CN103773479A - Method for producing clean gasoline - Google Patents
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- CN103773479A CN103773479A CN201210410946.6A CN201210410946A CN103773479A CN 103773479 A CN103773479 A CN 103773479A CN 201210410946 A CN201210410946 A CN 201210410946A CN 103773479 A CN103773479 A CN 103773479A
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Abstract
The invention discloses a method for producing clean gasoline. The method comprises the following steps: (1) making a gasoline raw material contact an adsorption desulfurization catalyst in a refining reactor in the presence of hydrogen, adsorbing and removing sulfides from the gasoline, and meanwhile, performing selective hydrogenation to remove diene from the gasoline;(2) introducing the gasoline refined in the step (1) into an etherification reactor, reacting olefin in the gasoline with alcohol to generate ether to obtain an etherified gasoline product in the presence of a solid high-acid catalyst at the temperature of higher than 95 DEG C, wherein the solid high-acid catalyst is a high-temperature-resistant high-acid catalyst with the heat-resistance temperature of 125 DEG C to 250 DEG C and the acid site strength H0 greater than minus 8. According to the method provided by the invention, sulfur and the diene are removed from the gasoline, the etherate content of a gasoline product is greatly improved, and a clean gasoline product with high octane rating can be obtained.
Description
Technical field
The present invention relates to a kind of method of treated gasoline, more particularly, relate to a kind of method of gasoline refining and etherificate production clean gasoline product.
Technical background
Along with the increasingly stringent of legislations of environmental protection, countries in the world and area are also increasingly strict to the restriction of the olefin(e) centent in gasoline and sulphur content in recent years, and market to the demand of high-grade gasoline also along with the development of automobile market constantly increases.From July 1 in 2010, Qi China will progressively implement state's IV emission standard in the whole country, and standard-required sulfur content in gasoline is not more than 50 μ g/g, and olefin(e) centent is not more than 25v%.The gasoline of China nearly 80% is from catalytic cracking process, and all the other gasoline components are few, is in harmonious proportion ability, and China's catalytic cracking gasoline olefine content is conventionally at 40 ~ 50v%, and aromaticity content, less than 20v%, does not have oxygenatedchemicals substantially.In order to produce the low alkene gasoline of low-sulfur, existing hydrogenating desulfurization technology can cause because of olefin saturated the loss of gasoline octane rating unavoidably, and being reacted with fatty alcohol, active olefin component generates corresponding ether, to reduce olefin(e) centent and vapour pressure in gasoline, improve gasoline octane rating, improve the effective ways of quality of gasoline, also can increase gasoline output simultaneously, improve the added value of corresponding fatty alcohol.
Etherification technology existing and comparative maturity has iso-butylene MTBE processed, C 5 fraction TAME processed and Etherification of Light FCC Gasoline technology at present.Industrial most employing storng-acid cation exchange resin is as catalyzer, and also useful load type heteropolyacid and molecular sieve are as catalyzer.Typical etherification technology generally includes several parts such as raw materials pretreatment, etherification reaction and Methanol Recovery.In raw material, need the impurity removing to comprise sulphur, alkali nitrogen, metallic cation, diolefine etc., Main Means has alkali cleaning, washing and hydrogenation etc., and processing step is more, and operation energy consumption is high.
CN101245257A discloses side line etherification method a kind of and that absorption-stabilization system by catalytic cracking is integrated, the method is to enter methyltertiarvbutyl ether reactor after the side line discharge Extract phase materials of Fcc Stabilizer 95% to 50% tower height mixes with fatty alcohol, under catalyst action, carry out etherification reaction, its reaction product enters tower without separation by the side entry feed mouth that is positioned at side line discharge below again and carries out fractionation, the liquefied gas that separation obtains obtains by stablizing tower top, obtains the stable gasoline that contains ether compound at the bottom of stabilizer tower.Its shortcoming is that raw material of etherification does not pass through pre-treatment, and catalyst deactivation is very fast, need constantly deliver to catalytic cracking reaction regeneration system rapidly and regenerate, and weak point is not have separating methanol system, and therefore add can not be excessive for methyl alcohol, causes alkene can not reach maximum conversion.
US6262314 discloses a kind of method that catalytic distillation process is prepared ether compound, the method is after C5 and/or C6 isomeric olefine and methanol mixed, first to carry out pre-reaction, pre-reaction comprises two fixed-bed reactor, first reactor takes off diene and pre-etherification reaction under the condition of facing hydrogen, in second reactor, isomeric olefine reaches etherificate equilibrium conversion, reaction mass finally enters catalytic distillation tower and carries out deep conversion, and adds a certain amount of methyl alcohol at catalytic distillation tower conversion zone.The catalyst cupport that pre-reaction process is used has precious metal palladium that hydrogenation activity is provided, and removes diene in raw material so that charging is processed, and extends the catalyst for etherification life-span.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, and a kind of method of producing clean gasoline is provided, and the method total olefin transformation efficiency in gasoline etherification process is high, and after upgrading, gasoline octane rating improves a lot.
A kind of method of producing clean gasoline provided by the invention, comprises the following steps:
(1), in refining reaction device, under the condition existing at hydrogen, gasoline stocks contacts with absorbing desulfurization catalyst, the sulfide in adsorbing and removing gasoline, and selective hydrogenation removes the diolefine in gasoline simultaneously;
(2) gasoline after refining in step (1) is introduced methyltertiarvbutyl ether reactor, under the existence of solid strong acid catalyst, be greater than in temperature under the condition of 95 ℃, alkene in gasoline reacts with alcohol and generates ether, obtain etherified gasoline product, described solid strong acid catalyst is that heat resisting temperature is the high temperature resistant strong acid type catalyzer that 125 ℃-250 ℃, acid site intensity are greater than H0=-8.
Preferably, increase afterwards fractionating step in step (1), by step (1), obtain refining after gasoline to introduce fractionation in separation column be light gasoline fraction and heavy naphtha, fractionation cut point is 50-75 ℃, and light gasoline fraction is introduced to methyltertiarvbutyl ether reactor.
The beneficial effect of a kind of method of producing clean gasoline provided by the invention is:
In method provided by the invention, the first process treating process desulfurization of full distillation gasoline raw material, de-diene, and then the gasoline after refining is carried out to degree of depth etherificate.In the etherification technology of gasoline of prior art, etherification reaction temperature is lower, and requires also lower to the strength of acid of catalyzer.Generally only have tertiary carbon alkene to participate in etherification reaction, secondary carbene does not react.Compared with prior art, method provided by the invention not only tertiary carbon alkene participates in etherification reaction, and normal olefine (secondary carbon olefin) also participates in etherification reaction, thereby increase substantially the etherification product content of product, the alcohol of more cheapnesss is joined in gasoline indirectly by a kind of mode of etherate, receive thereby can improve gasoline liquid, reduce gasoline cost.Reduce sulphur content and the olefin(e) centent of gasoline, improved gasoline octane rating.And from embodiment, method provided by the invention, the etherate content in full distillation gasoline product is greater than 20wt%, and olefin(e) centent reduces more than 60%, and octane value improves 4-5 unit.
Accompanying drawing explanation
Fig. 1 is a kind of a kind of embodiment schematic flow sheet of method of producing clean gasoline;
Fig. 2 is the schematic flow sheet of regular price gasoline etherificate method for modifying in prior art;
Fig. 3 is a kind of another kind of embodiment schematic flow sheet of method of producing clean gasoline.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
A kind of method of producing clean gasoline provided by the invention, comprises the following steps:
(1), in refining reaction device, under the condition existing at hydrogen, gasoline stocks contacts with absorbing desulfurization catalyst, the sulfide in adsorbing and removing gasoline, and selective hydrogenation removes the diolefine in gasoline simultaneously;
(2) gasoline of step (1) after refining is introduced methyltertiarvbutyl ether reactor, under the existence of solid strong acid catalyst, temperature is greater than under the condition of 95 ℃, alkene in gasoline reacts with alcohol and generates ether, obtain etherified gasoline product, described solid strong acid catalyst is that heat resisting temperature is the high temperature resistant strong acid type catalyzer that 125 ℃-250 ℃, acid site intensity are greater than H0=-8.
Preferably, increase afterwards fractionating step in step (1), by in step (1), obtain refining after gasoline to introduce fractionation in separation column be light gasoline fraction and heavy naphtha, fractionation cut point is 50-75 ℃, and the light gasoline fraction after fractionation is introduced to methyltertiarvbutyl ether reactor.
Wherein said fractionator overhead extraction has the light gasoline fraction of etherification activity, and described light gasoline fraction is C4-C7 hydrocarbon fraction mixture, and boiling range is 30-75 ℃; At the bottom of tower, obtain heavy naphtha, described heavy naphtha is C8-C12 hydrocarbon-fraction, and boiling range is 75-250 ℃.Described separation column operational condition is: 30 ℃ ~ 50 ℃ of overhead condensation temperature, and 110 ℃ ~ 150 ℃ of column bottom temperatures, tower top pressure 0.01MPa ~ 0.3MPa, trim the top of column is than 0.5 ~ 3.
In method provided by the invention, in step (1), the operational condition of refining reaction device is: temperature is 320 ℃ ~ 460 ℃, preferably 340 ℃ ~ 440 ℃; Pressure is 0.5MPa ~ 4.0MPa, preferably 1.0MPa ~ 3.5MPa; Air speed is 2h
-1~ 20h
-1, preferably 4h
-1~ 10h
-1; Reaction is for hydro condition, and hydrogen hydrocarbon volume ratio is 0.1 ~ 0.8, and preferably 0.2 ~ 0.5.
In method provided by the invention, the absorbing desulfurization catalyst described in step (1) is load zinc oxide, contains or does not contain group VIII metal oxide, and carrier is the loaded catalyst of silicon oxide and/or aluminum oxide.Preferably, take total catalyst weight as benchmark, in oxide compound, in described absorbing desulfurization catalyst, contain the zinc oxide of 15wt% ~ 60wt%, the nickel oxide that contains 0 ~ 15wt% and/or cobalt oxide, and the carrier of surplus.
In step (1), described refining reaction device can be the form of fixed bed, moving-bed or fluidized-bed.
In method provided by the invention, gasoline after refining in step (2) is introduced in methyltertiarvbutyl ether reactor, be that heat resisting temperature is not less than 125 ℃, acid site intensity and is greater than under the high temperature resistant strong acid type catalyzer existence of H0=-8 containing the gasoline fraction of alkene and alcohol at described solid strong acid catalyst, be 95 ℃-catalyzer heat resisting temperature in temperature, be generally 95 ℃ ~ 200 ℃, preferably 100 ℃-150 ℃; Pressure is 0.1-5.0MPa, preferably 0.2-1.0MPa; Liquid hourly space velocity is 1-5h
-1; Alfin ratio is (0.6 ~ 4): 1, and preferably (0.9 ~ 2.6): under 1 condition, secondary carbon olefin, tertiary carbon alkene and alcohol etherification reaction in described gasoline, after reaction product methanol removal, obtain etherified gasoline.
Wherein, described alcohol is methyl alcohol and/or ethanol, particular methanol.Weight hourly space velocity is too high, and raw material reaction is incomplete, and olefin conversion declines, and the too low catalyst levels that increases of charging weight hourly space velocity has reduced the processing power of etherification reaction, and facility investment increases.
Methyltertiarvbutyl ether reactor described in step (2) is one or more the combination in fixed bed, expanded bed, mixed phase bed and catalytic distillation tower, also can separation column be set between on-catalytic distillation reactor product is carried out to pre-separation, the restriction that is beneficial to disequilibrate, improves transformation efficiency.
Alkene in gasoline can be divided into tertiary carbon alkene and secondary carbene by the type of composition double-linked carbon, has at least an alkene that belongs to tertiary carbon atom to belong to tertiary carbon alkene in two carbon atoms of composition olefinic double bonds, the secondary carbene of genus in addition.In method provided by the invention, described alfin ratio is the mol ratio of the alkene (comprising tertiary carbon alkene and secondary carbon olefin) in alcohol and gasoline.
In method provided by the invention, described acid site intensity H0 lower than-8, heat resistance is not less than one or more in catalyzer and the modified molecular sieve catalyst that the strongly-acid high-temperature catalyst of 125 ℃ is selected from halogen modified ion exchange resin, perfluorinated sulfonic acid type resin, heteropolyacid or carried heteropoly acid.More preferably halogen modified ion-exchange resin catalyst or perfluorinated sulfonic acid type resin catalyst.
Described strength of acid is greater than the modification strongly acidic cation-exchange catalyzer that H0=-8, heat resistance be not less than 125 ℃ and refers to after halogen atom modification, more than strength of acid reaches H0=-8, and can be more than 95 ℃ the strong acid ion exchange resin catalyzer of life-time service.This fire resistant and highly acidic resin at least can obtain by following two kinds of approach.A kind of approach is to introduce halogen atom on the phenyl ring of sulfonated styrol resin skeleton, for example chlorine atom, because the strong electron attraction of halogens not only can make phenyl ring stable but also can improve the acidity of sulfonic acid group on phenyl ring, can make like this more than the strength of acid of resin catalyst reaches H0=-8, and can be more than 150 ℃ life-time service, this resinoid can conveniently buy from the market, such as the Amberlyst45 resin that abroad ROHM & HASS company produces, the D008 resin that Ji Zhong chemical plant, domestic Hebei produces etc.Another kind of fire resistant and highly acidic resin is perfluorinated sulfonic acid type resin, this resinoid is because the hydrogen on its skeleton is all replaced by fluorine, due to the strong electrophilic of fluorine, make it have superpower acidity and the thermostability of superelevation, strength of acid H0 reaches-12, and heat resisting temperature reaches more than 250 ℃, its exemplary is the Nafion resin that DuPont company produces.
In method provided by the invention, described heteropoly acid catalyst comprises heteropolyacid, heteropolyacid salt, and the catalyzer of carried heteropoly acid, heteropolyacid salt.The strength of acid H0 of heteropolyacid and acid salt thereof can reach-13.15, and can be up to more than 300 ℃ life-time service.Described heteropolyacid comprises the heteropolyacid of Kegin structure, Dawson, Anderson structure, Silverton structure.The preferably heteropolyacid of keggin structure, as 12 phospho-wolframic acid (H
3pW
12o
40xH
2o), 12 silicotungstic acid (H
4siW
12o
40xH
2o), 12 phosphomolybdate (H
3pMo
12o
40xH
2o), 12 molybdovanaphosphoric acid (H
3pMo
12-yv
yo
40xH
2o) etc.The preferred acid Tricesium dodecatungstophosphate of described heteropolyacid salt salt (Cs
2.5h
0.5p
12wO
40), its sour H0 is lower than-13.15, and specific surface area can reach 100m
2more than/g.Described carried heteropoly acid or the carrier of heteropolyacid salt are selected from SiO
2and/or activated carbon.
Described strength of acid is greater than the modified molecular sieve catalyst of H0=-8, and the H0 that comprises part acid site is lower than one or more in-8 modification H β, HY, HSZM-5, preferably modification H β, HSZM-5 molecular sieve.The higher temperature of reaction of unmodified molecular sieve ability generally can be used at the temperature up to 500 ℃, but H
0strong acid center amount lower than-8 is little, therefore needs molecule to carry out modification to improve the acidity of molecular sieve.The molecular sieve catalyst of the preferred fluorine of the present invention, phosphorus modification.
In method provided by the invention, described gasoline stocks refers to that boiling range scope falls into the petroleum hydrocarbon fraction of 30 ℃ ~ 250 ℃, and usually, described gasoline stocks is that carbon molecule number is the mixture of C4 ~ C12 hydrocarbon component.Can be selected from coker gasoline, pyrolysis gasoline and the catalytically cracked gasoline etc. that are rich in alkene.
Olefin(e) centent in preferred described gasoline stocks is 5-70wt%.Gasoline is by C
4~ C
11the mixture of multiple hydrocarbon composition, comprises alkene, alkane, naphthenic hydrocarbon and aromatic hydrocarbons, and wherein alkene is the reactant that can carry out etherificate.Due to along with carbon number increase, the content of active olefin significantly reduces, in gasoline, in the component of carbonatoms more than 7, various active olefin content is little, all below 0.3wt%, and because more macromolecular active olefin is in the time carrying out etherification reaction with methyl alcohol, its etherification reaction speed is very slow, the corresponding ether of more difficult generation.
In method provided by the invention, preferably, by the first catalytically cracked gasoline method through washing dealkalize, just basic cpd carries out etherification reaction with methyl alcohol after removing again.Owing to containing a small amount of basic cpd in catalytically cracked gasoline, the catalyzer that etherification reaction adopts is that the basic cpd in an acidic catalyst gasoline can neutralization reaction occur with acidity of catalyst center, and make catalyzer lose catalytic activity, therefore preferably before etherificate, must be removed through pre-treatment.The method of employing washing can.
In method provided by the invention, described methyltertiarvbutyl ether reactor can be selected arbitrarily by following: fixed-bed reactor, shell-and-tube reactor, adiabatic reactor, stirred-tank reactor, the tower reactor of catalytic distillation etc.Wherein catalyzer distillation tower reactor, because breaking through Equilibrium limit, improves the transformation efficiency of etherification reaction.
In method provided by the invention, if methanol concentration < 1w% in final product does not need methyl alcohol to reclaim; If residual methanol concentration is higher, methyl alcohol is reclaimed.When containing excessive methyl alcohol in reaction product, the present invention does not limit for the separation method of methyl alcohol, can adopt the separate mode of any appropriate, and such as adopting the conventional method such as component distillation, extraction to be isolated, the methyl alcohol of recovery returns to use again.
Described Methanol Recovery unit can be various forms of packing towers, sieve-tray tower, valve tray column or its combination, adopts deionized water as extraction agent.Deionized water adds from methanol extraction tower top, enters containing methyl alcohol hydrocarbon stream from extraction tower bottom, and the hydrocarbon stream after separating methanol is from extraction overhead extraction, containing the extraction liquid of methyl alcohol from extraction at the bottom of tower.The operational condition of described methanol extraction tower is: 10 ℃ ~ 50 ℃ of temperature, pressure 0.01MPa ~ 0.3MPa, hydrocarbon water volume ratio 1:0.5 ~ 2.
Method provided by the invention, olefin conversion is high, thereby the alcohol of more cheapnesss is joined in gasoline indirectly by a kind of mode of etherate, increase substantially etherificate content in product gasoline, reduced olefin(e) centent, improved octane value, receive thereby can improve gasoline liquid, reduce gasoline cost.Visible by analysis, not only the tertiary carbon alkene in gasoline participates in etherification reaction, and normal olefine (secondary carbon olefin) also participates in etherification reaction.In general, compared with gasoline etherification method of the prior art, gasoline etherification process in the method for production clean gasoline provided by the invention, tertiary carbon alkene per pass conversion is higher than 60%, secondary carbene transforms higher than 80%, total olefin is reduced in more than 60%, and if olefin(e) centent in raw material is at 45wt%, product olefin(e) centent can be reduced to below 20wt%.And having guaranteed that more methyl alcohol enters in gasoline products by etherification reaction, the liquid of product is received generally more than 110wt%.From comparative example and embodiment, in gasoline products, etherificate content has improved 15%-18%, and octane value has improved 4-5 more than unit.
The present invention will be further described with reference to the accompanying drawings, but the present invention is not therefore subject to any restriction.
The schematic flow sheet of a kind of embodiment that accompanying drawing 1 is a kind of method of producing clean gasoline provided by the invention, as shown in Figure 1, gasoline stocks enters refining reaction device 2 through pipeline 1, under the condition of facing hydrogen, contacts the reaction such as adsorption desulfurize, de-diene occurs simultaneously with absorbing desulfurization catalyst.Content of sulfur in gasoline after refining can be down to below 10ppm, substantially, not containing diene, can be used as high-quality raw material of etherification.Treating process may generate C2-C4 component with partial cracking reaction, after refined unit, needs to arrange the de-C4 of stabilizer tower, if cracking is less, can directly carry out fractionation cutting to it.
Gasoline after refining enters fractionation in separation column 4 through pipeline 3, and separation column 4 tower top dischargings are light gasoline fraction, and its composition is mainly C4-C7; At the bottom of separation column tower, discharging is heavy naphtha, and chief component is C8-C12 cut.If gasoline stocks neutral and alkali nitrogen content is higher, can the light gasoline fraction after cutting be washed and be refined, remove the basic nitrogen wherein catalyst for etherification with toxic action.
After light gasoline fraction and a certain amount of methanol mixed from pipeline 8, enter in methyltertiarvbutyl ether reactor 9 through pipeline 6.In methyltertiarvbutyl ether reactor 9, load heat-resisting strong acid type solid catalyst, reaction conditions under, the tertiary carbon alkene in light gasoline fraction and secondary carbon olefin react with methyl alcohol generate etherification product.Etherified gasoline is drawn through pipeline 10.If methanol concentration < 1w% in final product, does not need methyl alcohol to reclaim; If residual methanol concentration is higher, methyl alcohol is reclaimed.
After being rich in the etherificate of methyl alcohol, logistics enters methanol extraction tower 16 bottoms through pipeline 10, adopt deionized water as extraction agent, deionized water enters extraction tower through pipeline 17 from tower top, hydrocarbon material flow after separating methanol is through pipeline 18 from overhead extraction, and separation column 4 materials at bottom of towers, catalytic distillation tower 11 materials at bottom of towers obtain being rich in the high-quality gasoline product of ether after mixing.The mixture flow of methyl alcohol and water is discharged at the bottom of tower through pipeline 19.
The schematic flow sheet of the another kind of embodiment that accompanying drawing 2 is a kind of method of producing clean gasoline provided by the invention, if different with Fig. 1 is that the etherificate after product etherificate transformation efficiency of discharging through pipeline 10 is inadequate, can be through catalytic distillation tower 11 and the further etherification reaction of methyltertiarvbutyl ether reactor 14.In catalytic distillation tower 11, utilize the limit coronite separation of catalytic distillation process can obtain higher etherificate transformation efficiency, tower top is discharged unreacted gasoline and methyl alcohol, obtains etherified gasoline at the bottom of tower; Overhead stream can enter methyltertiarvbutyl ether reactor 14 through pipeline 12 and further transform, to obtain higher etherificate transformation efficiency.
By the following examples the present invention is further described, but not thereby limiting the invention.
Preparation example 1
The preparation method of refining with adsorbents catalyzer: a certain amount of diatomite and zinc oxide are put into grinding machine for grinding and become powder, this mixture is mixed to making beating with deionized water, the solid content slurries that are 30wt%, and then add a certain amount of aluminium colloidal sol, and with hydrochloric acid adjust pH be 3 left and right, then in 75 ℃ of stirring 2.5h, be cooled to 60 ℃, spray drying forming; 150 ℃ dry after 4 hours, then roasting 2h makes carrier at 650 ℃; By carrier granule flood with nickel nitrate solution, produce dipping after granular mixture; Granular mixture after described dipping is dried to 2 hours at 150 ℃, then roasting was made 1 ~ 3mm particle through compression molding after 2 hours at 600 ℃, obtained refining with adsorbents catalyzer.Wherein: diatomite, aluminium colloidal sol, zinc oxide and nickelous nitrate weight of material are than being SiO
2: Al
2o
3: ZnO:Ni=2:1:5:1.
Comparative example 1
Comparative example 1 illustrates that regular price gasoline is refined and the effect of etherification method.
Comparative example 1 adopts the flow process shown in Fig. 2, full distillation gasoline enters separation column and carries out cut cutting, overhead extraction comprises the light gasoline fraction of C5 and part C6 component, light gasoline fraction first removes mercaptan sulfur wherein by caustic extraction, then remove the impurity such as basic nitrogen and metal ion wherein by water elution, finally enter hydrogenator by selective hydrogenation and removing diene, the light gasoline fraction after refining enters methyltertiarvbutyl ether reactor as raw material of etherification and carries out etherification reaction.The heavy naphtha fractionating out enters hydrogenator and carries out hydrogenating desulfurization.Light gasoline fraction after heavy naphtha and etherificate after hydrogenating desulfurization is mixed to get clean gasoline product.
Wherein, full distillation gasoline is taken from Qingdao refinery, and its main character is in table 1.Separation column cutting temperature is 75 ℃.The de-diene catalyzer of hydrogenation adopts RLF-10w(to be produced by Chang Ling catalyzer branch office of China Petrochemical Corp.).The operational condition of the de-diene of light gasoline fraction hydrogenation is: 120 ℃ of temperature of reaction, pressure 1.5MPa, hydrogen-oil ratio 200, air speed 4h
-1.The catalyzer loading in methyltertiarvbutyl ether reactor is D005-II (being produced by Dandong Mingzhu Special Type Resin Co., Ltd.), and temperature of reaction is 65 ℃ ~ 70 ℃, and alfin mol ratio is 1.02, and pressure is 1.0MPa, and liquid hourly space velocity is 2.0h
-1; Methyl alcohol does not reclaim.Heavy naphtha selective hydrodesulfurization adopts catalyzer RSDS-22(to be produced by Chang Ling catalyzer branch office of China Petrochemical Corp.).Gasoline property is in table 2.
Embodiment 1
Embodiment 1 illustrates the effect of a kind of method of producing clean gasoline provided by the invention.
Adopt the flow process shown in accompanying drawing 3 to test.Full distillation gasoline is introduced in refining reaction device the de-diene of desulfurization under hydro condition, then entering separation column fractionation is light gasoline fraction and heavy naphtha, after light gasoline fraction washing, enter methyltertiarvbutyl ether reactor and react generation etherified gasoline with alcohol, unnecessary methyl alcohol enters in methanol extraction tower and reclaims methyl alcohol.Light gasoline fraction after etherificate and heavy naphtha are mixed to get to clean gasoline product.
Gasoline stocks is with comparative example 1.Refining reaction device loads the refining with adsorbents catalyzer of being prepared by preparation example 1, and operational condition is: temperature of reaction is 360 ℃, and pressure is 2.0MPa, and air speed is 5h
-1, hydrogen hydrocarbon volume ratio is 0.3.Separation column cutting temperature is 75 ℃, methyltertiarvbutyl ether reactor loading catalyst be Amberlyst 45 catalyzer (commercially available, by styrene-divinylbenzene suspension copolymerization, make through chlorination, sulfonation again, heat resisting temperature is 170 ℃), temperature of reaction is 110-120 ℃, alfin mol ratio 1.02.Methanol extraction tower adopts deionized water as extraction agent.The operational condition of methanol extraction tower is: 30 ~ 50 ℃ of temperature, pressure 0.1MPa, hydrocarbon water volume ratio 1:1.Gasoline property is in table 2.
Embodiment 1 illustrates the effect of a kind of method of producing clean gasoline provided by the invention.
Experiment process, raw material and method are with embodiment 1, and difference is that refining reaction device adopts fluidisation bed form, adopts the refining with adsorbents catalyzer of preparation in preparation example 1,429 ℃ of refining reaction temperature, pressure 2.6MPa, air speed 6.5h
-1, hydrogen hydrocarbon volume ratio 0.28.Gasoline property is in table 2.
Table 1
| Component and content w% | The full distillation gasoline in Qingdao refinery |
| Normal paraffin | 4.4 |
| Isoparaffin | 34.0 |
| Alkene | 26.9 |
| Naphthenic hydrocarbon | 5.4 |
| Aromatic hydrocarbons | 29.0 |
| Diene | 0.4 |
| Density, kg/m 3 | 731.8 |
| Sulphur content, ppm | 804 |
| Nitrogen content, ppm | 50.2 |
| RON | 83.5 |
Table 2
| Petroleum naphtha character | Comparative example 1 | Embodiment 1 | |
| Sulphur content, μ g/ |
7 | 9 | 3 |
| Diene content, μ g/g | 100 | 30 | ＜10 |
| Alkali nitrogen, μ g/ |
2 | 4 | 3 |
| Gasoline products character | ? | ? | ? |
| Etherate content, wt% | 7.1 | 25.2 | 22.1 |
| Sulphur content, μ g/g | 37 | 26 | 8 |
| Olefin(e) centent wt% | 22.5 | 14.7 | 14.5 |
| RON | 83.9 | 88.1 | 88.4 |
Claims (13)
1. a method of producing clean gasoline, is characterized in that, comprises the following steps:
(1), in refining reaction device, under the condition existing at hydrogen, gasoline stocks contacts with absorbing desulfurization catalyst, the sulfide in adsorbing and removing gasoline, and selective hydrogenation removes the diolefine in gasoline simultaneously;
(2) gasoline after refining in step (1) is introduced methyltertiarvbutyl ether reactor, under the existence of solid strong acid catalyst, be greater than in temperature under the condition of 95 ℃, alkene in gasoline reacts with alcohol and generates ether, obtain etherified gasoline product, described solid strong acid catalyst is that heat resisting temperature is the high temperature resistant strong acid type catalyzer that 125 ℃-250 ℃, acid site intensity are greater than H0=-8.
2. according to the method for claim 1, it is characterized in that, step (1) afterwards, step (2) increases fractionating step before, by in step (1), obtain refining after gasoline fraction to introduce fractionation in separation column be light gasoline fraction and heavy naphtha, fractionation cut point is 50-75 ℃, and light gasoline fraction is introduced to methyltertiarvbutyl ether reactor.
3. according to the method for claim 1 or 2, it is characterized in that, the boiling range of described gasoline stocks is 30 ℃ ~ 250 ℃.
4. according to the method for claim 1 or 2, it is characterized in that, the absorbing desulfurization catalyst described in step (1) is load zinc oxide, contains or does not contain group VIII metal oxide, and carrier is the loaded catalyst of silicon oxide and/or aluminum oxide.
5. according to the method for claim 4, it is characterized in that, take total catalyst weight as benchmark, in oxide compound, in described absorbing desulfurization catalyst, contain 15wt% ~ 60wt% zinc oxide, the nickel oxide that contains 0 ~ 15wt% and/or cobalt oxide, and the carrier of surplus.
6. according to the method for claim 1 or 2, it is characterized in that, in step (1), the operational condition of refining reaction device is: temperature is 320 ℃ ~ 460 ℃; Pressure is 0.5MPa ~ 4.0MPa; Air speed is 2h
-1~ 20h
-1; Hydrogen to oil volume ratio is 0.1 ~ 0.8.
7. according to the method for claim 6, it is characterized in that, in step (1), the operational condition of refining reaction device is: temperature is 340 ℃ ~ 440 ℃; Pressure is 1.0MPa ~ 3.5MPa; Air speed is 4h
-1~ 10h
-1; Hydrogen to oil volume ratio is 0.2 ~ 0.5.
8. according to the method for claim 1 or 2, it is characterized in that, the methyltertiarvbutyl ether reactor operational condition in step (2) is that temperature of reaction is 95 ℃-catalyzer heat resisting temperature, and pressure is 0.1-5.0MPa, and liquid hourly space velocity is 1-5h
-1, alfin mol ratio is (0.6 ~ 4): 1.
9. according to the method for claim 8, it is characterized in that, the methyltertiarvbutyl ether reactor operational condition in step (2) is that temperature of reaction is 100 ℃-150 ℃, and pressure is 0.2-1.0MPa, and liquid hourly space velocity is 1-5h
-1, alfin ratio is (0.9 ~ 2.6): 1.
10. according to the method for claim 1 or 2, it is characterized in that, the fire resistant and highly acidic catalyzer described in step (2) is selected from one or more in catalyzer and the modified molecular sieve catalyst of halogen modified Zeo-karb, heteropolyacid or carried heteropoly acid.
11. according to the method for claim 10, it is characterized in that, the fire resistant and highly acidic catalyzer described in step (2) is selected from halogen modified Zeo-karb or perfluorinated sulfonic acid type resin catalyst.
12. according to the method for claim 1 or 2, it is characterized in that, described alcohol is methyl alcohol and/or ethanol.
13. according to the method for claim 1 or 2, it is characterized in that, step (1) afterwards, described gasoline stocks after refining again through water elution except basic nitrogen compound and metal ion wherein.
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| CN112745184A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Method for producing isooctene by overlapping mixed C4 raw material with high olefin content |
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