noxious substances is having a strong impact on Air quality in the vehicle exhaust, and for this reason, countries in the world all define more and more stricter standard to the oil quality as motor spirit, especially aspect sulphur content, are tending towards strict qualification day by day.As everyone knows, the sulphur in the gasoline mainly comes from catalytic cracking (FCC) gasoline.The raw material of processing along with FCC develops to the heaviness direction, will cause the sulphur content of FCC gasoline further to increase.Therefore, the sulphur content of reduction FCC gasoline is to reduce the key point of finished product content of sulfur in gasoline.
Sulphur in the gasoline comprises thio-alcohol, thioether class, disulfide class and thiophene-based (comprising thiophene and thiophene derivant) etc.In the gasoline standard that acts as a fuel, its mercaptan sulfur content and total sulfur content have been stipulated ceiling value.When mercaptan sulfur content exceeds standard or total sulfur content must carry out mercaptan removal or desulfuration purification to gasoline when exceeding standard.
Aspect mercaptan removal; The alkali lye extracting is a kind of traditional method of refining hydrocarbon material; Be widely used in the processing of hydrocarbon materials such as LPG liquefied petroleum gas, gasoline, diesel oil, petroleum naphtha, alkane, alkene; Its method is that hydrocarbon fluid is contacted with alkali lye, and the mercaptan in the hydrocarbon stream is through generating thiolate with alkaline reaction and from oil product, removing.And if the alkali lye that contains thiolate directly discharges the both uneconomical environmental requirement that also do not meet.Thereby the method for using oxidation usually makes thiolate be oxidized to disulphide makes the alkali lye that contains thiolate obtain regeneration (consulting U.S. Pat 2853432,2921020,4705620).Through in used alkali lye, injecting air and oxide catalyst; The thiolate that is dissolved in the alkali lye is oxidized to disulphide; Make alkali liquid regeneration thus; Alkali lye after the regeneration uses (consulting U.S. Pat 3574093,4666689) through disulphide continued in settlement separate or the varsol extracting regeneration alkali lye, significantly reduces the discharging of salkali waste thus.
When adopting traditional extraction process to handle lighting end, the disulphide that is produced in the alkali liquid regeneration process removes with the reformed naphtha extracting usually, and extracting has the reformed naphtha of disulphide to need carrying device to arrive the reformer processing outward.And, since feed during alkali liquid regeneration to contain the oxygen air greatly excessive usually, and excess air flows into phase-separation system with alkali lye usually, discharges in phase-separation system.Do two shortcomings like this: the one, the air that flows into phase-separation system is prone in alkali lye, to form aeration regeneration alkali lye and disulphide mutually or contain solvent phase settlement separate of disulphide; Make the solvent that still is entrained with disulphide in the regeneration alkali lye or contains disulphide; When regeneration alkali lye returns extraction system and recycles, can the disulphide back suction be mentioned in the lighting end, be difficult to reach and handle the purpose that distillate carries out desulfurization with alkali lye; The 2nd, the regeneration micro-air that alkali lye contained is difficult to remove fully after release air; When regeneration alkali lye returns extraction system and recycles; The micro-air of at least a portion mercaptan in alkali lye in the lighting end and still stay and but be not absorbed in the lighting end in the alkali lye with generating disulphide the effect of alkali lye round-robin oxide catalyst under, sweetening effectiveness like this also can reduce.
Therefore, the improvement of this method is mainly concentrated on separate (the consulting U.S. Pat 4705620, US4362614 and US3574093) of disulphide and regeneration alkali lye.In addition, U.S. Pat 2921020 also utilizes oxygen residual in the regeneration alkali lye and oxide catalyst that the hydrocarbon stream of handling through extracting is carried out secondary treatment, further to remove mercaptan remaining in the hydrocarbon stream.
Aspect gasoline desulfur, method is a lot.Wherein, hydrotreatment is a kind of common selecteed method, because hydrotreatment is easy to the sulphur in the gasoline is sloughed.Yet in hydrogenation process, the alkene in the gasoline is converted into the low octane rating component easily, thereby makes hydrotreatment often be accompanied by bigger loss of octane number.For fear of loss of octane number, there are many sulfur methods relevant to be developed with hydrogenation.
USP3957625 has reported a kind of method of gasoline desulfur.Said method is that gasoline is cut into weight two portions, reduces the sulphur content (the less reduction of olefin content in gasoline) in the gasoline through the mode of heavy naphtha being carried out the selective hydrogenation processing.
USP6610197B2 has reported a kind of method of gasoline desulfur.Said method is that gasoline is cut into weight two portions, and non-hydrotreatment is carried out in lighting end, and hydrotreatment is carried out in last running, reduces the sulphur content in the gasoline with this.
USP6623627B1 has reported a kind of working method of low-sulphur oil.Said method is that gasoline is cut into basic, normal, high boiling point three part cuts; The low boiler cut that wherein contains mercaptan contacts selectively removing mercaptan with alkali lye; The mid-boiling point cut that contains thiophene carries out desulfurization through extracting; The extract that contains thiophene and the high boiling fraction of mid-boiling point cut carry out desulphurization reaction in hydrodesulfurizationzone zone, make the gasoline products that sulphur content reduces thus.
CN02121594.4 has reported a kind of method of producing low-sulphur oil.Said method is that gasoline is cut into gently, weighs two portions cut, and lighting end adopts the extractive mode of alkali lye to handle, and last running adopts the mode of selective hydrogenation to handle.
Summary of the invention
The object of the invention just is to overcome the above-mentioned shortcoming of prior art, and a kind of combined method of improved gasoline desulfur is provided.
The combined method of gasoline desulfur provided by the invention comprises:
1) gasoline is cut into gently, weighs two portions cut, last running is divided into large and small two portions fluid again, and the part by weight of small portion last running and most of last running is 1:1～500;
2) lighting end contacts with alkali lye, and the mercaptan in the lighting end is gone into to generate thiolate in the alkali lye by extracting;
3) make thiolate in the alkali lye under the effect of air and metal phthalocyanine catalyst, be oxidized to disulphide, make alkali liquid regeneration;
4) regeneration alkali lye and the mixture of disulphide contacts with small portion last running from step 1), and disulphide is gone in the last running by extracting;
5) the small portion last running that contains disulphide with the mixture of regeneration alkali lye settlement separate after, regeneration alkali lye returns step 2);
6) the small portion last running that contains disulphide mixes with most of last running, under the effect of selective hydrogenation catalyst, carries out the selective hydrodesulfurization reaction;
7) from last running after the desulfurization of step 6) with from step 2) mercaptan removal after lighting end mix, remove mercaptan newly-generated in the hydrogenation process and become product; Remove mercaptan newly-generated in the hydrogenation process again after perhaps removing hydrogen sulfide from last running after the desulfurization of step 6), afterwards with from step 2) mercaptan removal after lighting end mix and become product.
Method provided by the invention is said from flow process and is comprised consecutive fractionating system, extraction system, oxidation system, phase-separation system, hydrogenation system and deodorization system.Phase-separation system comprises again that specifically three systems---separation removal system, settling separation system and coalescence remove system.
Specifically, the combined method of gasoline desulfur provided by the invention may further comprise the steps:
1) through separation column gasoline is cut into gently, weighs two portions cut; Last running is divided into large and small two portions fluid again; Wherein most of mercaptan and the alkene in the gasoline has been concentrated in lighting end, and last running has been concentrated other sulfide of the major part in the gasoline and contained a small amount of mercaptan.
Related gasoline stocks comprises: catalytic cracking (FCC) gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline or its mixture.
The fractionation cutting temperature of said gasoline is between 50～120 ℃, and between preferred 60～100 ℃, the yield of lighting end and last running is respectively 30～60 heavy % and 40～70 heavy % of gasoline stocks.The part by weight of small portion last running and most of last running is 1:1～500, preferred 1:1～100.
2) contain mercaptan and contact at extraction system with the alkali lye that is substantially free of disulphide with the lighting end of alkene, the mercaptan in the lighting end is absorbed into and generates thiolate in the alkali lye, and the lighting end that removes the reduction of mercaptan and sulphur content separates the back and flows out with extracting alkali lye.
The service temperature of extraction system is between 5～100 ℃, and preferably between 25～75 ℃, the pressure that is adopted is usually between 0.1～2.0MPa.The alkali lye volume that is adopted for the lighting end volume between 1～50%, preferably between 5～40%.
Alkali lye used in the present invention comprises any known alkaline reagents with extracting mercaptan ability from gasoline.Ideal alkali lye is generally the aqueous solution of alkali metal hydroxide, for example sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate etc.If necessary, can use the aqueous solution of the aqueous solution, ammoniacal liquor and organic quaternary ammonium hydroxide of alkaline earth metal hydroxidess such as calcium hydroxide, hydrated barta.Can add auxiliary agent in the alkaline reagents, like low-carbon alcohol: methyl alcohol, ethanol, Virahol etc., the compounds of nitrogenous, phosphorus, oxygen, sulphur, arsenic, antimony and basic nitrogen compound etc.Supply the sodium hydroxide solution of the special ideal alkali lye of the present invention's use, preferably use the sodium hydroxide solution of 5～25% (weight) for about 1～50% (weight).
3) alkali lye that contains thiolate from extraction system flows into oxidation system; Under the effect of purifying air of being injected and metal phthalocyanine catalyst; Thiolate in the alkali lye is oxidized to disulphide, and alkali lye is able to regeneration, and unnecessary air discharges from the top of oxidation system.
The catalyzer that uses in the oxidation system is metal phthalocyanine catalyst, and preferred phthalocyanine cobalt compounds such as sulfonated phthalocyanine cobalt are as oxide catalyst.Phthalocyanine cobalt class catalyzer can use through being dissolved in the alkali lye or in alkali lye, forming stable milk sap, also can use through loading on porous material such as the gac form with fixed bed, preferably adopts last mode to use catalyzer.The oxygenant that employed sulfur oxide alkoxide is a disulphide is from airborne oxygen.After oxidation system was handled, the thiolate in the alkali lye changed into disulphide, and alkali lye is regeneration therefore.The air that is injected is for purifying air; Air capacity equals at least to make that mercaptan salt is oxidized to the required stoichiometric quantity of disulphide in the alkali lye; Be generally 2～4 times of stoichiometric quantity, the catalyzer that is injected is 5～1000ppm at the content of alkali lye, preferred 10～400ppm.The pressure of oxidation system and generally is lower than the pressure of extraction system between 0.1～2.0MPa.
The airflow that before oxidation system, injects discharges at the oxidation system top after oxidation system.If possible, can light ends unit be set, be used for reclaiming alkali lye, rather than flow into phase-separation system release with regeneration alkali lye with the effusive micro-lighter hydrocarbons of air at the oxidation system top.The metal phthalocyanine catalyst that before oxidation system, adds flows and circulation with alkali lye.
4) flow into the separation removal system of phase-separation system from the mixture of the regeneration alkali lye of oxidation system and disulphide and trace oxygen; Contact with small portion last running from the gasoline fractionating system; Disulphide in the alkali lye is gone in the last running by extracting; Simultaneously, if also have a trace oxygen, the effect of metal phthalocyanine catalyst that can be in alkali lye down and the thiol reactant in the last running and being removed in the regeneration alkali lye after the release air.
The separation removal system can adopt simple vertical tower, jar or similar containers, also can adopt the vertical tower, jar or the similar containers that contain suitable contact device.Contact can be adopted known variety of way, as and stream, adverse current or be the fixed bed mode of medium with the gac.The temperature of the regeneration alkali lye that is mixed with disulphide that the temperature of separation removal system is equivalent to flow into is between 5～100 ℃, preferably between 25～75 ℃.The pressure of separation removal system and generally is lower than the pressure of oxidation system between 0.1～2.0MPa.Volume ratio 1:1～the 1:100 of small portion last running and regeneration alkali lye, preferred 1:1～1:50.
5) flow into settling separation system from the small portion last running that contains disulphide of separation removal system and the mixture of isolating disulphide and removing the regeneration alkali lye of trace oxygen.After settlement separate, regeneration alkali lye returns extraction system and continues the mercaptan in the extracting lighting end, and the small portion last running that contains disulphide can be used for the disulphide of extracting alkali lye once more.
At settling separation system, usually use as fillers such as steel wire, sand, glass as coalescing agent with the coalescence of promotion disulphide in oil phase, and use residence time of 0.5～2.0 hour usually, with the separation of further promotion phase.Temperature and pressure that settling separation system and coalescence remove system are respectively natural temperature and natural pressure.
6) remove through coalescence from the small portion last running that contains disulphide of settling separation system and mix with most of last running after system handles removes contained micro-alkali lye and other impurity; Also can before coalescence is handled, circulate and be used for the disulphide of extracting alkali lye; Mix with all the other most of last running afterwards, flow into hydrogenation system and under the effect of selective hydrogenation catalyst, carry out the selective hydrodesulfurization reaction from fractionating system.
Said hydrogenation catalyst and hydroconversion condition are with reference to patent documentation CN02121594.4; Hydrogenation catalyst is VIB or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports; Preferred catalyzer contains one or more and the alumina host in molybdenum and/or tungsten, nickel and/or cobalt, auxiliary agent magnesium, macropore and the mesopore zeolite; In oxide compound and with the total catalyst weight is benchmark; The content of said molybdenum and/or tungsten is that the content of 3～20 heavy %, nickel and/or cobalt is that 0.3～2 heavy %, auxiliary agent Mg content are 1～7 heavy %, and the content of said zeolite is 5～60 heavy %.The condition of said selective hydrodesulfurization is: hydrogen dividing potential drop 1.0～3.2MPa, 200～300 ℃ of temperature of reaction, liquid hourly space velocity 2.0～6.0h
-1, hydrogen to oil volume ratio 200～600.
7) from last running after the desulfurization of hydrogenation system with mix from the lighting end behind the extraction desulfurization alcohol of extraction system, get into fixed bed deodorization system then and under the effect of fixed bed metal phthalocyanine catalyst, remove mercaptan newly-generated in the hydrogenation process and become product.Perhaps carry and remove the last running of hydrogen sulfide back end hydrogenation and also can directly get into fixed bed deodorization system and remove mercaptan newly-generated in the hydrogenation process, become product with mixing afterwards from the lighting end behind the extraction desulfurization alcohol of extraction system through gas.
Said fixed bed deodour method is in the presence of oxygen and alkaline reagents, with gasoline and catalytic amount be that the negative ions of carrier contacts the shaped metal phthalocyanine catalyst with the porous material, react.The pressure of fixed bed deodorization system is between 0.1～2.0MPa, and optimum operation pressure is between 0.2～0.8MPa.The temperature of fixed bed deodorization system is between 5～100 ℃, and preferably between 25～75 ℃, liquid hourly space velocity is 1～8h
-1, preferred 1～4h
-1
Said alkaline reagents is selected from the aqueous solution of inorganic alkali lye and/or alkaline organic compound, and the inorganic alkali lye of ideal is generally the aqueous solution of alkali metal hydroxide, for example sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate etc.If necessary, can use aqueous solution, ammoniacal liquor of alkaline earth metal hydroxidess such as calcium hydroxide, hydrated barta etc., the aqueous solution of the preferred organic quaternary ammonium hydroxide of the aqueous solution of said alkaline organic compound.
Said fixed bed deodorization reaction is preferably carried out under the situation that acvator exists simultaneously; Said acvator is the mixture of polar compound and/or compounds, and said polar compound can be water, is selected from the low-carbon alcohol of methyl alcohol, ethanol and/or Virahol, reaches the basic nitrogen compound like alkyl amine, hydroxyalkyl amine.Said compounds can be quaternary ammonium compounds, rattle compounds,
compounds, antimony compounds, oxygen compounds and sulfonium compounds etc.; As cationic atom is respectively N, P, As, Sb, O and S etc., preferred quaternary ammonium salt and/or quaternary ammonium hydroxide.Said acvator accounts for content in the pending gasoline between 10～10000ppm, between preferred 50～800ppm.Said alkaline reagents and said acvator can mix the back with pending gasoline to be used, also can be pre-soaked or be adsorbed on the support of the catalyst and use with metal phthalocyanine.
Said fixed bed deodorization catalyst is to be carrier with the porous material, and load accounts for 0.1～10 heavy % of catalyzer gross weight, and the metal phthalocyanine of preferred 0.1～3.0 heavy % constitutes.Pre-soaked or when being adsorbed on the support of the catalyst, its weight accounts for 0.1～80 heavy % of catalyzer gross weight, preferred 0.1～60 heavy % when said alkaline reagents and said acvator.
The preferred negative ions of said metal phthalocyanine is made up of metal phthalocyanine with positive ion group and the metal phthalocyanine with negative ion group the shaped metal phthalocyanine.Metal phthalocyanine is selected from magnesium phthalocyanine, titanium phthalocyanines, hafnium phthalocyanine, vanadyl phthalocyanine, tantalum phthalocyanine, molybdenum phthalocyanine, manganese phthalocyanine, iron-phthalocyanine, cobalt phthalocyanine, platinum phthalocyanine, palladium phthalocyanine, copper phthalocyanine, silver-colored phthalocyanine, zinc phthalocyanine, tin phthalocyanine etc., preferred cobalt phthalocyanine and vanadyl phthalocyanine.Said metal phthalocyanine is selected from sulphonate, carboxylate salt and quaternary ammonium salt, compounds of metal phthalocyanine etc.Said metal phthalocyanine with positive ion group is selected from sulphonate, the carboxylate salt of metal phthalocyanine; The sulphonate of preferred cobalt phthalocyanine comprises a kind of in the tetrasulfonate (four sulfonated phthalocyanine cobalts) of trisulfonate (three sulfonated phthalocyanine cobalts), cobalt phthalocyanine of disulfonate (two sulfonated phthalocyanine cobalt), the cobalt phthalocyanine of monosulfonate (single sulfonated phthalocyanine cobalt), the cobalt phthalocyanine of cobalt phthalocyanine or any mixture wherein.Said metal phthalocyanine with negative ion group is selected from quaternary ammonium salt, the compounds of metal phthalocyanine, the quaternary ammonium salt of preferred cobalt phthalocyanine, and its general formula is CoPc [N (R
1R
2R
3) A]
a, wherein Pc is the symbol of general expression phthalocyanine substruction, R
1, R
2, R
3Be the identical or different alkyl with 1～3 carbon atom, A is a halide anion, and most preferred is I
-, a is quaternized degree, and its value is 1～4, and most preferred is 4.
Said porous material as the deodorization catalyst carrier is selected from the material that contains aluminium, silicon, earth alkali metal, transition metal, rare earth metal and carbon; Like aluminum oxide, silicon oxide, silico-aluminate, quicklime, Natural manganese dioxide, titanium oxide, natural and artificial clay, natural and permutite, from the blacking of mineral material (like coal and oil etc.), vegetable material (like wood chip, shell fruit stone etc.) and synthetic resins etc. etc., preferred activated carbon.The specific surface of porous carrier is at 10～1500m
2Between/the g, preferred 100～1200m
2Between/the g.
Gasoline desulfur combination process provided by the invention has the following advantages:
From the last running that cuts out, tell sub-fraction last running; Be used for the disulphide that lighting end alkali lye extractive process is generated is absorbed; And within this combination process, handle; Can avoid selecting for use outer other varsol (like petroleum naphtha, rocket(engine)fuel etc.) of this combination process to be used for this part disulphide of extracting on the one hand, and select hydrogenation unit else and handle, thereby avoid tooling cost to increase; On the other hand; Because this sub-fraction last running contains a certain amount of mercaptan, during disulphide in extracting regeneration alkali lye, if also have trace oxygen in the regeneration alkali lye; Under the effect of metal phthalocyanine catalyst that can be in alkali lye with last running in thiol reactant and be removed, thereby the efficient that the alkali lye of effectively avoiding regenerating returns lighting end alkali lye extraction system when using continuously makes regeneration alkali lye heavily absorb mercaptan in the lighting end because of the existence of micro amount of oxygen reduces.
Description of drawings
Accompanying drawing is the schematic flow sheet of the inventive method.Accompanying drawing is only represented preferred schema; And do not provide the details such as opertaing device of relevant container, well heater, water cooler, pump, compressor, mixing tank, valve, technological process, only express promptly that to understand the present invention be basic or non-obvious equipment situation to knowing those skilled in the art.
Now do detailed introduction with regard to accompanying drawing.Feed gasoline gets into fractionating system 2 through pipeline 1, and the gasoline lighting end is flowed out through pipeline 4, and gasoline last running is flowed out back separated into two parts fluid inflow line 6 and pipeline 5 from pipeline 3.Gasoline lighting end from fractionating system gets into extraction system 7 through pipeline 4.The alkali lye of fresh alkali lye or containing metal phthalocyanine catalyst gets into extraction system 7 through pipeline 10, and lighting end contacts in extraction system 7 convection current with alkali lye.By alkali lye extracting mercaptan and the lighting end of desulfurization is left extraction system 7 through pipeline 8.
The alkali lye that is rich in thiolate flows into oxidation systems 13 through pipeline 9, and and mixes through the oxygenant (airborne oxygen) that pipeline 11 gets into oxidation systems 13.Usually, during like needs, fresh alkali lye and catalyzer can be through pipeline 12 inputs.Flow into of the top release of the air of oxidation system 13 from oxidation system.
Mix the separation removal system 15 that flow into phase-separation system through pipeline 14 with small portion last running (through pipeline 6) from the mixture of regeneration alkali lye, disulphide and the trapped air of oxidation system 13 from fractionating system 2.
Flow into the settling separation system 17 of phase-separation system from pipeline 16 from the oily alkali mixture of separation removal system 15.After settlement separate; Regeneration alkali lye flows out and returns extraction system through pipeline 10 from pipeline 18 and recycles; And flow out through pipeline 19 with the mutually unmixed double distilled phase-splitting that contains disulphide of alkali lye basically; Can in pipeline 20 inflow line 6, return the disulphide that separation removal system 15 is used for extracting alkali lye continuously, also can flow directly into coalescence and remove system 22 through pipeline 21.
The said double distilled phase-splitting that contains disulphide is flowed out coalescences through pipeline 24 and is removed system 22 (remove the micro-alkali lye that possibly carry and discharge through pipeline 23); And with all the other most of last running remix from pipeline 5 from fractionating system 2, flow into hydrogenation system 27 with hydrogen through pipeline 25 then from pipeline 26.
Said last running and hydrogen contact under the effect of selective hydrogenation catalyst and carry out the selective hydrodesulfurization reaction, carry through gas and flow out hydrogenation system 27 after removing hydrogen sulfide.
The said hydrogenation last running after gas is carried from hydrogenation system 27 mixes through the lighting end that pipeline 28 and extracting from pipeline 8 remove mercaptan mutually; And and from the oxygenant (airborne oxygen) of pipeline 29 and (if possible from the acvator of pipeline 30; Also can not add acvator) mix after pipeline 31 gets into fixed bed deodorization systems 32 and remove last running newly-generated mercaptan in hydrogenation process, the finished product are through pipeline 33 or after sedimentation, flow out.
Embodiment
Employed catalyst for selectively hydrodesulfurizing is provided by Sinopec Group's Chang Ling oil-refining chemical head factory catalyst plant among the embodiment, and trade names are RSDS-01.
Through instance method of the present invention is further described below.
Embodiment 1
The effect of this instance explanation the inventive method.
In this example, adopt the raw material catalytic cracking gasoline A in the schema his-and-hers watches 1 shown in the drawings to carry out the selective desulfurization processing.The cutting temperature of gasoline A is 101 ℃.The yield of cutting back lighting end and last running is respectively 45 heavy %, 55 heavy %, and the part by weight of small portion last running B and most of last running C is about 1:28, and essential property is seen table 1.In extraction system, the volume ratio of alkali lye and hydrocarbon stream is 2:8, and temperature is a normal temperature, pressure 0.5MPa.In oxidation system, the content of sulfonated phthalocyanine cobalt is 100ppm in the alkali lye.The IR of oxidation system air and alkali lye volume ratio are 1:4.5, the pressure 0.34MPa of oxidation system, 50 ℃ of temperature.Temperature and pressure that three sub-systems of phase-separation system---extracting removes system, settling separation system and coarse separation system are natural temperature and natural pressure.Be about 1:7 from the small portion last running B that is used for absorption and regeneration alkali lye disulphide of separation column and the volume ratio of alkali lye.This sub-fraction last running B mixes back entering hydrogenation system and carries out hydrotreatment with other last running C.In the hydrogenation system, the reactive hydrogen dividing potential drop is 1.6MPa, 280 ℃ of temperature of reaction, liquid hourly space velocity 4.0h
-1, hydrogen to oil volume ratio 400.Last running mixes with lighting end from extraction system behind the hydrogenation, flows into fixed bed mercaptan removal system then and carries out mercaptan removal and handle.40 ℃ of the temperature of fixed bed mercaptan removal system, pressure 0.3MPa, liquid hourly space velocity is 2.0h
-1Raw material A is after above-mentioned processing, and the result is as shown in table 1.Table 2 has provided sulphur, mercaptan sulfur content and the alkali lye of disulphide front and back in the small portion last running B extracting alkali lye by sodium mercaptides (in the sulphur) content before and after the last running B extracting.Can find out; Small portion last running B can be with the complete extracting of the disulphide in the alkali lye; And the mercaptan sulfur from extracting front and back last running and the variation of the sodium mercaptides content in the alkali lye can be found out, unnecessary air still contains trace oxygen after from regeneration alkali lye, discharging in the alkali lye; But can be with thiol reactant among the last running B and be removed (the mercaptan sulfur major part among the last running B is converted into disulphide and still stays among the last running B, is absorbed on a small quantity to become sodium mercaptides in the alkali lye).After the inventive method processing, the desulfurization degree of raw material A is up to 89.4%, and the alkene saturation exponent has only 10.3%, and the anti-knock index loss has only 0.7 unit, has obtained the effect of higher selective desulfurization.
Table 1
Table 2
Embodiment 2
The effect of this instance explanation the inventive method.
In this example, adopt the raw material catalytic cracking gasoline D in the schema his-and-hers watches 3 shown in the drawings to carry out the selective desulfurization processing.The cutting temperature of gasoline D is 84 ℃.The yield of cutting back lighting end and last running is respectively 39 heavy %, 61 heavy %, and the part by weight of small portion last running E and most of last running F is about 1:72, and essential property is seen table 3.In extraction system, the volume ratio of alkali lye and hydrocarbon stream is 2:8, and temperature is a normal temperature, pressure 0.5MPa.In oxidation system, the content of sulfonated phthalocyanine cobalt is 100ppm in the alkali lye.The IR of oxidation system air and alkali lye volume ratio are 1:4.5, the pressure 0.34MPa of oxidation system, 50 ℃ of temperature.Temperature and pressure that three sub-systems of phase-separation system---extracting removes system, settling separation system and coarse separation system are natural temperature and natural pressure.Be about 1:14 from the small portion last running that is used for absorption and regeneration alkali lye disulphide of separation column and the volume ratio of alkali lye.This sub-fraction last running E mixes back entering hydrogenation system and carries out hydrotreatment with other last running F.In the hydrogenation system, the reactive hydrogen dividing potential drop is 1.6MPa, 280 ℃ of temperature of reaction, liquid hourly space velocity 4.0h
-1, hydrogen to oil volume ratio 400.Last running mixes with lighting end from extraction system behind the hydrogenation, adds fixed bed mercaptan removal system then and carries out mercaptan removal and handle.40 ℃ of the temperature of fixed bed mercaptan removal system, pressure 0.3MPa, liquid hourly space velocity is 2.0h
-1Raw material D is after above-mentioned processing, and the result is as shown in table 3.Table 4 has provided sulphur, mercaptan sulfur content and the alkali lye of disulphide front and back in the small portion last running D extracting alkali lye by sodium mercaptides (in the sulphur) content before and after the last running D extracting.Can find out; Small portion last running D can be with the complete extracting of the disulphide in the alkali lye; And the mercaptan sulfur from extracting front and back last running and the variation of the sodium mercaptides content in the alkali lye can be found out, unnecessary air still contains trace oxygen after from regeneration alkali lye, discharging in the alkali lye; But can be with thiol reactant among the last running D and be removed (the mercaptan sulfur major part among the last running D is converted into disulphide and still stays among the last running D, is absorbed on a small quantity to become sodium mercaptides in the alkali lye).After the inventive method processing, the desulfurization degree of raw material D is up to 91.8%, and the alkene saturation exponent has only 24.7%, and the anti-knock index loss has only 1.4 units, has obtained the effect of higher selective desulfurization.
Table 3
Table 4
Claims (14)
1. the combined method of a gasoline desulfur comprises:
1) gasoline is cut into gently, weighs two portions cut; The fractionation cutting temperature of gasoline is between 50～120 ℃; The yield of lighting end and last running is respectively 30～60 heavy % and 40～70 heavy % of gasoline stocks; Last running is divided into large and small two portions fluid again, and small portion last running is 1: 1～500 with the weight yield ratio of most of last running;
2) lighting end is contacted with alkali lye, the mercaptan in the lighting end is gone into to generate thiolate in the alkali lye by extracting;
3) make thiolate in the alkali lye under the effect of air and metal phthalocyanine catalyst, be oxidized to disulphide, make alkali liquid regeneration;
4) regeneration alkali lye and the mixture of disulphide contacts with small portion last running from step 1), and disulphide is gone in the last running by extracting;
5) the small portion last running that contains disulphide with the mixture of regeneration alkali lye settlement separate after, regeneration alkali lye returns step 2);
6) the small portion last running that contains disulphide mixes with most of last running, carries out the selective hydrodesulfurization reaction;
7) from last running after the desulfurization of step 6) with from step 2) mercaptan removal after lighting end mix, remove mercaptan newly-generated in the hydrogenation process and become product; Remove mercaptan newly-generated in the hydrogenation process again after perhaps removing hydrogen sulfide from last running after the desulfurization of step 6), afterwards with from step 2) mercaptan removal after lighting end mix and become product.
2. according to the described method of claim 1, it is characterized in that said gasoline stocks is selected from: catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline or its mixture.
3. according to the described method of claim 1, it is characterized in that the fractionation cutting temperature of said gasoline is between 60～100 ℃.
4. according to the described method of claim 1, it is characterized in that small portion last running is 1: 1～100 with the weight yield ratio of most of last running.
5. according to the described method of claim 1, it is characterized in that, extractive temperature between 25～100 ℃, pressure between 0.1～2.0MPa, the alkali lye volume that is adopted for the lighting end volume between 1～50%.
6. according to the described method of claim 1, it is characterized in that employed alkali lye is the aqueous solution of alkali metal hydroxide.
7. according to the described method of claim 1, it is characterized in that alkali lye is the sodium hydroxide solution of about 1～50% (weight).
8. according to the described method of claim 1, it is characterized in that, discharge at the top of the unnecessary air of step 3) from oxidation system.
9. according to the described method of claim 1, it is characterized in that said metal phthalocyanine catalyst is a phthalocyanine cobalt compounds.
10. according to the described method of claim 1, it is characterized in that the air capacity of being injected equals to make alkali lye mercaptan salt to be oxidized to the required stoichiometric quantity of disulphide at least, the catalyzer that is injected is 5～1000ppm at the content of alkali lye.
11. according to the described method of claim 1, it is characterized in that, in the volume ratio 1: 1～1: 100 of step 4) small portion last running with regeneration alkali lye.
12. according to the described method of claim 1, it is characterized in that, in the volume ratio 1: 1～1: 50 of step 4) small portion last running with regeneration alkali lye.
13. according to the described method of claim 1, it is characterized in that, handle through coalescence in the last running of step 6) small portion and mix with most of last running after removing contained micro-alkali lye and other impurity from fractionating system.
14., it is characterized in that circulating in the last running of step 6) small portion is used for the disulphide of extracting alkali lye, after coalescence is handled, mixes with most of last running according to the described method of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102079991B (en) * | 2009-11-26 | 2013-09-04 | 中国石油化工股份有限公司 | Method for removing escapable sulfides from heavy hydrocarbons |
| CN102533325B (en) * | 2010-12-31 | 2014-05-28 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
| CN102851068B (en) * | 2011-06-29 | 2015-02-25 | 中国石油化工股份有限公司 | Gasoline desulfurization method |
| CN102851069B (en) * | 2011-06-29 | 2014-12-31 | 中国石油化工股份有限公司 | Gasoline desulfurization method |
| CN103374383B (en) * | 2012-04-27 | 2015-09-23 | 中国石油化工股份有限公司 | The dissolved oxygen deodour method of light-end products and device |
| CN103450924B (en) * | 2012-05-29 | 2015-06-24 | 北京安耐吉能源工程技术有限公司 | Method of removing mercaptan in oil product other than hydrogenation |
| CN103695035B (en) * | 2012-09-28 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of combined method of producing super low-sulfur oil |
| CN104371786B (en) * | 2013-08-14 | 2017-05-24 | 中国石油化工股份有限公司 | Alkali lye desulfurization method and device of liquefied petroleum gas |
| US10240096B1 (en) * | 2017-10-25 | 2019-03-26 | Saudi Arabian Oil Company | Integrated process for activating hydroprocessing catalysts with in-situ produced sulfides and disulphides |
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