CN102093909B - Method for removing thiophene sulfur-containing compound from petroleum - Google Patents
Method for removing thiophene sulfur-containing compound from petroleum Download PDFInfo
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Abstract
The invention discloses a method for removing a thiophene sulfur-containing compound from petroleum, which belongs to the field of petrochemical industry and relates to a method for alkylation desulfation. The method comprises the following steps of: performing an alkylation reaction on the thiophene sulfur-containing compound in a petroleum component and olefin under the catalytic effect of a cation exchange resin which is complexed with Fe<3+> ions and is taken as a catalyst to transform the thiophene sulfur-containing compound into a high-boiling-point sulfur-containing compound; and separating the sulfur-containing compound from a hydrocarbon compound by fractionating on the basis of difference between boiling points. The catalyst used in the method is a composite catalyst with a complex structure, and the Fe<3+> ions undergo a complexation reaction with an active sulfonic acid group on a resin framework to form a new activity center, so that the acid catalytic activity of the resin is remarkably enhanced, selectivity to alkylation of thiophene is high, a small quantity of secondary reactions is performed, conversion rate is high, and the yield of product petroleum can be incrased. By the method, alkylation of the sulfur-containing compound and distillation and separation of light hydrocarbon components are performed in the same reaction-distillation tower.
Description
Technical field:
The invention belongs to petrochemical industry, relate to the method for petroleum oil product alkylating desulfurization.
Background technology
The development need oil refining enterprise of modern industry provides increasing high-grade fuel, but along with the continuous increase of sulfur crude processing amount and the generally employing of Catalytic Cracking Technique of Heavy Oil, makes crude oil processed products comprise that the sulphur content of gasoline, diesel oil enlarges markedly.After these sulfocompound burnings, produce a large amount of oxysulfides, seriously pollute environment for human survival.For this reason, each industrially developed country of the world to various power fuels particularly the sulphur content of gasoline, diesel oil formulated more and more stricter quality standard.The sulphur content of " world's fuel oil standard " regulation III level gasoline standard is less than 30ppm.Sulphur content≤the 50ppm of the Europe IV standard regulation gasoline coming into effect for 2005.China is less than 150ppm in the sulphur content of the GB III regulation gasoline that on July 1st, 2007 comes into effect.The low sulfuration of gasoline, diesel oil has become the inexorable trend of world today's clean fuel development.The progress of Clean Fuel Production technology in recent years and development are carried out round environmental regulation and the quality standard of increasingly stringent just.The core of so-called " cleaning " refers to the sulphur content that significantly reduces gasoline, also limits alkene, aromatic hydrocarbons and benzene content in gasoline simultaneously.Meeting society is to refine oil and the challenge that oil product industry faces and the historic mission of bearing to the growing demand of clean fuel.
Desulfurization is one of significant process of oil purification, and existing several different methods, for removing the sulfocompound of gasoline and diesel oil, is broadly divided into hydrogenating desulfurization and the large class of non-hydrogenating desulfurization two at present.Hydrodesulfurization oil yield is high, color good, but its process cost is high, and industrial condition harshness needs high temperature, high pressure and highly active catalyzer.The side reaction product of hydrogenating desulfurization can make the lost of life of catalyzer.In addition, contained aromaticity sulfur-containing organic compound in gasoline component, as: thiophene and derivatives, is difficult to remove completely by hydrogenating desulfurization.Simultaneously no matter which kind of gasoline component is after hydrotreatment, the octane value that all can make gasoline due to alkene saturated reduction in various degree, and some hydrogen addition technologies also can cause the reduction of yield of gasoline.
Along with progress and the reach of science of technology, in development hydrogenating desulfurization technology, non-hydrodesulfurization is also developed rapidly, as adsorption desulfurize, oxidation sweetening, biological desulphurization and abstraction desulfurization etc. in recent years.Wherein oxidative desulfurization techniques is compared more ripely, receives the concern of various equivalent modifications.
The oxidising process that prior art mainly concentrates on Removal of Sulfur Compounds from Gasoline comprises the selection of oxygenant and catalyzer, and oxidation products separates with hydrocarbon compound, has proposed multiple different technical scheme.
U.S. Pat 6402939 (2002) discloses a kind of method of utilizing ultrasonic wave to promote liquid mineral oil oxidation sweetening, oxygenant used is the aqueous solution of 1-30% (volume) hydrogen peroxide, apply ultrasonic wave in the oil/water two-phase system of the liquid mineral oil of sulfur-bearing, hydrogen peroxide, quaternary ammonium salts tensio-active agent, accelerate and promote the oxidising process of sulfocompound in oil product, adding of quaternary ammonium salts tensio-active agent, be conducive to the polarity sulphur compound of oxidation generation to the transfer of water, reach accelerating oxidation and the object separating.Apply ultrasonic wave in reaction system, be conducive to theoretically increase the collision frequency of sulfocompound and oxidizer molecule in oil product.The carrying out of accelerated reaction.But applying ultrasonic wave to the oil product system being on a grand scale, suitability for industrialized production has certain technical difficulty.Can the corresponding cost that improves oil product.
U.S. Pat 6406616 (2002) discloses a kind of take hydrogen peroxide as oxygenant, and formic acid is an acidic catalyst, gasoline is carried out to the method for oxidation sweetening.Its process is that sour gasoline component is mixed in reactor with the water that contains hydrogen peroxide and formic acid.At normal pressure with under temperature (the being less than 120 ℃) condition relaxing, thiophene sulfocompounds is oxidized to sulfone or sulfoxide, after the water and separation of oil that contains reclaimable catalyst and sulfone compound, sends into regeneration system rapidly, remove sulfone and make catalyst regeneration.The oil phase that contains a small amount of sulfone compound is delivered to alumina adsorption post and further a small amount of sulfone compound is removed from oil product.Alumina adsorbant can be used Mathanol regenerating.
French Patent FR2802939 (2001) discloses a kind of liquid hydrocarbon mixture/water two-phase system that contains superoxide or persulphate that makes and has been turbulence state, impels the thiophene sulfocompounds in hydrocarbon mixture to be oxidized to sulfone and sulfoxide.Described superoxide can be the persulphate of hydrogen peroxide, organo-peroxide, basic metal or alkaline-earth metal.And record this sulfur method and can be applicable to the desulfurization of gasoline, kerosene and catalytic cracking distillate.
The open a kind of oxygenant that uses of U.S. Pat 5961820 (1999), carbonyl compound and oxyhydroxide remove the method for petroleum fractions and sulfur content in coal compound.Oxygenant used is hydrogen peroxide, and carbonyl compound is ketone compounds, as acetone etc.Oxyhydroxide is alkali metal hydroxide.The mixture of sulfur-bearing oil cut or coal and hydrogen peroxide, acetone, sodium hydroxide in this technique, in room temperature to 121 ℃ temperature range, carries out under 1-2 normal atmosphere, after reaction finishes, separates sulfocompound, obtains super low sulfur petroleum fractions or coal.Containing the ketone compounds of carbonyl as solvent through recycling and reusing.
Japanese Patent JPJ4072387 (1992) discloses a kind of method of the desulfurization of fuel oil, the method be with oxidizer treatment be derived from oil, liquefied coal coil comprises gasoline, kerosene, diesel oil, light-weight fuel oil and heavy fuel oil (HFO).Described oxygenant can be selected from oxygen, ozone and organo-peroxide, and oil fuel can direct oxidation, or is oxidized after first mixing with organic solvent-acetone again.It has higher boiling point sulfocompound after oxidation, can separate with oil product by distillation.Also can utilize the difference of sulfur-containing organic compound and oil product components dissolved degree or fusing point, adopt solvent extraction, deep refrigeration and chromatographic column isolation technique are removed.
More than be oxidation style, reaction system is two-phase system, the oxidising process of sulfocompound is carried out on oil/water interface, needs sufficient mixing just can have high transformation efficiency, and reacting that required an acidic catalyst is dissolved in water can etching apparatus and have a discharge of spent acid.Cause environmental pollution; After oxidation, sulfocompound need be used solvent extraction, and solid adsorbent absorption, changes into the methods such as sulfate precipitation, makes it to separate with oil product, and separation efficiency is subject to the restriction of extraction agent, sorbent material, precipitation agent character.
In order to overcome the deficiency of above-mentioned oxidation sweetening, another kind of advanced sulfur method-alkylation conversion method is in research and industrialized developing stage.The research and development of prior art concentrate on the multiple different technical elements such as the selection of catalyst for alkylation reaction and the selection of preparation, alkylating reagent, high boiling point sulfocompound and separating of hydrocarbon mixture, and wherein the selection of catalyst for alkylation reaction and preparation are one of emphasis of research and development.
So-called alkylating desulfurization method, under an acidic catalyst exists, sulfur-bearing aromatic compound in hydrocarbon mixture reacts the material that changes into higher with alkylating reagent, difference based on boiling point adopts fractionating method, the sulfocompound of higher is separated with hydrocarbon mixture, reach the object of desulfurization.It is generally acknowledged that acid material can catalysis sulfur-bearing aromatic compound and the alkylated reaction that occurs of alkene or alcohol, can select liquid acid, solid acid or liquid acid load on the load acid on solid carrier, as phosphoric acid, sulfuric acid, boric acid, fluosulfonic acid, trifluoromethanesulfonic acid and dihydroxyfluoboric acid and BF
3, BCl
3, AlCl
3, AlBr
3, AlCl
3hCl mixture etc.Solid carrier can be selected silicon oxide, aluminum oxide, sieve and silica-sesquioxide, aluminum oxide or clay etc.Also can select composite solid-acid catalyst, this catalyzer reacts preparation with aluminum tetrachloride by phosphoric acid.The alkylated reaction of this catalyst thiophene and propylene, a propyl group thiophene and many propyl group thiophene of generation higher.The alkylated reaction of catalysis toluene and propylene generates cymene.
The weak point of existing alkylating desulfurization technology is:
1, liquid acid or liquid acid is loaded on to load acid catalysis mercaptan from gasoline on solid carrier and the alkylated reaction of thiophene sulfocompounds, in reaction, by product is more, low conversion rate, and be difficult for and product separation.When washing product, produce a large amount of spent acid and easily cause environmental pollution.Also can there is in addition serious equipment corrosion.
2, in existing solid acid catalyst catalytic gasoline component, the selectivity of the alkylated reaction of sulfocompound is not high.Also can there is alkylated reaction in the aromatic hydrocarbons in gasoline, the high boiling alkylaromatic hydrocarbon of generation can be in fractionation process be abandoned with together with the sulfur-bearing aromatic compound of higher simultaneously.Will make so a considerable amount of aromatic hydrocarbons in gasoline component together be removed, reduce the output of gasoline products.
3, in gasoline component, the alkene of 5-7 carbon atom has higher octane value, also can polymerization reaction take place under alkylation reaction condition, and change into high boiling fluorinated polymer and lose.
Summary of the invention:
The present invention proposes the removal methods of thiophene sulfocompounds in a kind of gasoline, described gasoline fraction is made up of hydrocarbon mixture, and with sulfur-bearing phenolic compound, if thiophene and thionaphthene are as main detrimental impurity.
The removal methods of thiophene sulfocompounds in gasoline of the present invention (abbreviation sulfur method), adopt alkylating desulfurization method, the method is under an acidic catalyst exists, make sulfur-bearing aromatic compound contained in hydrocarbon mixture change into sulfur-bearing aromatic compound heaviness, that boiling point is higher by reacting with alkylating reagent, based on boiling point by fractionation, high boiling sulfocompound is separated with hydrocarbon mixture, reach the object of desulfurization, thereby obtain the high-clean gasoline product of ultra-low sulfur.
Implementing ultimate principle of the present invention is to carry out alkylated reaction by the sulfur-bearing aromaticity impurity in gasoline and alkylating reagent, is translated into the heaviness product of higher.For example thiophene changes into by reaction the thiophene that alkyl replaces.
While making alkylating reagent with propylene, thiophene changes into 2-sec.-propyl thiophene, and monoalkyl replaces, and replacement can occur on a position or β position of sulphur atom.In alkylation process, alkyl has replaced the hydrogen atom in initial sulfocompound, and its molecular weight is increased, and its boiling point is higher than the boiling point of initial sulfocompound, thereby is conducive to and the separating of hydrocarbon mixture.
Be applicable to the olefines that is mainly as alkylating reagent in sulfur method of the present invention, also comprise alcohol compound, this class alkylating reagent requires to contain 3 to 10 atoms, because reactivity ratio's alcohols of alkene is high, conventionally selects alkene to do alkylating reagent.As alkylating reagent, most other alkene of the reactivity ratio of ethene, methyl alcohol and ethanol and alcohol are low, thereby the lacking of use.The applicable alkene that does alkylating reagent comprises naphthenic hydrocarbon.The cycloolefin and the molecular formula that replace are:
alkene, wherein R
1alkyl, R
2or hydrogen or alkyl, preferably R
1alkyl, each R
2from hydrogen and alkyl, select separately.Suitable cycloolefin and substituted cycloalkene comprise cyclopentenes, 1-methyl cyclopentene, tetrahydrobenzene etc., and suitable alkene comprises propylene, butylene, amylene, 1,3-hexadiene, 1-heptene, octene etc.The alkene of lower molecular weight is the alkylating reagent that reactive behavior is high in thiophene and thionaphthene alkylated reaction.Be present in C in petroleum naphtha as component
5, C
6alkene is than the C of higher molecular weight
7alkene activity is high.It is most suitable that the alkene that contains 3-5 carbon atom is used as alkylating reagent, because their reactive behavioies are high, and they homopolymerization also occurs generate dimer and the tripolymer of 6-10 carbon atom and be just in time within the scope of gasoline boiling range.If therefore product is used as blending component, these volatility homopolymer are desirable high-octane number components, and they are removed Shi Buhui at high boiling point sulfocompound by fractionation and lose.
Apply the thiophene sulfocompounds that sulfur method of the present invention can remove, refer to any aromaticity organic compound that at least contains a sulphur atom in its molecular structure on its aromatic nucleus.This class material comprises thiophene and benzothiophenes, the example of this class material includes, without being limited to thiophene, 2-thiotolene, 3 methyl thiophene, 2,3-thioxene, 3-ethylthiophene, thionaphthene, 2-methylbenzene thiophthene, 2,3-dimethyldibenzothiophene and 3-ethylbenzene thiophthene.
Any acidic substance all can catalysis sulfur-bearing aromatic compound and the alkylation reaction of alkene or alcohol.Although liquid acid can be used as catalyzer as sulfuric acid, solid acid catalyst is suitable especially, because solid acid catalyst can be filled in distillation column.Loading catalyst is in distillation column, and the fractionation by distillation of catalytic alkylation reaction and product is carried out simultaneously.
Sulfur method of the present invention is to adopt complexing to have Fe
3+the Zeo-karb of ion is as catalyzer, make the alkene that thiophene sulfocompounds and gasoline contain self carry out alkylated reaction, make it to be converted into the sulfocompound that boiling point is higher, based on the difference of boiling point, separate with hydrocarbon compound by fractionation, reach the object of the high-clean gasoline that obtains ultra-low sulfur.
Sulfur method of the present invention comprises following particular content:
(1) complexing has Fe
3+the preparation of the macroporous cation exchange resin catalyst of ion
1. the transition of Zeo-karb
Macropore sulfonic acid ion exchange resin is generally Na while dispatching from the factory
+type need carry out acid treatment in the time of first use, makes it be converted into Hydrogen.Fresh resin is soaked 24 hours in deionized water, then the dilute hydrochloric acid that is 2-4% with percentage concentration flows through the separator column that the resin soaking is housed with the linear velocity of 3-4 m/h, in the time that separator column lower end has hydrochloric acid to flow out, close outlet valve, resin was soaked after 30 minutes, then open outlet valve by hydrochloric acid with the same linear velocity separator column of flowing through.Until a certain amount of hydrochloric acid stream, after separator column, continuous repeatedly rinses resin with deionized water, until leacheate is neutral.Then remove the moisture in resin in separator column with nitrogen purging, thus the transition that completes resin.
2. complexing has Fe
3+the preparation of the cation resin catalyzing agent of ion.
Hydrogen resin cation (R.C.) dried resin, through distillation washing, after being dried, being got 40-60g and is added in 500ml there-necked flask, then add 300-360ml1, and 2-ethylene dichloride stirs 12-16 hour at 30-35 ℃ of temperature, then adds 40-60g FeCl
3, under reflux state, react 12-16 hour, filtration separates complexing Fe
3+ion Zeo-karb, clarifies vacuum-drying at 60-65 ℃ of temperature with 1,2-ethylene dichloride washing resin to filtrate.Preparation complexing has Fe
3+when the cation resin catalyzing agent of ion, FeCl
3with the part by weight of macroporous polystyrene Zeo-karb be 1: 1～1.6.
3. mercaptan from gasoline, the alkylation of thiophene sulfocompounds.
There is Fe with complexing
3+the large hole cation exchanger resin of ion is catalyzer, boiling spread is at 60-190 ℃ of gasoline component, mercaptan in gasoline component and thiophene sulfocompounds are under the katalysis of catalyzer, with the low molecular weight olefins that contains 5-7 carbon atom that in gasoline component, self contains at 180-210 ℃, under 6-30 atmospheric pressure, react 1-2 minute, be converted into the heavy sulfocompound of higher.
Advantage of the present invention:
1, in gasoline component, active mercaptan removes by easy alkali cleaning or alkali-free sweetening technique conventionally, and complicated thiophenes removes the many of difficulty, need to adopt the selection hydrodesulfurizationprocess process of severe reaction conditions, and belongs to and face hydrogen system.Hydrogenation unit investment cost is relatively costly, and desulphurization cost is higher.The derivative that particularly dibenzothiophene wherein and alkyl thereof replace, as 4-MDBT, 4,6-dimethyldibenzothiophene, because its molecular structure exists larger sterically hinderedly to hydrogenation reaction, is difficult to remove completely.
Compared with hydrodesulfurization, the present invention's reaction is carried out under mild conditions, and its investment and process cost are only 1/3 of hydrogenating desulfurization technology.
2, catalyzer adopts complexing to have Fe
3+the large hole cation exchanger resin (NKC-9) of ion is made catalyzer, and compared with liquid sulfuric acid, phosphoric acid, this class aprotic acid catalyzer does not discharge free hydrogen ion, and not etching apparatus easily and product separation, has higher catalytic activity.
This resinoid volume is subject to the impact of solvent action little, is suitable for packed column operation, is easy to serialization and produces.In production process, do not have spent acid to discharge, do not pollute the environment.
3. the selected complexing of the present invention has Fe
3+the cation exchange resin as catalyst of ion, for having the composite catalyst of chelation structure, Fe
3+active sulfonic acid group generation complex reaction on ion and resin matrix, forms new active centre, and the surface acidity of resin is obviously strengthened, and the alkylation of mercaptan from gasoline, thiophene and alkene is had to highly selective, and side reaction is few, and transformation efficiency is high.Low for the alkylation of aromatic hydrocarbons and the polymerization activity of alkene, greatly suppress the carrying out of side reaction, improve the yield of product gasoline.In simultaneous reactions process, do not produce free acid, can not produce pollution and the corrosion of equipment etc. of spent acid to environment.
4, can adopt reaction distillation mode, heaviness reaction and the distillation of sulfocompound are carried out in same tower, be the catalytic section that is filled with resin catalyst on the top of hydrocarbon mixture distillation tower, distillment is brought the light benzine component containing alkene into catalytic section, the sulfocompound generation alkylated reaction in this section of petroleum naphtha component.。
Through above-mentioned reaction process, the sulfocompound generation heaviness in gasoline, thereby boiling point and all raisings accordingly of thermostability, this is just for it separates with the distillation method of mixture of light hydrocarbons the condition that provides necessary.
In this reaction system, catalyzed reaction liberated heat makes liquid light hydrocarbons component vaporization, has avoided the rising of temperature of reaction system, has avoided secondary reaction.The oil gas of vaporization is under top of tower condensation and partial reflux.Clean backflow, constantly rinses catalyzer, greatly the work-ing life of extending catalyst.Also can there is the oligomeric and isomerization reaction of alkene in the catalytic section of reactive distillation column simultaneously, contribute to improve the octane value of gasoline.
accompanying drawing explanation:
Accompanying drawing 1 has Fe for middle part is provided with complexing
3+reaction-the distillation tower of the cation exchange resin catalyst bed of ion
Embodiment:
Embodiment 1.
Complexing has Fe
3+the preparation of Zeo-karb (NKC-9) catalyzer of ion:
Macropore sulfonated phenylethylene-divinyl copolymerization Zeo-karb is converted into h type resin, after distilled water wash is dry, gets 30g and add in 250ml tri-hole flasks, add 250ml, 1,2-ethylene dichloride, is heated to 30 ℃ of stirrings and within 12 hours, makes resin particle fully swelling, then adds 30gFeCl
3, under reflux state, react 16 hours, make Fe
3+in ion and resin matrix, sulfonate radical generation complex reaction, leaches resin, washs to filtrate and clarifies with 1,2-ethylene dichloride, takes out resin, 60 ℃ of vacuum-dryings 24 hours, for subsequent use.
Embodiment 2.
Alkylating desulfurization test:
In the autoclave stirring at band, add boiling spread 150 grams of the feed naphthas of 62～210 ℃, complexing has Fe
3+0.48 gram of the strong acid cation exchange resin catalyst of ion, 180 ℃ of temperature, under pressure 6 normal atmosphere, reacts 1 minute.The difference of reaction product based on boiling point separated by gas-chromatography.Sulphur content in cut detects with sulfur chemiluminescence detection device, and it is 18.5ppm that boiling point is in the gasoline component sulphur content of 62～177 ℃.
Embodiment 3.
Alkylating desulfurization test:
In the autoclave stirring at band, add the analog gasoline component 120g being made up of octane, thionaphthene, 2-methyl butene, its sulphur content is 850ppm, then adds 0.56 gram of complexing to have Fe
3+the storng-acid cation exchange resin of ion, low whipping speed is, under 500rpm, 204 ℃, 10 normal atmosphere, to react 2 minutes.The difference of reaction product based on boiling point separated by gas-chromatography, and the sulphur content in cut is measured with sulfur chemiluminescence detection device.Boiling point is in component sulphur content within the scope of gasoline boiling range and is reduced to 15ppm.
Embodiment 4.
Alkylating desulfurization test:
In the autoclave stirring at band, adding 100g sulphur content is the catalytically cracked gasoline component of 1050ppm, adds 0.501g complexing to have Fe
3+the storng-acid cation exchange resin complex compound catalyst of ion, under 600rpm rotating speed, in 190 ℃, 15 atmospheric nitrogen atmospheres, react 1.5 minutes, the difference of reaction product based on boiling point separates through gas chromatographic column, sulphur content in cut is measured with sulfur chemiluminescence detection device, and boiling point is in component sulphur content within the scope of gasoline boiling range and is reduced to 15ppm.
Embodiment 5.
Alkylating desulfurization test:
In the autoclave stirring at band, adding mol ratio is heptane, the thiophene of 100: 0.2: 0.2, the mixture 100g of 1-hexene, and sulphur content is 600ppm, then adds 0.89g complexing to have Fe
3+the strong acid cation exchange resin catalyst of ion, under 500rpm rotating speed, in 200 ℃, 30 atmospheric nitrogen atmospheres, react 2 minutes, product separates through gas chromatographic column based on boiling point difference, measure with x-ray fluorescence spectrometry instrument, the sulphur content being in the cut within the scope of gasoline boiling range is 16ppm.
Embodiment 6.
Thiophene alkylation test:
In the autoclave stirring at band, add 42g thiophene, 70g amylene, 0.5g complexing has Fe
3+the storng-acid cation exchange resin complex compound catalyst of ion stirs 2 minutes under 180 ℃, 29 normal atmosphere, produces 95.2g diamyl thiophene, and the theoretical yield based on thiophene is 98.5%.
The proportion 0.917 (20 ℃) of product
250～262 ℃ of boiling spreads
Sulphur content 14.15% (theoretical value is 14.3%)
Embodiment 7.
Thiophene alkylation test:
In the autoclave stirring at band, add 100g boiling spread to be in 70～100 ℃ of cracked gasoline components, wherein contain C6～C7 alkene of 55%, 25g thiophene and 0.62g complexing have Fe
3+the strong acid cation exchange resin catalyst of ion, stirring reaction 2 minutes under 192 ℃, 6 normal atmosphere, produces the alkylthrophene of 185～200 ℃ of 36g boiling points, and mean density is 0.92～0.95.
Embodiment 8.
Adopt middle part to be provided with complexing and have Fe
3+reaction-the distillation tower of the cation exchange resin catalyst bed of ion, the alkylating desulfurization example that the alkylated reaction of organic compounds containing sulfur and the fractionation by distillation of light hydrocarbon components are carried out in same tower:
Equipment used is as shown in Figure of description Fig. 1.In Fig. 1 the middle part of reaction-distillation tower between two supporting layers for complexing has Fe
3+the catalyzing cation exchange resin bed of ion, the alkene generation alkylated reaction that contains 5-7 carbon atom that in the mercaptan in catalytic bed district gasoline component and thiophene sulfocompounds and gasoline component, self is contained, is converted into heavy sulfocompound.At this section, the heat that reaction is emitted makes the light constituent vaporization in gasoline rise along tower, and catalyzer has the effect of separation column column plate concurrently simultaneously, expands contact area, the rate of mass transfer in quickening fractionation process and the contact area of vapour/liquid two-phase.Adopt this reactive mode, the heaviness reaction of organic compounds containing sulfur and the fractionation by distillation of light hydrocarbon components are carried out in same tower.Utilize reaction heat to make light hydrocarbon component vaporization avoid the rising of system temperature of reaction.The liquid olefin component partial reflux that overhead condensation gets off.Constantly rinse catalytic section, prevented the overheated of catalyzer, the work-ing life of extending catalyst greatly.In catalytic section, catalyzer can make alkene generation oligomerization and isomerization reaction simultaneously.Lower polyolefins and isomerization product have high octane value, and its boiling point is not high again, in the boiling range scope of gasoline.Therefore be also conducive to improve the octane value of gasoline.
Operational condition is:
Catalyst levels is the 0.5～1wt% that processes gasoline component weight;
Catalyst bed layer height is 60～120cm;
The linear velocity of gasoline stocks oil ingredient is 30～50cm/s;
The boiling range scope of gasoline stocks oil ingredient is 60-192 ℃;
Temperature of reaction is 180-210 ℃, and reaction pressure is 6-30 normal atmosphere, reaction times 1-2 minute;
Trim the top of column ratio is 8～10: 1.
The component sulphur content that boiling point is within the scope of gasoline boiling range is reduced to below 15ppm.
Claims (2)
1. a removal methods for thiophene sulfocompounds in gasoline, is characterized in that there is Fe with complexing
3+the Zeo-karb of ion is as catalyzer, and the thiophene sulfocompounds in catalytic gasoline component and alkene carry out alkylated reaction, makes it to be converted into the sulfocompound that boiling point is higher, based on the difference of boiling point, separates with hydrocarbon compound by fractionation;
Described catalyzer is by Fe
3+ion and macropore vinylbenzene Zeo-karb are made through complex reaction, wherein FeCl
3with the part by weight of macroporous polystyrene Zeo-karb be 1: 1～1.6; Its preparation method is: after the washing of Hydrogen resin cation (R.C.), being dried, be added in ethylene dichloride, stir 12-16 hour, then add FeCl at 30-35 ℃ of temperature
3, under reflux state, react 12-16 hour, filtering to isolate complexing has Fe
3+ion Zeo-karb, clarifies with 1,2-ethylene dichloride washing resin to filtrate, vacuum-drying at 60-65 ℃ of temperature, and making complexing has Fe
3+the cation resin catalyzing agent of ion;
Thiophene sulfocompounds in described catalytic gasoline component and alkene carry out alkylated reaction makes it to be converted into the sulfocompound that boiling point is higher, and the process separating with hydrocarbon compound by fractionation, is to be provided with complexing at middle part to have Fe
3+in the same reaction-distillation tower of the cation exchange resin catalyst bed of ion, complete, its process conditions is:
Catalyst levels is the 0.5～1wt% that processes gasoline component weight;
Catalyst bed layer height is 60～120cm;
The linear velocity of gasoline stocks oil ingredient is 30～50cm/s;
The boiling range scope of gasoline stocks oil ingredient is 60-192 ℃;
Temperature of reaction is 180-210 ℃, and reaction pressure is 6-30 normal atmosphere, reaction times 1-2 minute;
Trim the top of column ratio is 8～10: 1;
The component sulphur content that boiling point is within the scope of gasoline boiling range is reduced to below 15ppm.
2. the application of the removal methods of thiophene-type sulfide in gasoline as claimed in claim 1, it is characterized in that applying the thiophene sulfocompounds that the method removes is thiophene, 2-thiotolene, 3 methyl thiophene, 2,3-thioxene, 3-ethylthiophene, thionaphthene, 2-methylbenzene thiophthene, 2,3-dimethyldibenzothiophene and 3-ethylbenzene thiophthene.
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| JP7336541B2 (en) | 2019-06-12 | 2023-08-31 | ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップ | Process for producing diacyl peroxide |
| BR112021024870A2 (en) * | 2019-06-12 | 2022-01-18 | Nouryon Chemicals Int Bv | Method for isolating carboxylic acid from an aqueous side stream of an organic peroxide production process |
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