CN109097104B - A kind of FCC gasoline method for modifying - Google Patents

A kind of FCC gasoline method for modifying Download PDF

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CN109097104B
CN109097104B CN201811057464.0A CN201811057464A CN109097104B CN 109097104 B CN109097104 B CN 109097104B CN 201811057464 A CN201811057464 A CN 201811057464A CN 109097104 B CN109097104 B CN 109097104B
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catalyst
acid
carrier
zsm
molecular sieve
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CN109097104A (en
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鲍晓军
王廷海
岳源源
王学丽
刘杰
袁珮
朱海波
白正帅
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Fuzhou University
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Fuzhou University
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Priority to JP2021524084A priority patent/JP7083967B2/en
Priority to PCT/CN2018/122105 priority patent/WO2020052145A1/en
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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]
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The present invention relates to a kind of FCC gasoline method for modifying, FCC gasoline is under catalyst for pre-hydrogenation effect, by pre-hydrogenator, carry out mercaptan etherificate, double-bond isomerism reaction, pre-hydrotreating reaction effluent is cut into light, heavy naphtha, isomerization reaction occurs under the action of heterogeneous catalyst for light gasoline fraction, and heavy naphtha carries out selective hydrodesulfurization under hydrodesulfurization-heterogeneous catalyst effect, while linear alkene tautomerizes to single branched-chain alkene or single branched paraffin；Heavy naphtha after reaction enters back into octane value recovering unit, contacts with octane value recovering catalyst, carries out double branched chain isomer reactions；Last light, heavy naphtha reconciles to obtain low alkene, ultra-low sulfur, the high clean gasoline product of octane number.

Description

A kind of FCC gasoline method for modifying
Technical field
The present invention relates to a kind of FCC gasoline method for modifying.
Background technique
FCC gasoline is made of mixed the hydro carbons of C4-C12 and micro sulfide, oxide and metal arsenide etc. Close object, according to the difference of the oil property of each oil refining enterprise and processing route, FCC gasoline be by 18~55v% alkene, 12~ The mixture of aromatic hydrocarbons and the alkane composition of 20v%, the octane performance of each component is aromatic hydrocarbons > alkene ≈ isoparaffin > alkane.I State's high-sulfur, high olefin content and the FCC gasoline compared with low octane rating account for about 70%, and low sulfur content, low olefin-content, high-octane rating Alkylate oil, the ratio of isomerized oil and reformate it is lower, this makes cleaning needs while carry for China's FCC gasoline Desulfurization, Olefin decrease and the triple task objects for keeping octane number.
CN201010224554.1 provides a kind of production method of ultra-low sulfur and high-octane number gasoline.The production method packet It includes: entering full distillation gasoline raw material inferior in reactive distillation column, with thioetherification, thioetherification reaction occurs and goes forward side by side The cutting of row fraction, makes low-boiling mercaptan and thiophene sulfides be converted into high boiling thioether and be transferred to heavy distillat gasoline In, the cutting cut point of light fraction gasoline and heavy distillat gasoline is 50-90 DEG C；Keep light fraction gasoline and hydro carbons highly-branched chain isomerous Catalyst contact；Connect heavy distillat gasoline with catalyst for selectively hydrodesulfurizing and supplement desulfurization-hydro carbons isomery/aromatization catalyst Touching；Treated light fraction gasoline and heavy distillat gasoline are mixed, super-low sulfur high-knock rating gasoline is obtained.The invention is suitable for bad The modification of matter gasoline especially can obtain preferable desulfurization to the catalytically cracked gasoline inferior of ultra-high-sulfur(UHS), high alkene, Olefin decrease is imitated Fruit, and can maintain or improve the octane number of product after reacting and keep higher product yield.
Currently, in the quality of gasoline upgrade technique that domestic oil refining enterprises are generally selected, using Prime-G technology as the height of representative Selective desulfurization technique supplements desulfurization work using pre-add hydrogen-weight gasoline cutting-heavy petrol selective hydrodesulfurization-heavy petrol Skill principle.But due to specific gasoline stocks composition and content is different and gasoline products standard is different, gasoline upgrading technique and institute It is also larger with catalyst difference.
Summary of the invention
The present invention provides a kind of FCC gasoline method for modifying, specifically a kind of catalytically cracked gasoline through pre-add hydrogen, be cut into, Isomerization reaction, heavy naphtha hydrodesulfurization-isomery occur for weight gasoline fraction, light gasoline fraction, then carry out double branched chain isomers Etc. processes produce low alkene, ultra-low sulfur, the method for clean gasoline with high octane.
A kind of FCC gasoline method for modifying, FCC gasoline, by pre-hydrogenator, carry out under catalyst for pre-hydrogenation effect Mercaptan etherificate, double-bond isomerism reaction, pre-hydrotreating reaction effluent are cut into light, heavy naphtha, and light gasoline fraction is urged in isomery Isomerization reaction occurs under the action of agent, heavy naphtha carries out selective hydrogenation under hydrodesulfurization-heterogeneous catalyst effect Desulfurization, while linear alkene tautomerizes to single branched-chain alkene or single branched paraffin；Heavy naphtha after reaction enters back into octane number Recovery unit is contacted with octane value recovering catalyst, carries out double branched chain isomer reactions；Last light, heavy naphtha reconciles to obtain Clean gasoline.
Above-mentioned FCC gasoline passes through pre-hydrogenator, carries out mercaptan etherificate, double-bond isomerism reaction, and reaction condition is as follows: anti- 80-160 DEG C of temperature, reaction pressure 1-5MPa is answered, liquid volume air speed 1-10h-1, hydrogen to oil volume ratio 3-8:1；Catalyst for pre-hydrogenation Including carrier and active component, carrier includes alumina composite carrier and the 5-25wt% choosing that 75-95wt% has macroporous structure From ZSM-5, ZSM-11, ZSM-12, ZSM-35, modenite, amorphous silicon aluminium, SAPO-11, MCM-22, Y molecular sieve or beta One or more of molecular sieve, alumina composite carrier contain the witch culture cadmium ferrite of 0.1-12wt%, and alumina composite carries The 1-70% in the total hole the 1-85% in the total hole the mesoporous Zhan of body, macropore Zhan.Preferably, the 5-70% in the total hole mesoporous Zhan, preferably macropore account for The 5-45% in total hole.Carrier surface load active component cobalt, molybdenum, nickel, one or more of tungsten remembered with oxide, active group Dividing content is 0.1~15.5%.
Further preferably, reaction condition is as follows: 90-145 DEG C of reaction temperature, reaction pressure 1-4MPa, liquid volume air speed 1-8h-1, hydrogen to oil volume ratio 3-6:1；
Pre-hydrotreating reaction of the invention is mainly small molecule mercaptan, thioether under the action of catalyst for pre-hydrogenation, with diene Thioetherification reaction, while double-bond isomerism (i.e. terminal olefine is converted into internal olefin) occur for hydrocarbon, and remaining alkadienes is saturated.In sulphur Inhibit the side reactions such as olefinic polymerization, overcracking, overcracking while etherified, double-bond isomerism reacts, to improve catalyst Activity and selectivity improves liquid yield.
It include the witch culture cadmium ferrite of 0.1-12wt% in the alumina composite carrier with macroporous structure, carrier is situated between The 1-70% in the total hole the 1-85% in the total hole hole Zhan, macropore Zhan.Preferably, the 5-70% in the total hole mesoporous Zhan, the preferably total hole macropore Zhan 5-45%.
A kind of preparation method of the alumina composite carrier with macroporous structure, is added to kneader for silicon source and sesbania powder In be uniformly mixed, inorganic acid solution and organic polymer is added, mediates uniformly, then adds witch culture cadmium ferrite, mediates equal After even, by extrusion, molding, drying, roasting, alumina support is obtained.
The above-mentioned alumina composite carrier powder with macroporous structure and ZSM-5, ZSM-11, ZSM-12, ZSM-35, mercerising One or more of zeolite, SAPO-11, MCM-22, Y molecular sieve or beta molecular sieve powder are uniformly mixed, and add sesbania Powder deionized water mixes, and inorganic acid is added, and stirs, dry, and calcination process obtains mixed carrier.Load active component cobalt again, molybdenum, Nickel, tungsten, cobalt in catalyst, molybdenum, nickel, tungsten remembered with oxide, content 0.1-15.5%.
The above-mentioned alumina support source of aluminium for preparing is one or more of boehmite, aluminium oxide, aluminum sulfate.Aluminium Source is also possible to one or more of kaolin, rectorite, perlite, montmorillonite.
Further improvement to carrier, a kind of improvement alumina support include the silica of 0.1-12wt%, tungsten in carrier The 1-80% in the total hole doped lanthanum ferrite 0.1-10wt%, the mesoporous Zhan of carrier, the 1-55% in the total hole macropore Zhan.Preferably, mesoporous to account for 1-65%, the more preferable 5-55% in total hole, the preferably 5-45% in the total hole macropore Zhan, more preferable 10-35%, carrier micropore, it is mesoporous, Macropore uneven distribution.
Preferably, witch culture cadmium ferrite is 0.3-9wt%, more preferable 0.3-5wt%, witch culture in above-mentioned alumina support Tungsten accounts for the 0.1-8wt% of witch culture cadmium ferrite in cadmium ferrite.
The organic polymer is one of polyvinyl alcohol, Sodium Polyacrylate, polyethylene glycol, polyacrylate or several Kind, preferably polyacrylic acid or Sodium Polyacrylate.
Compared to addition cadmium ferrite (LaFeO3), witch culture cadmium ferrite is added in alumina support, be re-introduced into selected from ZSM-5, In ZSM-11, ZSM-12, ZSM-35, modenite, amorphous silicon aluminium, SAPO-11, MCM-22, Y molecular sieve or beta molecular sieve One or more prepare complex carrier, Supported Co, molybdenum, nickel, tungsten active component, catalyst effectively facilitates thioetherification reaction, together When double-bond isomerism (terminal olefine is converted into internal olefin), and remaining alkadienes is saturated, especially double-bond isomerism selectivity ratio It is higher.
Carrier is further improved, is preferably added to silica, the preparation side of improved alumina support in alumina support Boehmite and sesbania powder are added in kneader and are uniformly mixed by method, and inorganic acid or organic acid soln and organic poly- is added Object is closed, mediates uniformly, then adds witch culture cadmium ferrite, is uniformly mixed that obtain alumina precursor spare；Organic polymer Acid solution in silicon source is added, the organic polymer of unit content is higher than the content of organic polymer in silicon source in alumina precursor 1.5 times or more.After mixing, it is mixed with alumina precursor, through extrusion, molding, drying, roasting, obtains alumina support. The silicon source can be sodium metasilicate or silicon powder, and Tungstenic compound includes ammonium tungstate, ammonium metatungstate, ammonium paratungstate etc..The nothing Machine acid is nitric acid, hydrochloric acid, sulfuric acid, and organic acid is oxalic acid, citric acid, nitrilotriacetic acid, tartaric acid, acetic acid or malic acid.
The further improvement of above-mentioned alumina support, the silicon source can be sodium metasilicate or silicon powder, be also possible to diatom One or both of soil, opal, silicon source is also possible to one of kaolin, rectorite, perlite, montmorillonite or several Kind.
Kaolin, rectorite, perlite, montmorillonite powder activation process sub-molten salt medium be NaOH-H2O, by alumina Miberal powder end is uniformly mixed in mass ratio for 1:0.2-2 with sub-molten salt medium, at a temperature of 100-400 DEG C, activation time 0.5- 4h.Diatomite, opal activation process be by diatomite at a temperature of 500-1000 DEG C, roast 1-10h.Above-mentioned carrying alumina Witch culture cadmium ferrite in body is preferably provided with micro- mesoporous, and introducing has micro- mesoporous witch culture cadmium ferrite, and the catalyst of preparation is advantageous In inhibiting the side reactions such as cracking hydrocarbon to occur, purpose product selectivity is improved.
A kind of preparation method with micro- mesoporous witch culture cadmium ferrite, citric acid are dissolved in stirring and dissolving in deionized water, Then lanthanum nitrate and ferric nitrate are added in citric acid, stirring and dissolving, Sodium Polyacrylate or polyacrylic acid, Sodium Polyacrylate is added Or the additional amount of polyacrylic acid is the 0.1-9wt%, preferably 0.1-6.0wt% of witch culture cadmium ferrite.Tungstenic compound is added, Remembered with oxide, tungsten accounts for the 0.1-8wt% of witch culture cadmium ferrite, and stirring after reaction, obtains finished product through drying, roasting, grinding.
Alumina support of the present invention is the alumina composite carrier with macroporous structure.
In improved alumina support, the organic polymer of unit content is than organic polymer in silicon source in alumina precursor High 1.5 times of the content of object or more.It can be effectively improved the pore structure of carrier, on the one hand make that carrier micropore, mesoporous, macropore is uneven Distribution reduces the side reactions such as olefinic polymerization, overcracking and occurs, improves selectivity, and yield of gasoline is high, is conducive to device long period Operating；On the other hand be conducive to carrier surface and produce more active sites load centres, improve catalyst activity.
The carrier of catalyst for pre-hydrogenation of the present invention includes to have the alumina composite carrier of macroporous structure and be selected from ZSM-5, ZSM-11, ZSM-12, ZSM-35, modenite, amorphous silicon aluminium, SAPO-11, MCM-22, Y molecular sieve or beta points One or more of son sieve, Supported Co, molybdenum, nickel, one or more of tungsten, for gasoline removing alkadienes and mercaptan, sulphur Ether, while double-bond isomerism terminal olefine is converted into internal olefin；And it is saturated remaining alkadienes.Catalyst not only effectively facilitates terminal olefine and turns Internal olefin improves octane number, and advantageously reduces the recracking reaction of low-carbon isohydrocarbon, reduces olefinic polymerization, overcracking Side reactions are waited, active selectable is improved, yield of gasoline is high.
Above-mentioned cobalt, molybdenum, nickel, tungsten active component can be their various salts or their own oxide, vulcanization Object, nitride, one or more of phosphide.
The preparation method of catalyst for pre-hydrogenation includes the following steps: that cobalt will be contained, and the active ingredients substances of molybdenum, nickel, tungsten are made into Maceration extract, impregnated carrier roast 3-9 hours at 4-8 hours, 450-800 DEG C dry at 120-180 DEG C, obtain pre-add hydrogen and urge Agent.
Catalyst is further improved, the catalyst further includes selected from ZSM-5, ZSM-11, ZSM-12, ZSM-35, silk One or more of light, SAPO-11, MCM-22, Y molecular sieve or beta molecular sieve.
It is 50-70 DEG C that pre-hydrotreating reaction effluent, which cuts cut point, and light gasoline fraction is under the action of heterogeneous catalyst Isomerization reaction occurs, heterogeneous catalyst has the alumina composite carrier and SAPO- of macroporous structure with above-mentioned catalyst for pre-hydrogenation The composite material that the proportion of 11 molecular sieves 80-90:10-20 in mass ratio obtains is carrier, and load quality percentage composition is 5- 18% active component Mo, Co and Ni and be made.
Heavy naphtha reaction effluent of the present invention carries out selectivity under hydrodesulfurization-heterogeneous catalyst effect and adds Hydrogen desulfurization, while linear alkene tautomerizes to the reaction process condition of single branched-chain alkene or single branched paraffin are as follows: reaction temperature 190- 330 DEG C, reaction pressure 1.2-3.5MPa, volume space velocity 2.5-5h-1, hydrogen to oil volume ratio 160-460:1.
Catalytic gasoline selective hydrodesulfurizationmodification-heterogeneous catalyst, including carrier and active component, carrier are pre-add hydrogen Catalyst used carrier, carrier surface load phosphomolybdic acid, phosphotungstic acid or P-Mo-Wo acid, phosphomolybdic acid, phosphotungstic acid or phosphorus in catalyst Molybdenum wolframic acid remembered with oxide, content 0.1-16.5%.
It being further improved, above-mentioned catalyst surface impregnates active component again and obtains improving catalyst, by weight percentage, Catalyst includes the metal active constituent of 0.1-14.5%, and active component is selected from cobalt, molybdenum, nickel, one or more of tungsten.
Hydrodesulfurization-heterogeneous catalyst of the present invention is born using the macroporous aluminium oxide comprising witch culture cadmium ferrite as carrier Carry phosphomolybdic acid tungsten, phosphotungstic acid or P-Mo-Wo acid and/or cobalt, molybdenum, nickel, one or more of tungsten, for gasoline hydrogenation selectivity Desulfurization-isomery not only effectively facilitates single branched chain isomer, improves octane number, and advantageously reduce the recracking of low-carbon isohydrocarbon Reaction reduces the side reactions such as olefinic polymerization, overcracking and occurs, and improves active selectable, and yield of gasoline is high.The catalyst is used for Catalytically cracked gasoline produces the clean gasoline for meeting state five, six standard of state.
Reaction effluent enters back into octane value recovering unit, in the case where alkane value restores catalyst action, carries out double branched chain isomers, The condition of reaction are as follows: 180-450 DEG C of reaction temperature, reaction pressure 0.6-4.8MPa, air speed 0.5-8h-1, hydrogen to oil volume ratio 50- 450:1。
Double branched chain isomers include that single branched-chain alkene or single branched paraffin tautomerize to double branched paraffins.
The octane value recovering catalyst includes ZSM-5 molecular sieve, and the octane value recovering catalyst is with weight percent Meter includes the mesoporous H-type Zn-ZSM-5 molecular sieve of 32-88% faintly acid or the mesoporous H-type Zn-ZSM-5 molecular sieve of improved faintly acid, Preferably 42-83%；0-66% boehmite, macroporous aluminium oxide or zinc-aluminum hydrotalcite binder are as carrier, preferably 8- 55%；Impregnate 0.5-16% metal active constituent, preferably 1-12%；The metal active constituent is Fe, Co, Ni, Mo and W One or more of, carrying method is infusion process, preferably equi-volume impregnating or multiple maceration.
In the present invention, the mesoporous H-type Zn-ZSM-5 molecular sieve of the faintly acid, mesoporous pore size concentrate on 4.5-36nm, Specific surface area is 320-650m2/g；Zinc oxide content is the 0.15-12% of molecular sieve total weight.
In the present invention, the mesoporous Zn-ZSM-5 molecular sieve of improved faintly acid, mesoporous pore size concentrate on 4.5-36nm, compare table Area is 320-650m2/g；Zinc oxide content is the 0.15-12% of molecular sieve total weight, and molecular sieve surface Zn content compares molecule It is high to sieve internal Zn content, it is preferably 0.2-2 times high.
The present invention also provides a kind of preparation methods of mesoporous Zn-ZSM-5 molecular sieve, include the following steps:
(1) at a certain temperature, by deionized water, silicon source, zinc source, acid source, template (SDA) and silicon source in stirring condition Lower be uniformly mixed is prepared into gel, and adjusting molar ratio of material is (0.003-0.07) Al2O3:(0.03-0.3)Na2O:1SiO2: (8-45)H2O:(0.05-0.2)SDA:(0.001-0.15)ZnO；
(2) it will be transferred in the stainless steel cauldron containing polytetrafluoroethyllining lining after the gel aging obtained in step (1) Seal crystallization, to crystallization after, crystallization product is cooling, be filtered to remove mother liquor, filter cake is washed with deionized to neutrality, does It is dry to obtain Zn-ZSM-5 molecular sieve；
(3) by Zn-ZSM-5 molecular sieve obtained in step (2) through a series of processing such as exchange, filtering, drying, roasting, Obtain H-type Zn-ZSM-5 molecular sieve.
The present invention is further improved mesoporous Zn-ZSM-5 molecular sieve, after obtaining H-type Zn-ZSM-5 molecular sieve, passes through dipping Method impregnates zinc compound on the surface of H-type Zn-ZSM-5 molecular sieve again and is modified, so that molecular sieve surface Zn content score Son sieves internal Zn content height, preferably incipient impregnation, obtains the improvement H-type Zn-ZSM-5 molecular sieve of Zn modification, i.e. improvement Zn- ZSM-5 molecular sieve.Wherein, the zinc compound is one or more of zinc nitrate, zinc acetate, zinc chloride and zinc sulfate, It is preferred that zinc acetate.
Silicon source described in step (1) can be conventional commercial silicon source, can also be with one of diatomite, opal or two Kind, silicon source can be conventional commercial silicon source, be also possible to one or more of kaolin, rectorite, perlite, montmorillonite, Zinc source is also possible to one or both of smithsonite, zincite.
SDA described in step (1) is one or more of trimethylamine (TMA), methyl ethylamine, pyrroles, beautiful jade, is also possible to Common tetrapropylammonium hydroxide (TPAOH), 4-propyl bromide (TPABr), 1,6- hexamethylene diamine, n-butylamine, in hexylene glycol One or more of one or more, preferably trimethylamine (TMA), methyl ethylamine, pyrroles, beautiful jade.
Aging temperature described in step (2) is 30-85 DEG C, preferably 40-80 DEG C；Ageing time is 1-24h, preferably 2- 16h。
Crystallization temperature described in step (2) is 120-210 DEG C, preferably 130-185 DEG C；Divide 1-5 sections of temperature programmings, preferably 1-3 sections；Preferably be segmented not isothermal heating, non-isothermal temperature-gradient method processing, heating rate first quick and back slow, before 100 DEG C with The heating rate of 6-8 DEG C/min heats up, and 20-30 DEG C is a warming-up section, and the temperature section processing time is 0.5-5 hours；100- It is heated up between 200 DEG C with the heating rate of 3-5 DEG C/min, 10-20 DEG C is a warming-up section, and temperature section handles the time as 0.5- 8 hours.The present invention is handled using non-isothermal temperature-gradient method, is conducive to nucleation rate and the life of Zn-ZSM-5 Crystallization of Zeolite process Long rate control can control mesoporous size and quantity, and then the activity and purpose product selectivity of catalyst can be improved. Crystallization time is 10-96h, preferably 24-72h.
420-780 DEG C of maturing temperature, preferably 450-650 DEG C described in step (3)；Calcining time 1-8h；Exchange reagent For one of hydrochloric acid, nitric acid, sulfuric acid, ammonium chloride or ammonium nitrate；
The surface modification of molecular sieve described in step (3) uses incipient impregnation zinc compound, wherein the quality of ZnO Score is 0.5-15%, preferably 0.5-10%.
Octane value recovering catalyst of the invention includes Zn-ZSM-5 molecular sieve of the one-step synthesis method skeleton containing Zn, molecular sieve Synthetic method is simple, causes crystal structure to change since Zn enters framework of molecular sieve, and generation is mesoporous, while improving Zn's Dispersibility, this will be such that reactant diffusional resistance reduces, and improve anti-carbon performance.
Zn-ZSM-5 molecular sieve surface Zn content is higher than Zn content inside molecular sieve, surface Zn atom and Al hydroxyl phase interaction With causing strong acid remitted its fury to reduce the acid strength of molecular sieve to middle strong acid, it is secondary anti-to reduce cracking hydrocarbon etc. from the root It should occur, improve the selectivity of double branched chain isomer hydrocarbon.
The present invention provides the production method of a kind of low alkene, ultra-low sulfur and clean gasoline with high octane, and specifically one Kind catalytically cracked gasoline is cut into light, heavy naphtha, light gasoline fraction isomery, heavy naphtha hydrodesulfurization-through pre-add hydrogen Isomery, then carry out the method that the processes such as double branched chain isomers produce low alkene, ultra-low sulfur, clean gasoline with high octane.This hair Bright method further decreases the olefin(e) centent of gasoline and keeps the octane of gasoline while realizing FCC gasoline ultra-deep desulfurization Value, obtains the clean gasoline for meeting six standard of state, to improve the economic benefit of refinery significantly.It molecular sieve of the present invention and urges Agent can be used for five gasoline of catalytically cracked gasoline producing country.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention System.Source chemicals used in the present invention are commercial product.
One, catalyst for pre-hydrogenation is prepared
(1) catalyst for pre-hydrogenation 1 is prepared
1, preparation has micro- mesoporous witch culture cadmium ferrite
Under stirring condition, by 2.2mol La (NO3)3It is dissolved in 100mL water, citric acid stirring and dissolving is added；It adds 4.2mol Fe(NO3)3, 160g Sodium Polyacrylate is then added, the aqueous solution of the ammonium metatungstate containing 10g is added, continues to stir 30min, drying, roasting, grinding obtain micro- mesoporous witch culture cadmium ferrite.
2, alumina support is prepared
It is spare that citric acid is added in the micro- mesoporous witch culture cadmium ferrite of 2.2g, by 300g boehmite powder and the field 20.0g Cyanines powder is added in kneader, and is uniformly mixed, and nitric acid, 8g Sodium Polyacrylate are added, and is mediated uniformly, is then added micro- mesoporous Witch culture cadmium ferrite is uniformly mixed, and is clover shape by kneading-extruded moulding.It is 8 hours dry at 120 DEG C, 700 DEG C of roastings It burns 4 hours, obtains the alumina support 1 containing micro- mesoporous witch culture cadmium ferrite.Carrier pore structure is as shown in table 1.
3, catalyst for pre-hydrogenation 1 is prepared
Alumina support 1 and sesbania powder, acidification of amorphous sial, deionized water are mediated and are stirred, and are answered through drying and roasting Carrier 1-1 is closed, ammonium heptamolybdate and nickel nitrate are added in distilled water, maceration extract is made into and impregnates above-mentioned complex carrier 1-1, obtain Catalyst precursor 140 DEG C drying after, in 500 DEG C of roasting 6h, obtain catalyst 1.Catalyst 1 mainly forms: containing micro- Jie The alumina support of hole witch culture cadmium ferrite be 73.2wt%, alumina content 4.8wt%, silica content 5.2wt%, Nickel oxide content is 7.7wt%, and oxidation molybdenum content is 9.1wt%.
(2) catalyst for pre-hydrogenation 2 is prepared
1, witch culture cadmium ferrite is prepared
Under stirring condition, by 2.2mol La (NO3)3It is dissolved in 100mL water, citric acid stirring and dissolving is added；It adds 4.2mol Fe(NO3)3, the aqueous solution of the ammonium metatungstate containing 10g is added, continues to stir 30min, drying, roasting, grinding obtain Witch culture cadmium ferrite.
2, alumina support is prepared
Citric acid is added in 2.2g witch culture cadmium ferrite, 300g boehmite powder and 20.0g sesbania powder are added to It in kneader, and is uniformly mixed, adds nitric acid, 8g Sodium Polyacrylate, mediate uniformly, witch culture cadmium ferrite is then added, mix It closes uniformly, is clover shape by kneading-extruded moulding.8 hours dry at 120 DEG C, 700 DEG C roast 4 hours, obtain tungstenic The alumina support 2 of doped lanthanum ferrite.Carrier pore structure such as table 1.
3, catalyst for pre-hydrogenation 2 is prepared
With catalyst 1, zsm-5 is introduced in carrier, obtains complex carrier 2-1, compound load will be impregnated containing the maceration extract of molybdenum, cobalt Body 2-1, obtained catalyst precursor, in 530 DEG C of roasting 5h, obtain catalyst 2 after 140 DEG C of drying.2 main groups of catalyst It is 71.5WT% at: the alumina support of tungstenic doped lanthanum ferrite, zsm-5 content 7WT%, molybdenum oxide 10.8wt%, cobalt oxide Compound 10.7wt%.
(3) catalyst for pre-hydrogenation 3 is prepared
The preparation of alumina support 3 containing micro- mesoporous witch culture cadmium ferrite is with catalyst 1, except that micro- mesoporous tungsten is mixed Miscellaneous cadmium ferrite accounts for carrier 6wt%.The preparation of catalyst is silicon source with the montmorillonite after activation with catalyst 1.Except that living Property group be divided into molybdenum, tungsten, catalyst 3 mainly forms: the alumina support containing micro- mesoporous witch culture cadmium ferrite is 75.6wt%, oxidation Aluminium content is 4.0wt%, silica content 4.0wt%, molybdenum oxide 10.1wt%, tungsten oxide 6.3wt%.
(4) catalyst for pre-hydrogenation 4 is prepared
Prepare modified alumina support
2g Sodium Polyacrylate is dissolved in nitric acid, is added 28g silicon powder, is stirred evenly, and silicon powder-Sodium Polyacrylate is obtained Mixture takes 1/10 amount spare, and it is spare that citric acid is added in the micro- mesoporous witch culture cadmium ferrite of 2.0g.By 310g boehmite Powder and 22.0g sesbania powder are added in kneader, and nitric acid is added, and add 28g Sodium Polyacrylate nitric acid solution, and are mixed equal It is even, above-mentioned silicon powder-Sodium Polyacrylate mixture is added, mediates uniformly, micro- mesoporous witch culture cadmium ferrite is then added, is mixed It uniformly, is clover shape by kneading-extruded moulding.7 hours dry at 130 DEG C, 650 DEG C roast 5 hours, obtain micro- mesoporous The alumina support 4 of witch culture cadmium ferrite and silica.
The preparation of catalyst is with catalyst 2, except that active component is tungsten, nickel, molybdenum, catalyst 4 is mainly formed: containing The alumina support of micro- mesoporous witch culture cadmium ferrite is 71.7wt%, zsm-5 content 5WT%, tungsten oxide 7.8wt%, nickel oxygen Compound 3.2wt%, molybdenum oxide 12.3wt%.
(5) catalyst for pre-hydrogenation 5 is prepared
Under stirring condition, by 2.0mol La (NO3)3It is dissolved in 100mL water, citric acid stirring and dissolving is added；It adds 4.0mol Fe(NO3)3, the aqueous solution of the ammonium metatungstate containing 12g is added, continues to stir 30min, drying, roasting, grinding obtain Witch culture cadmium ferrite.
The preparation of the alumina support 5 of tungstenic doped lanthanum ferrite is with catalyst 4, except that witch culture cadmium ferrite accounts for load Body 3wt%, with after activation diatomite and kaolin be silicon source silicon source.Catalyst 5 mainly forms: tungstenic doped lanthanum ferrite and oxygen The alumina support of SiClx is 74.0wt%, zsm-5 content 4WT%, molybdenum oxide 12.9wt%, tungsten oxide 9.1wt%.
(6) catalyst for pre-hydrogenation 6 is prepared
Catalyst preparation with catalyst 4, difference be catalyst in modenite is added, catalyst 6 mainly forms: containing 4 content 80.1wt% of alumina support, the modenite content 6.8wt% of micro- mesoporous witch culture cadmium ferrite and silica, molybdenum oxygen Compound 10.4wt%, tungsten oxide 2.7wt%.With after activation diatomite and kaolin be silicon source silicon source.
(7) catalyst for pre-hydrogenation 7 is prepared
Catalyst preparation with catalyst 6, difference be catalyst in beta molecular sieve is added, catalyst 7 mainly forms: 4 content 72.8wt%, beta molecular sieve content 6.7wt% of alumina support containing micro- mesoporous witch culture cadmium ferrite and silica, Molybdenum oxide 10.4wt%, nickel oxide 10.1wt%.With after activation diatomite and kaolin be silicon source silicon source.
(8) pre-add hydrogen comparative catalyst 1 is prepared
Carrier is prepared with catalyst 4, and what is be only added is cadmium ferrite, and with catalyst 4, reaction condition is same for the preparation of catalyst Catalyst 4, reaction result is shown in Table 2.
Two, hydrodesulfurization-heterogeneous catalyst is prepared
(1) hydrodesulfurization-heterogeneous catalyst 1 is prepared
Using the carrier of catalyst for pre-hydrogenation 1 as carrier, P-Mo-Wo acid is impregnated, obtained catalyst precursor is dried at 140 DEG C After dry, in 600 DEG C of roasting 7h, hydrodesulfurization-heterogeneous catalyst 1 is obtained.Catalyst 1 mainly forms: containing micro- mesoporous witch culture iron The alumina support of sour lanthanum is 90.2wt%, phosphorus molybdenum tungsten oxide 9.8wt%.
(2) hydrodesulfurization-heterogeneous catalyst 2 is prepared
Using the carrier of catalyst for pre-hydrogenation 3 as carrier, phosphomolybdic acid is impregnated, obtained catalyst precursor is dried at 140 DEG C Afterwards, in 630 DEG C of roasting 5h, catalyst 2 is obtained.Hydrodesulfurization-heterogeneous catalyst 2 mainly forms: the oxygen of tungstenic doped lanthanum ferrite Change alumina supporter is 85.2WT%, phosphorus molybdenum oxide 14.8wt%.
(3) hydrodesulfurization-heterogeneous catalyst 3 is prepared
Using the carrier of catalyst for pre-hydrogenation 4 as carrier, impregnates phosphotungstic acid and ammonium molybdate (aoxidizes weight of molybdenum and accounts for catalyst 4.1%), catalyst 4 mainly forms: the alumina support containing micro- mesoporous witch culture cadmium ferrite is 88.9wt%, phosphorus tungsten oxide 7.0wt%.
(4) hydrodesulfurization-heterogeneous catalyst 4 is prepared
Using the carrier of catalyst for pre-hydrogenation 4 and modenite as carrier, dipping dipping P-Mo-Wo acid and cobalt nitrate (cobalt oxide Weight accounts for catalyst 3.6%), with after activation diatomite and kaolin be silicon source silicon source.Catalyst 4 mainly forms: tungstenic is mixed The alumina support of miscellaneous cadmium ferrite and silica is 86.8wt%, phosphorus molybdenum tungsten oxide 9.6wt%.
Three, light gasoline fraction heterogeneous catalyst is prepared
(1) light gasoline fraction heterogeneous catalyst 1 is prepared
Alumina composite carrier with macroporous structure and SAPO-11 molecular sieve in catalyst for pre-hydrogenation 1 are in mass ratio The proportion of 85:15 is mixed with sesbania powder, obtains carrier through kneading, molding, drying, roasting, then load quality percentage composition is 12% active component Mo, 6%Co and 9%Ni.
(2) light gasoline fraction heterogeneous catalyst 2 is prepared
Alumina composite carrier with macroporous structure and SAPO-11 molecular sieve in catalyst for pre-hydrogenation 4 are in mass ratio The proportion of 80:20 is mixed with sesbania powder, obtains carrier through kneading, molding, drying, roasting, then load quality percentage composition is 15% active component Mo, 5%Co and 9%Ni.
Four, octane value recovering catalyst is prepared
1, mesoporous Zn-ZSM-5 molecular sieve is prepared
(1) it weighs 0.44g NaAlO2 and 2.14g Zn (NO3) 26H2O to be dissolved in 49.55g deionized water, then drip Add 2.00g sulfuric acid (3mol/L), 0.93g TMA is added after stirring 5min, addition 14.20g waterglass (contains after stirring 1h The H2O of the Na2O and 65.3wt% of the SiO2 of 27.6wt%, 7.1wt%), 2h is mixed at room temperature, mixture rubs You become 0.003Al2O3:0.25Na2O:1SiO2:50H2O:0.24SDA:0.11ZnO at group.
(2) mixture that step (1) obtains is warming up to 75 DEG C of aging 6h, then poured this solution into band polytetrafluoroethylene (PTFE) In the stainless steel crystallizing kettle of lining, 130 DEG C of crystallization 12h are warming up to, then heat to 180 DEG C of static crystallization for 24 hours.After crystallization, Cooling is filtered to remove mother liquor, and washing to neutrality is dry at 120 DEG C, obtains crystallization product Zn-ZSM-5 molecular sieve.
It (3) is that 1:10 is added to concentration and is in the ammonium chloride solution of 1mol/L according to solid-to-liquid ratio by Zn-ZSM-5 molecular sieve, 4h is mixed at 60 DEG C, filters, drying in kind exchanges once again, is put into Muffle furnace the high temperature at 550 DEG C and roasts It burns 6h and obtains H-type Zn-ZSM-5 molecular sieve, the ZnO that then impregnating effect score is 5% again.
2, Ni-Mo/Zn-ZSM-5-Y molecular sieve catalyst is prepared
By the above-mentioned Zn-ZSM-5 molecular sieve and 11gY molecular sieve handled well of 30g, it is uniformly mixed with 30g deionized water, so Extruded moulding afterwards, dry 4h, 550 DEG C of roasting 5h obtain molecular sieve carrier at 120 DEG C, are then impregnated using multiple maceration Ni-Mo/Zn-ZSM-5 catalyst is made in the MoO3 of the NiO and 6.0wt% of 7.0wt%.
The alumina support specific surface area and pore-size distribution of 1 macropore of table
2 catalyst pre-hydrotreating reaction result of table
FCC gasoline is handled under the action of catalyst for pre-hydrogenation by pre-hydrogenator, removes alkadienes and sulphur Alcohol, thioether, while double-bond isomerism (i.e. terminal olefine is converted into internal olefin), and remaining alkadienes is saturated.Reaction temperature is 115 DEG C, reaction pressure 1.8MPa, liquid volume air speed is 5h-1, hydrogen to oil volume ratio 4:1, reaction result is shown in Table 2.Pre-add hydrogen is urged 2,3,4,7 reaction effluent of agent is cut into weight gasoline fraction under the conditions of 42 DEG C, and light gasoline fraction is in heterogeneous catalyst Effect is lower to occur isomerization reaction, and catalyst for pre-hydrogenation 2,3 carries out isomerization reaction, pre-add hydrogen with light gasoline fraction heterogeneous catalyst 1 Catalyst 4,7 carries out isomerization reaction with light gasoline fraction heterogeneous catalyst 2.240 DEG C of reaction temperature, reaction pressure 1.2MPa, sky Fast 0.5h-1, isopentane increment is 10% or more.Heavy naphtha is selected under hydrodesulfurization-heterogeneous catalyst 1-4 effect Property hydrodesulfurization, while linear alkene tautomerizes to single branched-chain alkene or single branched paraffin, reaction process condition are as follows: temperature of reactor 255 DEG C, reaction pressure 1.6MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio 260.Sampling analysis after reaction about 100h, as a result such as Shown in table 3.2,3,4 reaction effluent of catalyst enters back into octane value recovering unit, under the action of octane value recovering catalyst It carries out double branched chain isomers to react, 365 DEG C of reaction temperature, reaction pressure 1.6MPa, air speed 0.8h-1, hydrogen to oil volume ratio 270:1.Instead 4.6% or more Ying Houshuan branched paraffin increment, light, heavy naphtha obtains sulfur content after reconciling be respectively 6mg/kg, 5mg/kg, 8mg/kg, olefin(e) centent are respectively 11v%, 13v%, 10v%；Loss of octane number is respectively 0.3,0.3,0.2 clean gasoline, Meet six standard of state.
As shown in Table 2, catalyst for pre-hydrogenation 1-7 loss of octane number is low, and yield of gasoline is high, and Mercaptan removal rate is high, and activity is good, Catalyst can effectively inhibit the side reactions such as olefinic polymerization, overcracking to occur, and inhibit the cracking reaction of low-carbon hydro carbons, and gasoline is received Rate is high, is conducive to device long-term operation；The carrier surface of catalyst produces more active sites load centres, effectively improves Catalyst removal alkadienes and mercaptan, thioether, double-bond isomerism activity, catalyst have good activity and selectivity.Reaction fortune Row 600h, the product Mercaptan removal rate of catalyst for pre-hydrogenation 4 and 7 be 98.2%, 98.6%, loss of octane number be 0.2 unit, 0.3 unit, carbon deposition rate 0.3,0.2, liquid yield 99.6%, 99.0%.Internal olefin increment 0.37%, 0.42%, alkadienes Content removal efficiency 100%, 98.2%, catalyst reaction performance are stablized.Hydrodesulfurization-heterogeneous catalyst 1-4 desulfurization degree is high, activity Good, catalyst can effectively inhibit the side reactions such as olefinic polymerization, overcracking to occur, and the recracking for reducing low-carbon isohydrocarbon is anti- It answers, the carrier surface of catalyst produces more active sites load centres, effectively improves catalyst desulfurizing-heterogeneous activity, urges Agent has good hydrodesulfurization-heterogeneous activity and selectivity.
3 catalyst HDSs of table-isomerization reaction result
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art It all should belong to protection scope of the present invention.

Claims (11)

1. a kind of FCC gasoline method for modifying, it is characterised in that: it includes the following steps: that FCC gasoline is acted in catalyst for pre-hydrogenation Under, by pre-hydrogenator, mercaptan etherificate, double-bond isomerism reaction are carried out, pre-hydrotreating reaction effluent is cut into light, heavy petrol Isomerization reaction occurs under the action of heterogeneous catalyst for fraction, light gasoline fraction, and heavy naphtha is in hydrodesulfurization-isocatalysis Agent effect is lower to carry out selective hydrodesulfurization, while linear alkene tautomerizes to single branched-chain alkene or single branched paraffin；After reaction Heavy naphtha enters back into octane value recovering unit, contacts with octane value recovering catalyst, carries out double branched chain isomer reactions；Finally Gently, heavy naphtha reconciles to obtain clean gasoline；
In the octane value recovering unit octane value recovering catalyst by weight percentage, including the mesoporous H of 32-88% faintly acid Type Zn-ZSM-5 molecular sieve or the mesoporous H-type Zn-ZSM-5 molecular sieve of improved faintly acid, 0-66% boehmite, macropore oxidation Aluminium or zinc-aluminum hydrotalcite binder impregnate 0.5-16% metal active constituent as carrier, metal active constituent Fe, Co, Ni, One or more of Mo and W；
The preparation method of the mesoporous H-type Zn-ZSM-5 molecular sieve of improved faintly acid, includes the following steps:
(1) at a certain temperature, deionized water, silicon source, zinc source, acid source, template and silicon source are mixed under agitation Even to be prepared into gel, adjusting molar ratio of material is (0.003-0.07) Al2O3:(0.03-0.3)Na2O:1SiO2:(8-45)H2O: (0.05-0.2)SDA:(0.001-0.15)ZnO；
(2) it will be transferred in the stainless steel cauldron containing polytetrafluoroethyllining lining and seal after the gel aging obtained in step (1) Crystallization, to crystallization after, crystallization product is cooling, be filtered to remove mother liquor, filter cake is washed with deionized to neutrality, dry To Zn-ZSM-5 molecular sieve；
(3) Zn-ZSM-5 molecular sieve obtained in step (2) is obtained into H-type Zn- through exchange, filtering, drying, calcination process ZSM-5 molecular sieve；
(4) it impregnates zinc compound again on the surface of H-type Zn-ZSM-5 molecular sieve to be modified, so that molecular sieve surface Zn content It is higher than Zn content inside molecular sieve, obtain the mesoporous H-type Zn-ZSM-5 molecular sieve of improved faintly acid.
2. the method for modifying of FCC gasoline according to claim 1, it is characterised in that: the catalyst for pre-hydrogenation includes carrier And active component, carrier include that there is 75~95wt% the alumina composite carrier of macroporous structure and 5~25wt% to be selected from ZSM- 5, ZSM-11, ZSM-12, ZSM-35, modenite, amorphous silicon aluminium, SAPO-11, MCM-22, Y molecular sieve or beta molecular sieve One or more of, wherein including the witch culture ferrous acid of 0.1~12wt% in the alumina composite carrier with macroporous structure Lanthanum, the 1~85% of the total hole the mesoporous Zhan of alumina composite carrier, the 1~70% of the total hole alumina composite carrier macropore Zhan, carrier table Face load active component cobalt, molybdenum, nickel, one or more of tungsten remember that active component content is 0.1~15.5% with oxide.
3. the method for modifying of FCC gasoline according to claim 2, it is characterised in that: the aluminium oxide with macroporous structure Complex carrier include 0.1~12WT% silica, the witch culture cadmium ferrite of 0.1~10WT%, the mesoporous total hole Zhan 1~ The 1~40% of the total hole 80%, macropore Zhan, micropore, mesoporous, macropore uneven distribution in carrier.
4. the method for modifying of FCC gasoline according to claim 2, it is characterised in that: the pre-hydrotreating reaction condition is as follows: anti- 80-160 DEG C of temperature, reaction pressure 1-5MPa is answered, liquid volume air speed 1-10h-1, hydrogen to oil volume ratio 3-8:1.
5. the method for modifying of FCC gasoline according to claim 3, it is characterised in that: the aluminium oxide with macroporous structure The preparation method of complex carrier, which includes the following steps: for silicon source and sesbania powder to be added in kneader, to be uniformly mixed, and is added inorganic Acid or organic acid soln and organic polymer, mediate uniformly, then add witch culture cadmium ferrite, are uniformly mixed and obtain aluminium oxide Presoma is spare；Silicon source is added in the acid solution of organic polymer, after mixing, is mixed with alumina precursor, before aluminium oxide 1.5 times higher than the content of organic polymer in silicon source of organic polymer or more for driving unit content in body through extrusion, molding, are done Dry, roasting, obtains alumina support.
6. according to the method for modifying of any one of the claim 2-5 FCC gasoline, it is characterised in that: the witch culture cadmium ferrite For with micro- mesoporous witch culture cadmium ferrite, preparation method is as follows: citric acid is dissolved in stirring and dissolving in deionized water, then will Lanthanum nitrate and ferric nitrate are added in citric acid, and Sodium Polyacrylate or polyacrylic acid, Sodium Polyacrylate or poly- third is added in stirring and dissolving The additional amount of olefin(e) acid is 0.1~9wt% of witch culture cadmium ferrite, adds Tungstenic compound, is remembered with oxide, tungsten accounts for witch culture 0.1~8wt% of cadmium ferrite, stirring, after reaction, obtains finished product through drying, roasting, grinding.
7. the method for modifying of FCC gasoline according to claim 1, it is characterised in that: the hydrodesulfurization-heterogeneous catalyst packet Including carrier and active component, carrier includes the alumina composite carrier with macroporous structure, and alumina composite carrier contains 0.1~ The witch culture cadmium ferrite of 12wt%, the 1~85% of the total hole the mesoporous Zhan of alumina composite carrier, alumina composite carrier macropore Zhan is total The 1~70% of hole, carrier surface load phosphomolybdic acid, phosphotungstic acid or P-Mo-Wo acid, by weight percentage, phosphorus molybdenum in catalyst Acid, phosphotungstic acid or P-Mo-Wo acid remember that content is 0.1~16.5% with oxide.
8. the method for modifying of FCC gasoline according to claim 1, it is characterised in that: hydrodesulfurization-isomerization reaction process conditions Are as follows: 190-330 DEG C of reaction temperature, reaction pressure 1.2-3.5MPa, volume space velocity 2.5-5h-1, hydrogen to oil volume ratio 160-460:1.
9. the method for modifying of FCC gasoline according to claim 1, which is characterized in that the pre-hydrotreating reaction effluent cutting Temperature is 50-70 DEG C.
10. the method for modifying of FCC gasoline according to claim 1, it is characterised in that: light gasoline fraction heterogeneous catalyst is with pre- Hydrogenation catalyst has the alumina composite carrier of macroporous structure and matching for SAPO-11 molecular sieve 80-90:10-20 in mass ratio It is carrier than obtained composite material, load quality percentage composition is active component Mo, Co and Ni of 5-18% and is made.
11. the method for modifying of FCC gasoline according to claim 1, it is characterised in that: branch during the octane value recovering unit is double The condition of chain isomerism reaction are as follows: 180-450 DEG C of reaction temperature, reaction pressure 0.6-4.8MPa, air speed 0.5-8h-1, hydrogen oil volume Compare 50-450:1.
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