CN104342203B - A kind of catalysis conversion method producing stop bracket gasoline - Google Patents

A kind of catalysis conversion method producing stop bracket gasoline Download PDF

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Publication number
CN104342203B
CN104342203B CN201310325175.5A CN201310325175A CN104342203B CN 104342203 B CN104342203 B CN 104342203B CN 201310325175 A CN201310325175 A CN 201310325175A CN 104342203 B CN104342203 B CN 104342203B
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gasoline
reaction
stop bracket
weight
zeolite
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CN104342203A (en
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陈学峰
魏晓丽
谢朝钢
张久顺
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]

Abstract

A kind of catalysis conversion method producing stop bracket gasoline, the method is by the light gasoline fraction of boiling range 30 ~ 80 DEG C, introduce superposition reactor and polymerization catalyst contact reacts, the building-up reactions product obtained introduces aromatization reactor and aromatized catalyst contact reacts, and the aromatization products obtained is isolated to stop bracket gasoline.The inventive method can produce stop bracket gasoline cut by light gasoline fraction, reduces the olefin(e) centent of gasoline.

Description

A kind of catalysis conversion method producing stop bracket gasoline
Technical field
The present invention relates to a kind of catalysis conversion method of hydrocarbon ils in the absence of hydrogen, in particular, relate to a kind of catalysis conversion method producing stop bracket gasoline.
Background technology
Catalytic cracking (FCC) is the important method of producing gasoline, and Chinese commodity gasoline more than 80% is from fluid catalytic cracking (FCC) gasoline.But catalytically cracked gasoline octane value is generally lower than 93, olefin(e) centent its volume content higher is generally more than 35%, and the lower general volume content of aromaticity content is no more than 30% at 10 ~ 25%(GB17930-2011 regulation olefin(e) centent, and aromaticity content is no more than 40%).Visible, its olefin(e) centent higher than existing gasoline standard, its aromaticity content apart from existing gasoline standard (GB17930-2011 limit 40% also have very large space.
USP3784463 discloses a kind of method utilizing catalytic cracking process to improve gasoline octane rating.The method adopts the riser reactor of more than two or two, and wherein a riser tube is specifically designed to the low-quality gasoline of processing, makes it at a higher temperature catalytic cracking reaction occur.The method at high temperature carries out upgrading to gasoline, and some olefin is cracking again, causes gasoline waste larger.
The method of quantity flexibility disclosed in CN1069054A, adopts two independently riser tube and two corresponding settling vessels, uses same catalyzer, light petroleum hydrocarbon and heavy petroleum hydrocarbon are reacted under different reaction conditionss.In first riser reactor, the thermocatalyst that light hydrocarbons and revivifier come 600 ~ 700 DEG C, agent-oil ratio 10 ~ 40,2 ~ 20 seconds residence time, the heavy % of coke on regenerated catalyst 0.1 ~ 0.4 condition under react, with yield-increasing gas alkene, improve gasoline octane rating, remove the impurity such as sulphur nitrogen, improve gasoline stability, reducing atmosphere is provided, passivation is carried out to the heavy metal contaminants on catalyzer, for the cracking reaction carrying out heavy hydrocarbon in catalyst recirculation to second riser tube provides favourable condition.Heavy hydrocarbon reacts under Conventional riser catalytic cracking reaction condition.
CN160746A discloses a kind of catalysis conversion method improving gasoline octane number.The method be by low octane value gasoline by the upstream injecting lift pipe reactor of Conventional catalytic cracking feed(raw material)inlet, contact with the high temperature catalyst from revivifier, temperature of reaction be 600 ~ 730 DEG C, agent-oil ratio is 6 ~ 180, weight hourly space velocity is 1 ~ 180h -1condition under react.
Although the method for carrying out high temperature upgrading to gasoline in riser tube of above-mentioned employing contributes to improving institute produces gasoline octane rating, increase rate is limited, and the waste of gasoline comparatively greatly, the yield reduction of gasoline.
CN1237488A discloses a kind of riser reactor, and this reactor is vertically followed successively by the outlet area of pre lift zone coaxial each other, the first reactor, expanding second reaction zone, undergauge from bottom to up, has a level pipe at outlet area end.It is different with the processing condition of second reaction zone that this reactor both can optionally control the first reaction zone, and stock oil of different nature can be made again to carry out segmentation cracking, obtains required object product.Producing Trimethylmethane and being rich in the catalysis conversion method of isoparaffin gasoline based on above-mentioned new texture riser reactor is disclosed in CN1232069A, the method be by preheating after stock oil introduce the reducing reactor that comprises two reaction zones, contact with the cracking catalyst of heat, first reaction zone temperature 530 DEG C ~ 620 DEG C, 0.5 ~ 2.0 second reaction times; Second reaction zone temperature 460 ~ 530 DEG C, in 2 ~ 30 seconds reaction times, after reaction product isolated, reclaimable catalyst enters revivifier through stripping and burns Posterior circle use.The heavy % of Trimethylmethane content 20 ~ 40 in the liquefied gas adopting the method to produce, the heavy % of isoparaffin content 30 ~ 45 in gasoline family's composition, olefin(e) centent is reduced to 30 heavy below %, and its research octane number (RON) is 90 ~ 93, motor-method octane number is 80 ~ 84, improves limited to gasoline octane rating.
USP4268700A discloses a kind of method utilizing polymerization of low-carbon olefin to produce stop bracket gasoline.The oligomerisation of C3 and C4 component, the oligomerization of propene wherein in C3 component, in C4 component 80% iso-butylene and generate polymkeric substance in gasoline boiling range less than the n-butene oligomerisation of 40%.The gasoline fraction that unreacted C4 alkylating hydrocarbons generates can produce stop bracket gasoline with the polymkeric substance blending of C3, C4 component.But still contain comparatively polyene hydrocarbon in this kind of method product, and containing more diolefine, gasoline stability is poor.
In sum, carrying out high temperature upgrading to gasoline, to put forward the waste of high-octane method to gasoline larger, reduce the yield of gasoline, double-reaction area is produced the method being rich in isoparaffin gasoline and is improved limited to gasoline octane rating, and the quality of gasoline that the method for polymerization of low-carbon olefin is produced is difficult to meet the requirements, the olefin(e) centent of gasoline is high.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, provides a kind of method of producing stop bracket gasoline.
The invention provides a kind of method of producing stop bracket gasoline, comprising:
The light gasoline fraction of boiling range 30 ~ 80 DEG C is introduced superposition reactor reaction, with polymerization catalyst contact reacts; Reaction after product introduces aromatization reactor, contacts react with aromatized catalyst, is separated reclaimable catalyst and reaction oil gas, and reclaimable catalyst is Returning reactor after regeneration, obtains object product stop bracket gasoline after separating reaction oil gas.
The method of production stop bracket gasoline provided by the invention, use the raw material comprising light gasoline fraction, the boiling range of described light gasoline fraction, between 30 ~ 80 DEG C, can be the mixture of one or more in light FCC gasoline, catalytic pyrolysis petroleum naphtha, light coker naphtha, pyrolysis gasoline, pressure gasoline, gelatin liquefaction petroleum naphtha.In order to improve the productive rate of gasoline product, can also by the liquefied gas after separating ethene, propylene, coking gas, thermal cracking gas also can and described light gasoline fraction raw material together charging transform.
Described stop bracket gasoline, its boiling range is between 30 ~ 221 DEG C, and can be full cut or narrow fraction wherein, octane value be more than 92, such as, be 92 ~ 120 to be generally 92 ~ 110; Described stop bracket gasoline, be rich in aromatic component, aromaticity content wherein can be more than 40 % by weight, be such as 50 ~ 80 % by weight, usually can more than 60 % by weight, comprising the aromatic hydrocarbons of a large amount of many methyl branches, with the aromatic hydrocarbons weight in described stop bracket gasoline for benchmark, in the aromatic hydrocarbons of gasoline family's component, many methyl branches aromatic hydrocarbons accounts for more than 50 % by weight, such as, be 50 ~ 95 % by weight, and preferably more than 70 % by weight.Described many methyl branches aromatic hydrocarbons is the aromatic hydrocarbons only with one or more methyl chains on aromatic ring, such as, can be one or more in toluene, dimethylbenzene, trimethylbenzene, durene.
The operational condition of described superposition reactor is: temperature of reaction is 50 ~ 500 DEG C, preferably 100 ~ 400 DEG C, more preferably 100 ~ 300 DEG C, reaction pressure 1 ~ 10MPa, preferably 1 ~ 8MPa, more preferably 2 ~ 6MPa, reaction velocity 0.1 ~ 10h -1, preferred 0.5 ~ 8h -1, more preferably 1 ~ 6h -1.
The operational condition of described aromatization reactor is: temperature of reaction 150 ~ 500 DEG C, preferably 200 ~ 450 DEG C, more preferably 250 ~ 400 DEG C, reaction pressure 0.1 ~ 0.5MPa, agent-oil ratio (weight ratio) 1 ~ 100, preferably 10 ~ 80, more preferably 20 ~ 70, reaction times is 1 ~ 20 second, preferably 2 ~ 15 seconds, more preferably 2 ~ 8 seconds, water vapour can also be introduced, water vapor and stock oil (described superimposed product) mass ratio (abbreviation water-oil ratio) are 0 ~ 1 is such as 0.05 ~ 0.5, can be 0 ~ 0.1.
Production stop bracket gasoline method provided by the invention, utilize composite reaction, in petroleum naphtha, alkene oligomerization transforms the aromatic hydrocarbons generating many methyl branches again, containing having the substituent aromatic hydrocarbons of more short-side chain in the product obtained, effectively can reduce content of olefin in gasoline and improving gasoline octane rating.Method provided by the invention, can be used for the stop bracket gasoline blend component being produced low olefin-content by light gasoline fraction, the conversion of olefines in light gasoline fraction higher for olefin(e) centent can be obtained the aromatic component of many methyl branches with higher octane; Both effectively can improve gasoline product quality to meet the demand in market, increase economic efficiency again simultaneously.Method provided by the invention is particularly useful for producing stop bracket gasoline by the light gasoline fraction of high olefin content, and can reduce the olefin(e) centent in gasoline.Olefin(e) centent in gasoline such as even can be made to reduce and even can reach 60 % by weight, octane value raising even reaches 10 units.The inventive method can realization response condition control flexibly, controls simple, thus effectively promotes that object reaction is carried out.
Accompanying drawing explanation
Accompanying drawing is the schematic flow sheet of stop bracket gasoline production method provided by the invention.
Wherein: 3-compressor, 4-interchanger, 5-superposition reactor, 6-strainer, 7-circulation water pot, 13-riser tube, 15-settling vessel, 16-cyclonic separator, 18-inclined tube to be generated, 19-guiding valve to be generated, 20-regenerator sloped tube, 21-regenerates guiding valve, 22-catalyst cooler, 25-revivifier, 26-dispersion plate.Other is pipeline, and 1 is feedstock transportation pipeline, and 2 is water vapour pipeline, and 8 make up line for recirculated water, and 9 is recirculated water vent line.
Embodiment
The method of production stop bracket gasoline provided by the invention, the raw material used comprises light gasoline fraction, and the boiling range of described light gasoline fraction is between 30 ~ 80 DEG C, and it is mainly C5 ~ C7 hydrocarbon, wherein the content of C5 ~ C7 alkene is preferably 20 ~ 70 % by weight, and more preferably 30 ~ 60 % by weight.Described light gasoline fraction can be one or more in light FCC gasoline, catalytic pyrolysis petroleum naphtha, light coker naphtha, thermo-cracking petroleum naphtha, thermally splitting petroleum naphtha, gelatin liquefaction petroleum naphtha.
Too high hydrogen sulfide and mercaptans content easily make the activity of polymerization catalyst reduce and promote the generation of colloid in polymer gasoline, and basic nitrogen compound material can cause the activity decrease of polymerization catalyst, therefore.Under preferable case, the sulphur content of described light gasoline fraction is <20 μ g/g, basic nitrogen compound content <0.6 μ g/g.In described petroleum naphtha, water-content is no more than 1800 μ g/g, is preferably 600 ~ 1800 μ g/g.When described light gasoline fraction sulphur content and basic nitrogen compound thing content higher, can described light gasoline fraction be processed.Described process, can adopt existing method.Such as, in order to reduce sulphur content, can remove hydrogen sulfide through thanomin, then alkali cleaning is to remove mercaptan, eventually passes washing to wash away residual salt, the sulphur content in gasoline is met the demands.The content of preferred bases is no more than 0.5 μ g/g, and the method for described thanomin desulfurization, alkali cleaning, washing is existing method, can see document " petroleum gas desulfurization and liquid product doctor process " (Liaoning chemical industry, 1987,2:33 ~ 39).The method of de-basic nitrogen compound (basic nitrogen compound) can according to existing method, for example, see document " removing the method for nitrogenous compound in light FCC gasoline " (virgin phoenix bifurcation, Wu Mingqing.Refining of petroleum and chemical industry, 2011,42(12): 86-89)
In the method for production stop bracket gasoline provided by the invention, the operational condition of described superposition reactor is: temperature of reaction is 50 ~ 500 DEG C, preferably 100 ~ 400 DEG C, more preferably 100 ~ 300 DEG C, reaction pressure 1 ~ 10MPa, preferably 1 ~ 8MPa, more preferably 2 ~ 6MPa, reaction velocity (weight hourly space velocity) 0.1 ~ 10h -1, preferred 0.5 ~ 8h -1, more preferably 1 ~ 6h- 1.Preferably, temperature of reaction is 100 ~ 300 DEG C, and reaction pressure is 2 ~ 6MPa, and reaction velocity is 1 ~ 6h -1be beneficial to improve reaction product medium-chain olefins and naphthene content, be beneficial to subsequent reactions and improve gasoline octane rating.
In the method for production stop bracket gasoline provided by the invention, described polymerization catalyst is one or more in the loaded catalyst of phosphoric acid catalyst, acidic resins, loaded metal or metal oxide, sial solid acid catalyst and molecular sieve solid acid catalyst, described phosphoric acid catalyst can for being loaded in phosphoric acid on diatomite, carry phosphoric acid on the activated carbon, soak the quartz sand of peroxophosphoric acid, be loaded in the phosphoric acid on silica gel and one or more in cupric pyrophosphate; Described acidic resins such as acidic cation-exchange resin; Described solid acid catalyst is y-type zeolite, ZSM-5 zeolite, beta zeolite (β zeolite) such as, can through modification, such as, through non-metallic element and/or metallic element modification or unmodified ZSM-5 and/or β zeolite etc.Preferred polymerization catalyst is phosphoric acid catalyst or zeolite catalyst, more preferably containing the catalyzer of ZSM-5 type zeolite, owing to having strongly-acid and excellent Shape-selective, the superimposed of alkene and cyclisation can be promoted, described ZSM-5 is preferably HZSM-5 zeolite, the preferred HY zeolite of described y-type zeolite, described β zeolite preferred H β zeolite.Described zeolite catalyst comprises the matrix of zeolite and 0 ~ 90 % by weight of 10 ~ 100 % by weight; The matrix of zeolite and 20 ~ 90 % by weight of such as 10 ~ 80 % by weight, one or more in described matrix such as clay, silicon oxide, aluminum oxide, silica-alumina.
The method of production stop bracket gasoline provided by the invention, alkene in described light gasoline fraction can react in superposition reactor, obtain the reaction product mainly containing C10 ~ C14 alkene and a certain amount of naphthenic hydrocarbon, in described superimposed product, C10 ~ C14 alkene and naphthenic hydrocarbon account for more than 80% weight, be such as 80 ~ 95 % by weight, this is conducive to obtaining described stop bracket gasoline.
The method of production stop bracket gasoline provided by the invention, uses described light gasoline fraction for raw material production stop bracket gasoline; Can also using be separated or non-separating ethene, one or more in liquefied gas, coking gas or thermal cracking gas after propylene with described petroleum naphtha raw material together charging introduce superposition reactor as reaction raw materials and to contact with polymerization catalyst and react.Under preferable case, the content of petroleum naphtha described in described raw material is 70 ~ 100 % by weight, such as, be 70-90 % by weight, and the content of other raw material except described petroleum naphtha for being 0-30 % by weight, such as, is 10% ~ 30 % by weight.
The method of production stop bracket gasoline provided by the invention, flow out the oil gas of superposition reactor, directly can introduce aromatization reactor, also first such as can cross through removing catalyzer wherein and filter the catalyst fines wherein carried, then introducing described aromatization reactor reaction, reacting without being separated the aromatization reactor described in directly introducing after the catalyzer that preferred removing is wherein carried.
In the method for production stop bracket gasoline provided by the invention, the operational condition of described aromatization reactor is: temperature of reaction 100 ~ 500 DEG C, preferably 150 ~ 450 DEG C, more preferably 200 ~ 400 DEG C, reaction pressure 0.1 ~ 0.5MPa, agent-oil ratio 1 ~ 100, preferably 10 ~ 80, more preferably 20 ~ 70, reaction times is 1 ~ 20 second, preferably 2 ~ 15 seconds, more preferably 2 ~ 8 seconds, water vapor and stock oil mass ratio (abbreviation water-oil ratio) 0 ~ 1, such as 0 ~ 0.1.
In the method for production stop bracket gasoline provided by the invention, described aromatized catalyst is solid acid catalyst, such as, containing the catalyzer of zeolite.The described catalyzer containing zeolite comprises zeolite, inorganic oxide and optional clay, and each component accounts for total catalyst weight ratio respectively: zeolite 1 ~ 50 % by weight, inorganic oxide 5 ~ 99 % by weight, clay 0 ~ 70 % by weight; Its mesolite, as active ingredient, preferably includes mesopore zeolite and optional large pore zeolite, and described mesopore zeolite accounts for 50 ~ 100 % by weight of zeolite gross weight, and preferably 70 ~ 100 % by weight, large pore zeolite accounts for 0 ~ 50 % by weight of zeolite gross weight, and preferably 0 ~ 30 % by weight.Described mesopore zeolite can be selected from ZSM series zeolite and/or ZRP zeolite, and described ZSM series zeolite is selected from one or more in the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures.Described mesopore zeolite can carry out modification with non-metallic element and/or metallic element, described non-metallic element such as phosphorus, one or more in described metallic element such as Ga, Zn, Cd, Ni.Described mesopore zeolite is preferably past metal-modified ZSM series zeolite catalyst.Described large pore zeolite such as y-type zeolite, can be selected from Rare Earth Y (REY) zeolite, rare earth hydrogen Y(REHY) zeolite, overstable gamma zeolite form this group zeolite in one or more.Described inorganic oxide, as caking agent, is selected from silicon-dioxide (SiO 2) and/or aluminium sesquioxide (Al 2o 3).Clay, as matrix (i.e. carrier), can be selected from kaolin and/or halloysite.
In the method for production stop bracket gasoline provided by the invention, described aromatization reactor can be riser reactor, fluidized-bed reactor, fixed-bed reactor, downflow reactor, etc. linear speed reactor and the reactor that improves on above-mentioned reactor basis; Wherein, preferred riser reactor or fluidized-bed reactor.Described superposition reactor can be fixed-bed reactor, paste state bed reactor or moving-burden bed reactor, preferred fixed-bed reactor such as tubular fixed-bed reactor.
In the method for production stop bracket gasoline provided by the invention, subsequent separation system is entered from aromatization reactor reaction oil gas out, through being separated, target gasoline products can be obtained, aromatic hydrocarbons wherein containing more many methyl branches, aromatic hydrocarbons content in gasoline aromatic hydrocarbons of many methyl branches can be more than 50 % by weight, and described gasoline has higher octane value, usually being not less than 92, such as, can be 92 ~ 120.The octane value (RON) of described stop bracket gasoline is preferably not less than 95, is more preferably not less than 97.Gasoline also can isolate the light gasoline fraction of 30 ~ 80 DEG C further, the light gasoline fraction of 30 ~ 80 DEG C that separation obtains can enter superposition reactor and transform further together with described petroleum naphtha raw material, also directly can go out reaction unit, preferred described separation system is separated the light gasoline fraction obtained and enters superposition reactor transform together with light gasoline fraction raw material.
The method of production stop bracket gasoline provided by the invention, a kind of embodiment, by the light gasoline fraction of boiling range 30 ~ 80 DEG C through thanomin desulfurization, alkali cleaning and washing, and after de-basic nitrogen compound, preferably mixing with water such as distilled water makes the water-content in raw material be 600 ~ 1800 μ g/g, and be forced into required pressure, heat exchange is warmed up to temperature of reaction, introducing superposition reactor reacts, and the temperature of reaction of reactor can be controlled by the softening water circulated.The product of building-up reactions draws superposition reactor, direct introducing metre filter, remove through strainer that the catalyst powder brought out is last directly introduces aromatization reactor by bottom aromatization reactor, that comes with regenerator sloped tube is promoting the regeneration aromatized catalyst contact reacts upwards flowed under the effect of steam.The reaction oil gas of aromatization reactor is exported by aromatization reactor and enters settling vessel, being separated of oil gas and catalyzer is carried out under the effect of cyclonic separator, isolated oil gas enters subsequent separation system, the aromatized catalyst to be generated of isolated band charcoal directly enters the stripping stage of cyclonic separator lower end, after stripping, enter coke burning regeneration in catalyst regenerator, the regeneration aromatized catalyst of activity recovery returns in aromatization reactor and recycles after cooling.
Further illustrate method provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.
Fig. 1 is the schematic flow sheet of stop bracket gasoline production method provided by the invention.As shown in Figure 1, come to enter compressor 3 after raw material (comprising described petroleum naphtha) mixes with the distilled water of pipeline 2 from pipeline 1 and be pressurized to required pressure, and after interchanger 4 heat exchange is warming up to suitable temperature (being such as warming up to temperature of reaction), enters reactor 5 reacts.The temperature of reactor can be entered the pressure after reactor and control (recirculated water returns circulation water pot 7 by pipeline 10) by the softening water carrying out self-circulating water tank 7.Reaction product goes out from reactor underflow, removes the catalyst fines brought out through strainer 6, after enter bottom riser tube 13 through pipeline 11.Regeneration aromatized catalyst enters riser tube 13(wherein 21 for guiding valve from regenerator sloped tube 20, may be used for the flow controlling catalyzer), react with the hydrocarbons contact introducing riser tube 13 through pipeline 11 under the castering action of the pre-lift medium introduced through pipeline 12 and upwards flow.Reaction oil gas from riser tube 13 outlet enter settling vessel 15, and under the effect of cyclonic separator 16 separating reaction oil gas and catalyzer.Reaction product after separation enters subsequent separation system through pipeline 17, isolated catalyzer enters the stripping stage of settling vessel 15, after the stripping steam stripping of pipeline 14, enter revivifier 25 by inclined tube 18 to be generated regenerate (wherein 19 is guiding valve, may be used for the flow controlling catalyzer).Air enters revivifier 25 through pipeline 27, after dispersion plate 26 distributes, carry out coke burning regeneration with catalyst exposure.Catalyzer after regeneration enters riser tube 13 by regenerator sloped tube 20 and recycles after catalyst cooler 22 is lowered the temperature.Wherein introduce heat-eliminating medium such as water through pipeline 23 in catalyst cooler 22, draw the heat-eliminating medium after adding heating through pipeline 24.
The following examples will be further described present method, but therefore not limit present method.
The stock oil used in embodiment and the character of catalyzer list in table 1 and table 2.Catalyst A in table 2 is produced by the auspicious rich catalyst plant in Wenzhou, and catalyst B is produced by catalyzer asphalt in Shenli Refinery of Sinopec Group.
Embodiment 1
Raw materials used is light FCC gasoline, boiling range 30 ~ 80 DEG C, and wherein C5 ~ C7 alkene accounts for 45.4 % by weight, and other character, in table 1, uses polymerization catalyst A, aromatized catalyst B listed by table 2, the middle-scale device of successive reaction regenerative operation is tested.Light gasoline fraction enters superposition reactor, reactor interior reaction temperature 150 DEG C, weight hourly space velocity 2h -1, reaction pressure 3MPa; Reaction product (oil gas) introduce after filtering riser reactor reaction, reactor outlet temperature 300 DEG C, reactor outlet pressure 0.2Mpa, agent weight of oil than 25,4 seconds reaction times, water-oil ratio (weight ratio) 0.05.Be separated reclaimable catalyst and oil gas, reclaimable catalyst is Returning reactor after steam stripping regeneration, and oil gas enters separation system and is isolated to object product stop bracket gasoline, and operational condition, raw material and product slates list in table 1.As can be seen from Table 1, after reaction, gasoline yield is 87.52%, and research octane number (RON) (RON), up to 98, improves 7 units, and in gasoline family's composition aromatic hydrocarbons, the aromaticity content of many methyl branches is 55.3 % by weight.The superimposed product octane value of superposition reactor is 85.
Embodiment 2
With light FCC gasoline listed by table 1 for raw material (boiling range 30 ~ 80 DEG C, wherein C5 ~ C7 alkene accounts for 45.4 % by weight), use polymerization catalyst A and aromatized catalyst B listed by table 2, the middle-scale device of successive reaction regenerative operation is tested.Light FCC gasoline cut enters superposition reactor, temperature 300 DEG C, and weight hourly space velocity 2h -1, contact with polymerization catalyst A under reaction pressure 5Mpa condition and react; Reaction product enters riser reactor after filtering, temperature of reaction 350 DEG C, reaction pressure 0.2Mpa, agent-oil ratio (weight ratio) 60, in 6 seconds reaction times, contact with aromatized catalyst B under water-oil ratio (weight ratio) 0.05 condition and react, be separated reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after steam stripping regeneration, and reaction oil gas enters separation system and is isolated to object product stop bracket gasoline.Operational condition, raw material and and product slates list in table 1.As can be seen from Table 1, after reaction, gasoline yield is 83.41%, and research octane number (RON) (RON), up to 102, improves 11 units.In the aromatic hydrocarbons of gasoline, many methyl branches aromaticity content accounts for 65.12 % by weight.The superimposed product octane value of superposition reactor is 83.
Embodiment 3
With light FCC gasoline listed by table 1 for raw material, use polymerization catalyst A and aromatized catalyst B listed by table 2, the middle-scale device of successive reaction regenerative operation is tested.The described light gasoline fraction of boiling range 30 ~ 80 DEG C enters superposition reactor, and wherein C5 ~ C7 alkene accounts for 45.4 % by weight, temperature 190 DEG C, and weight hourly space velocity 2h -1, contact with catalyst A under reaction pressure 3Mpa condition and react.Reaction product enters riser reactor after filtering, temperature of reaction 300 DEG C, and reaction pressure 0.2Mpa(absolute pressure), agent-oil ratio (weight ratio) 50, in 6 seconds reaction times, contacts with catalyst B under water-oil ratio (weight ratio) 0.05 condition and reacts.Be separated reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after steam stripping regeneration, and reaction oil gas enters separation system and is isolated to object product stop bracket gasoline, and operational condition, raw material and product slates list in table 1.As can be seen from Table 1, after reaction, gasoline yield is 87.14%, and research octane number (RON) (RON), up to 108, improves 17 units.In the aromatic hydrocarbons of gasoline family's composition, many methyl branches aromatic hydrocarbons accounts for 75.3 % by weight.The superimposed product octane value of superposition reactor is 80.
Embodiment 4
With light FCC gasoline listed by table 1 for raw material, use polymerization catalyst A catalytic cracking catalyst B listed by table 2, the middle-scale device of successive reaction regenerative operation is tested.The light gasoline fraction that boiling range is 30 ~ 80 DEG C enters superposition reactor, and wherein C5 ~ C7 alkene accounts for 45.4 % by weight, temperature 300 DEG C, and weight hourly space velocity 2h -1, contact with catalyst A under reaction pressure 3Mpa condition and react.Reaction product enters riser reactor after filtering, temperature of reaction 300 DEG C, reaction pressure 0.2Mpa, agent-oil ratio (weight ratio) 50, in 6 seconds reaction times, contact with catalyst B under water-oil ratio (weight ratio) 0.05 condition and react, be separated reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after steam stripping regeneration, and reaction oil gas enters separation system and is isolated to object product stop bracket gasoline.Operational condition, raw material and product slates list in table 1.As can be seen from Table 1, after reaction, gasoline yield is 85.82%, and research octane number (RON) (RON), up to 104, improves 13 units.In gasoline family's composition aromatic hydrocarbons, the aromaticity content of many methyl branches is 67.2 % by weight, and the superimposed product octane value of superposition reactor is 82.
Embodiment 5
With light FCC gasoline listed by table 1 for raw material, use polymerization catalyst A catalytic cracking catalyst B listed by table 2, the middle-scale device of successive reaction regenerative operation is tested.The described light FCC gasoline cut (wherein C5 ~ C7 alkene accounts for 45.4 % by weight) of boiling range 30 ~ 80 DEG C enters superposition reactor, temperature 190 DEG C, and weight hourly space velocity 2h -1, react with catalyst exposure under reaction pressure 3Mpa condition.Reaction product enters riser reactor after filtering, and temperature of reaction 350 DEG C, reaction pressure 0.2Mpa, agent-oil ratio (weight ratio) 50, in 6 seconds reaction times, contacts with catalyst B under water-oil ratio (weight ratio) 0.05 condition and react.Be separated reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after steam stripping regeneration, and reaction oil gas enters separation system and is isolated to object product stop bracket gasoline, and operational condition, raw material and product slates list in table 1.As can be seen from Table 1, after reaction, gasoline yield is 86.57%, and research octane number (RON) (RON), up to 106, improves 15 units.In gasoline family's composition aromatic hydrocarbons, the aromatic hydrocarbons of many methyl branches accounts for 70.6 % by weight, and the superimposed product octane value of superposition reactor is 80.
Table 1
Table 2
The hydrothermal aging conditions of catalyzer: 800 DEG C, 100% water vapour, 12 hours.

Claims (14)

1. produce the method for stop bracket gasoline for one kind, comprise: the light gasoline fraction of boiling range 30 ~ 80 DEG C is introduced superposition reactor and polymerization catalyst contact reacts, the building-up reactions product obtained introduces aromatization reactor and aromatized catalyst contact reacts, the aromatization products obtained is isolated to stop bracket gasoline, and in described superimposed product, C10 ~ C14 alkene and naphthenic hydrocarbon account for more than 80% weight.
2. according to the method for production stop bracket gasoline according to claim 1, it is characterized in that, described light gasoline fraction sulphur content is no more than 20 μ g/g, and basic nitrogen compound content is no more than 0.6 μ g/g, water-content 600 ~ 1800 μ g/g.
3. according to the method for production stop bracket gasoline according to claim 1, it is characterized in that, described light gasoline fraction olefin(e) centent is 20 ~ 70 % by weight, and aromaticity content is no more than 20 % by weight.
4. according to the method for production stop bracket gasoline according to claim 1, it is characterized in that, described light gasoline fraction is one or more in light FCC gasoline, catalytic pyrolysis petroleum naphtha, light coker naphtha, thermo-cracking petroleum naphtha, thermally splitting petroleum naphtha, gelatin liquefaction petroleum naphtha.
5. according to the method for production stop bracket gasoline according to claim 1, it is characterized in that, in the aromatic hydrocarbons of described stop bracket gasoline, many methyl branches aromatic hydrocarbons accounts for more than 50 % by weight.
6. according to the method for production stop bracket gasoline according to claim 1, it is characterized in that, the reaction conditions of described superposition reactor comprises: temperature of reaction is 50 ~ 500 DEG C, reaction pressure is 1 ~ 10MPa, reaction weight hourly space velocity is 0.1 ~ 10h -1.
7. according to the method for production stop bracket gasoline according to claim 6, it is characterized in that, the temperature of reaction of superposition reactor is 100 ~ 300 DEG C, reaction pressure is 2 ~ 6MPa, reaction weight hourly space velocity is 1 ~ 6h -1.
8. according to the method for the production stop bracket gasoline described in claim 1,6 or 7, it is characterized in that, the operational condition of described aromatization reactor comprises: temperature of reaction is 150 ~ 500 DEG C, reaction pressure is 0.1 ~ 0.5MPa, agent weight of oil ratio is 1 ~ 100, the reaction times is 1 ~ 20 second, and water vapor and stock oil mass ratio are 0 ~ 0.1.
9. according to the method for production stop bracket gasoline according to claim 8, it is characterized in that, the operational condition of described aromatization reactor comprises: temperature of reaction is 200 ~ 450 DEG C, and agent weight of oil ratio is 10 ~ 80, and the reaction times is 2 ~ 15 seconds.
10. according to the method for production stop bracket gasoline according to claim 8, it is characterized in that, the operational condition of described aromatization reactor comprises: temperature of reaction 250 ~ 400 DEG C, agent-oil ratio 20 ~ 70,2 ~ 8 seconds reaction times.
11., according to the method for production stop bracket gasoline according to claim 1, is characterized in that, the catalyzer of described building-up reactions is one or more in phosphoric acid catalyst, acidic resins, sial solid acid catalyst and molecular sieve solid acid catalyst.
12. according to the method for production stop bracket gasoline according to claim 11, it is characterized in that, described phosphoric acid catalyst is one or more in the catalyzer that formed on silica gel of the catalyzer that formed on silica gel of catalyzer, phosphoric acid load that catalyzer, phosphoric acid that phosphoric acid load is formed over celite carry quartz sand that the catalyzer, the phosphoric acid dip that are formed on the activated carbon cross and formed and cupric pyrophosphate load; Described zeolite catalyst comprises the matrix of zeolite and 0 ~ 90 % by weight of 10 ~ 100 % by weight; Described zeolite is one or more in y-type zeolite, ZSM-5 zeolite, beta zeolite.
13. according to the method for production stop bracket gasoline according to claim 12, and it is characterized in that, described ZSM-5 is HZSM-5 zeolite, and described y-type zeolite is HY zeolite, and described β zeolite is H β zeolite.
14. according to the method for production stop bracket gasoline according to claim 1, and it is characterized in that, in the product of described building-up reactions, C10 ~ C14 alkene and naphthenic hydrocarbon account for 80 ~ 95 % by weight.
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CN101429452A (en) * 2007-11-08 2009-05-13 中国石油天然气股份有限公司 Method for producing high-octane gasoline

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