CN101275085A - Combined method for gasoline desulfurization - Google Patents
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- CN101275085A CN101275085A CNA2007100649820A CN200710064982A CN101275085A CN 101275085 A CN101275085 A CN 101275085A CN A2007100649820 A CNA2007100649820 A CN A2007100649820A CN 200710064982 A CN200710064982 A CN 200710064982A CN 101275085 A CN101275085 A CN 101275085A
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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 by 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 are tending towards strict qualification aspect sulphur content 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 prescribed 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 liquefied petroleum gas (LPG), 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 by generating thiolate with alkaline reaction and removing from oil product.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).By 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 significantly reduces the discharging of salkali waste thus by continuing to use (consulting U.S. Pat 3574093,4666689) behind the disulphide in settlement separate or the varsol extracting regeneration alkali lye.
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 easily forms aeration regeneration alkali lye and disulphide mutually or contain solvent phase settlement separate of disulphide in alkali lye, 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, the disulphide back suction can 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 under the effect of alkali lye round-robin oxide catalyst, so sweetening effectiveness 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.Described method is that gasoline is cut into weight two portions, reduces sulphur content (the less reduction of olefin content in gasoline) in the gasoline by heavy naphtha being carried out mode that selective hydrogenation handles.
USP6610197B2 has reported a kind of method of gasoline desulfur.Described 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 sulphur content in the gasoline with this.
USP6623627B1 has reported a kind of production method of low-sulphur oil.Described 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 by 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.Described 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
Purpose of the present 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, carries out the selective hydrodesulfurization reaction under the effect of selective hydrogenation catalyst;
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 specifically comprises three systems again---separation removal system, settling separation system and the coalescent system that removes.
Specifically, the combined method of gasoline desulfur provided by the invention may further comprise the steps:
1) by 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 described 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, potassium hydroxide, lithium hydroxide 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, as low-carbon alcohol: methyl alcohol, ethanol, Virahol etc., the compounds of nitrogenous, phosphorus, oxygen, sulphur, arsenic, antimony and basic nitrogen compound etc.The special ideal alkali lye that uses for the present invention is the sodium hydroxide solution of about 1～50% (weight), preferably uses the sodium hydroxide solution of 5～25% (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 regenerated, 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 by being dissolved in the alkali lye or forming stable milk sap in alkali lye, also can use by 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.
Discharge at the oxidation system top after oxidation system at the airflow that injects before the 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 added before oxidation system 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, in the regeneration alkali lye after the release air if also have a trace oxygen, under the effect of metal phthalocyanine catalyst that can be in alkali lye with last running in thiol reactant and be removed.
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.The volume ratio of small portion last running and regeneration alkali lye 1: 1～1: 100, 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 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, use is coalescent in oil phase with promotion disulphide as coalescing agent as fillers such as steel wire, sand, glass usually, and uses usually 0.5～2.0 hour the residence time, with the separation of further promotion phase.Settling separation system and coalescent temperature and the pressure that removes system are respectively natural temperature and natural pressure.
6) the small portion last running that contains disulphide from settling separation system mixes with most of last running after system handles removes contained micro-alkali lye and other impurity through coalescent removing, also can before coalescent processing, 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.
Described 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 molybdenum and/or tungsten, nickel and/or cobalt, auxiliary agent magnesium, in macropore and the mesopore zeolite one or more and alumina host, in oxide compound and with the total catalyst weight is benchmark, the content of described molybdenum and/or tungsten is 3～20 heavy %, the content of nickel and/or cobalt is 0.3～2 heavy %, the auxiliary agent Mg content is 1～7 heavy %, and the content of described zeolite is 5～60 heavy %.The condition of described 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, enter 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 enter 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.
Described 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
Described 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, potassium hydroxide, lithium hydroxide 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 described alkaline organic compound.
Described fixed bed deodorization reaction is preferably carried out under the situation that activator exists simultaneously, described activator is the mixture of polar compound and/or compounds, and described polar compound can be water, is selected from the low-carbon alcohol of methyl alcohol, ethanol and/or Virahol, reaches the basic nitrogen compound as alkyl amine, hydroxyalkyl amine.Described compounds can be quaternary ammonium compounds, rattle compounds, Arsenic compounds, antimony compounds, oxygen compounds and sulfonium compounds etc., is respectively N, P, As, Sb, O and S etc. as cationic atom, preferred quaternary ammonium salt and/or quaternary ammonium hydroxide.Described activator accounts for content in the pending gasoline between 10～10000ppm, between preferred 50～800ppm.Described alkaline reagents and described activator 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.
Described 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 described alkaline reagents and described activator.
The preferred negative ions of described metal phthalocyanine is made 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.Described metal phthalocyanine is selected from sulfonate, carboxylate salt and quaternary ammonium salt, compounds of metal phthalocyanine etc.Described metal phthalocyanine with positive ion group is selected from sulfonate, the carboxylate salt of metal phthalocyanine, the sulfonate 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.Described 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 basic structure, 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.
Described porous material as the deodorization catalyst carrier is selected from the material that contains aluminium, silicon, alkaline-earth metal, transition metal, rare earth metal and carbon, as aluminum oxide, silicon oxide, silico-aluminate, calcium oxide, magnesium oxide, titanium oxide, natural and artificial clay, natural and permutite, from the carbonaceous material of mineral material (as coal and oil etc.), vegetable material (as 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 other outer varsol of this combination process (as petroleum naphtha on the one hand, rocket engine fuel etc.) be used for this part disulphide of extracting, and the alternative hydrogenation unit is handled, 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 operating 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.
Be described in detail with regard to accompanying drawing now. Feed gasoline enters fractionating system 2 through pipeline 1, The gasoline light fraction is flowed out through pipeline 4, and gasoline heavy distillat is divided into two parts fluid after pipeline 3 flows out Inflow line 6 and pipeline 5. Gasoline light fraction from fractionating system enters extracting system through pipeline 4 System 7. The alkali lye of fresh alkali lye or containing metal phthalocyanine catalyst enters extraction system 7 through pipeline 10, Light fraction contacts in extraction system 7 convection current with alkali lye. By caustic extraction mercaptan and the light fraction of desulfurization Leave extraction system 7 by pipeline 8.
The alkali lye that is rich in mercaptides flows into oxidative systems 13 through pipeline 9, and and enters through pipeline 11 The oxidant of oxidative system 13 (airborne oxygen) mixes. Usually, during such as needs, fresh Alkali lye and catalyst can be through pipeline 12 inputs. Flow into the air of oxidative system 13 from oxidative system The top discharge.
From the mixture of regeneration alkali lye, disulphide and the air pocket of oxidative system 13 through pipe Line 14 mixes to flow into fraction heavy distillat (through pipeline 6) from fractionating system 2 and is separated The separation removal system 15 of system.
Oily alkali mixture from separation removal system 15 flows into the heavy of phase-separation system from pipeline 16 Piece-rate system 17 is fallen. After the sedimentation separation, regeneration alkali lye returns from pipeline 18 outflows and through pipeline 10 Extraction system recycles, and basically with the mutually unmixed double distilled phase-splitting that contains disulphide of alkali lye Flow out through pipeline 19, can in pipeline 20 inflow line 6, return separation removal system 15 and connect The continuous disulphide that is used for extracting alkali lye also can flow directly into the coalescent system that removes through pipeline 21 22.
The described double distilled phase-splitting that contains disulphide is flowed out the coalescent system 22 that removes through pipeline 24 and (is removed The micro-alkali lye that may carry is also discharged through pipeline 23), and with from pipeline 5 from fractionation train System all the other most of heavy distillat of 2 mix again, then with from the hydrogen of pipeline 26 through pipeline 25 Flow into together hydrogenation system 27.
Described heavy distillat contacts under the effect of selective hydrocatalyst with hydrogen to be carried out selectively Hydrodesulfurization reaction flows out hydrogenation system 27 after air lift removes hydrogen sulfide.
The described hydrogenation heavy distillat after air lift from hydrogenation system 27 through pipeline 28 with from pipe The light fraction that the extracting of line 8 removes mercaptan mixes mutually, and with from the oxidant (sky of pipeline 29 Oxygen in the gas) activator that reaches from pipeline 30 (if possible, also can not add activation Agent) mixing enters fixed bed deodorizing system 32 by pipeline 31 and removes heavy distillat in hydrogenation process Newly-generated mercaptan, final products are through pipeline 33 or flow out after sedimentation.
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.
Below by example method of the present invention is further described.
Embodiment 1
The effect of this example 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 sees 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 injection rate of air and alkali lye volume ratio are 1: 4.5 in the oxidation system, the pressure 0.34MPa of oxidation system, 50 ℃ of temperature.Temperature and pressure that three subsystems 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 with enter hydrogenation system after other last running C mixes and carry out hydrotreatment.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.As can be seen, 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, after unnecessary air discharges from regeneration alkali lye, still contain trace oxygen 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
The effect of this example 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 sees 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 injection rate of air and alkali lye volume ratio are 1: 4.5 in the oxidation system, the pressure 0.34MPa of oxidation system, 50 ℃ of temperature.Temperature and pressure that three subsystems 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 with enter hydrogenation system after other last running F mixes and carry out hydrotreatment.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.As can be seen, 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, after unnecessary air discharges from regeneration alkali lye, still contain trace oxygen 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 (16)
1. the combined method of a gasoline desulfur comprises:
1) gasoline is cut into gently, weighs two portions cut, 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. in accordance with the method for 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. in accordance with the method for claim 1, it is characterized in that the fractionation cutting temperature of described gasoline is between 50～120 ℃.
4. in accordance with the method for claim 1, it is characterized in that the fractionation cutting temperature of described gasoline is between 60～100 ℃.
5. in accordance with the method for claim 1, it is characterized in that the yield of lighting end and last running is respectively 30～60 heavy % and 40～70 heavy % of gasoline stocks.
6. in accordance with the method for 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.
7. in accordance with the method for 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%.
8. in accordance with the method for claim 1, it is characterized in that employed alkali lye is the aqueous solution of alkali metal hydroxide.
9. in accordance with the method for claim 1, it is characterized in that alkali lye is the sodium hydroxide solution of about 1～50% (weight).
10. in accordance with the method for claim 1, it is characterized in that, discharge at the top of the unnecessary air of step 3) from oxidation system.
11. in accordance with the method for claim 1, it is characterized in that described metal phthalocyanine catalyst is a phthalocyanine cobalt compounds.
12. in accordance with the method for 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.
13. in accordance with the method for 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.
14. in accordance with the method for 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.
15. in accordance with the method for claim 1, it is characterized in that, after coalescent processing removes contained micro-alkali lye and other impurity, mix with most of last running from fractionating system in the last running of step 6) small portion.
16. in accordance with the method for claim 1, it is characterized in that circulating in the last running of step 6) small portion is used for the disulphide of extracting alkali lye, mixes with most of last running after coalescent processing.
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