CN106867577B - A kind of method for gasoline desulfurization - Google Patents

A kind of method for gasoline desulfurization Download PDF

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CN106867577B
CN106867577B CN201710158467.2A CN201710158467A CN106867577B CN 106867577 B CN106867577 B CN 106867577B CN 201710158467 A CN201710158467 A CN 201710158467A CN 106867577 B CN106867577 B CN 106867577B
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zinc oxide
zinc
catalyst
alumina
complex carrier
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CN106867577A (en
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晁会霞
贾贞健
罗祥生
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Qinzhou University
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Qinzhou University
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of method for gasoline desulfurization, and using fixed bed reactors, catalyst is load-type nickel cobaltmolybdate catalyst, and the carrier of catalyst is the complex carrier of the aluminium oxide containing zinc oxide.Gasoline hydrodesulfurizationmethod process conditions are gentle, adaptable to different material, and loss of octane number is low, and desulfurization degree is high, are adapted to high sulfur content, the deep desulfuration of high olefin content gasoline.

Description

A kind of method for gasoline desulfurization
Technical field
The invention belongs to hydrodesulfurization technical field, more specifically using one kind with containing zinc oxide-alumina composite material The FCC gasoline Hydrobon catalyst for carrier is expected, for FCC gasoline selective hydrodesulfurization.
Background technology
With the continuous enhancing of people's environmental consciousness, in vehicle exhaust the discharge of poisonous and harmful substance will strictly be controlled System, thus it is more and more tighter as the oil quality requirement of engine fuel.Various countries are to motor petrol specification such as oxygen content, steaming for this Vapour pressure, benzene content, aromatic hydrocarbons total content, boiling point, olefin(e) centent and sulfur content etc. are proposed extremely harsh limitation index, with drop The discharge of low harmful substance.More than 80% it is at present FCC gasoline in China's gasoline product, since the general sulfur content of FCC gasoline exists 100-500v%, or even also high-sulfur, high olefin feedstock oil, sulfur content is in more than 500mg/kg, and olefin(e) centent is also above 40%. Have the characteristics that content of olefin in gasoline is high, arene content is low (being less than 20v%).Selective hydrodesulfurization technology adds in progress depth Hydrocarbon fraction saturation is inevitably caused during hydrogen desulfurization and reduces octane number, this requires Hydrobon catalyst desulfurization Avoid loss of octane number excessive as far as possible at the same time.
In existing Hydrobon catalyst, ZnO/A12O3It is its main active component, ZnO is in hydro-thermal spinel-type Composite oxides are a kind of up-and-coming inorganic non-metallic materials, and the composite material of zinc oxide and aluminium oxide is urged frequently as desulfurization Change material to be used to adsorb desulfurization and hydrodesulfurization field.It is mixed that the common preparation method of the domestic and international material includes infusion process, machinery Legal, coprecipitation and peptisation.Wherein, since infusion process and mechanical mixing use alumina material to lead to as predecessor The specific surface area of adjustment alumina material is crossed, both approaches can prepare the composite material of high specific surface area, but due to Aluminium oxide and zinc oxide interaction in composite material is weaker, and the loss of zinc oxide is easily produced during use, is typically The two is promoted to form spinelle using the method for high-temperature roasting to avoid the loss of zinc oxide；And coprecipitation and peptisation use Compound containing aluminum and zinc prepares zinc-aluminium precursor by precipitation or peptization, aluminum and zinc in preparation process by react produce compared with Strong interaction can be lost in avoid the zinc oxide during use, but the specific surface area that peptisation prepares material is minimum, It is set to be restricted when being used as catalysis material.
CN200710045746.4 discloses a kind of assistant for calalytic cracking for reducing content of sulfur in gasoline, which includes zinc Aluminate and the composite oxides of dispersed zinc oxide and optionally at least one rare earth metal oxide, by Zinc-aluminium bedded substance and the mixture of optional rare earth hydrous oxide with hydrotalcite-like compound are fired and obtained, chemistry Formula is ZnAl2O4·(1-9)ZnO·(0-0.5)RE2O3；Its preparation method is by sodium hydroxide and the dropwise addition of soluble inorganic sodium salt Into the mixed solution of zinc salt, aluminium salt and rare earth ion, the pH value of solution is 8-11, and 1-4h is roasted at 500-1000 DEG C.This is helped Blend and be applied in catalytic cracking process with conventional FCC catalyst and/or active enhanced aid after agent shaping, having reduces gasoline Sulfur content function simultaneously has excellent hydrothermal stability.To obtain gahnite structure, which needs to roast in higher temperature Burn, specific surface area is up to 120m after roasting2/g。
CN201210178395.5 (CN103449503A) discloses a kind of preparation method of nano zinc aluminum spinelle, it is made Preparation Method is that zinc salt is added to the water dissolving, adds silicon source, is stirred 10-30 minutes, adds expanding agent, stirring, at 20-100 DEG C Aging 30-60 minutes, dry, 500-1200 DEG C of roasting；Feed molar proportioning is Zn：Al：Water=1：2：16-35；With zinc oxide Quality for 100% calculate, the addition of expanding agent is 0.5-30%；Expanding agent is sucrose, glycerine, ammonium carbonate, bicarbonate One or more in ammonium, polystyrene emulsion, polyethylene glycol.The specific surface area of synthesized gahnite from 60 to 300m2/g.The zinc-aluminium proportioning that this method feeds intake is relatively low and preparation process adds expanding agent, only obtains gahnite, does not wrap Containing dispersed zinc oxide.CN201310625314.6 (CN103691441) discloses a kind of strong absorption, high visible degraded The preparation method of performance catalysis material, it is presoma which, which is related to one kind with ternary houghite, is obtained by high-temperature roasting High-specific-surface mesoporous structure gahnite and zinc oxide, nickel oxide nano composite photocatalyst material and preparation method thereof, The material is used for absorption and degraded to organic pollution.The invention utilizes zinc nitrate, nickel nitrate, aluminum nitrate, sodium carbonate and hydrogen It is raw material that oxidation, which is received etc., is configured to salting liquid and aqueous slkali respectively, under 80 DEG C simultaneously magnetic agitation, is mixed with constant flow pump； Reaction mixture is transferred in hydrothermal reaction kettle, the hydro-thermal process 5-10h at 130-180 DEG C；Before filtering, wash, being drying to obtain Drive body, by forerunner be put into Muffle furnace at 400-600 DEG C roast 2-6 it is small when, up to product, zinc, nickel, aluminium ion molar ratio are 1-3:1-3:1-3, specific surface area are more than 150m2/g.Need to carry out during this method synthesis of ternary houghite presoma Hydro-thermal process, and processing time is longer.
CN200310121344.X discloses a kind of preparation method of the Nano-class zinc oxide conductive powder body of adulterated al.The party Method is by the soluble-salt of zinc and doped chemical aluminium, gallium, indium, yttrium, scandium, tin, germanium, the mixing salt solution of soluble-salt of silicon and heavy Shallow lake agent is added drop-wise in water at the same time, is produced altogether under conditions of 40-75 DEG C of the temperature of whole reaction system and pH value 7.0-7.5 is controlled The zinc oxide precursor basic zinc carbonate of precipitation generation doping, by the roasting under the mixed atmosphere of hydrogen and argon gas, is made The super fine zinc oxide conductive powder material of doping is obtained, but material prepared by this method is be applied to conductive material, is adulterated The addition mole of element is only the 0.1-10% of zinc and doped chemical integral molar quantity.
CN200510028233.3 discloses a kind of preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas, this method with Zinc, magnesium and aluminium are active component, using cerium and vanadium as auxiliary agent, under the conditions of 60-80 DEG C, pH value 8-10, by zinc salt, magnesium salts, aluminium salt It is added drop-wise to the mixed solution of cerium salt in the mixed solution of sodium hydroxide and sodium carbonate, obtained coprecipitated product is in 400-600 DEG C roasting 6-8h, prepares zinc mangnesium-aluminium-cerium houghite, zinc, magnesium, the molar ratio of three kinds of metals of aluminium are 1.0 by coprecipitation: 1.0-4.5:1.0-2.0, the sulfur transfer additive prepared using the material have efficient SOx absorption and desorption performance and good machine Tool intensity.
CN200910087590.5 discloses a kind of desulfurizing agent for reforming stock oil and preparation method thereof, method for preparing catalyst It is related to blending method, eutectic method and coprecipitation, it is characterised in that its weight, which forms, is：ZnO：10%-40%, NiO：15%- 22%th, Al2O3：10%-17%, SiO2：5%-22%, surplus are the impurity that can not exempt from.
CN201310089762.9 (CN 103159238) disclose a kind of nano-scale stratiform complex hydroxide and its Fractional precipitation preparation method, be soluble-salt and the alkali for using metal for raw material, by fractional precipitation reaction make composition LDH laminates Metal ion precipitate respectively, and LDH is produced in second step precipitation process, specific surface area 140-280m2/g.Relative to altogether The precipitation method, although which employs precipitates twice, but the LDH material specific surface areas prepared are higher, but the invention is reacted Time is longer, the reaction time provided in embodiment when 10 is small more than.The purpose of the invention is that the stratiform for preparing Gao Bibiao is answered Hydroxide (LDH) is closed, the layered double hydroxide structural formula is complicated, may relate to various metals or its combination, prepares Process needs two steps to precipitate respectively, and the reaction time is longer.《Reduce the conjunction of research-gahnite of FCC gasoline sulfur content auxiliary agent Into and its cracking desulfurization performance》(author：Wang Peng；Sinopec Group,《Petroleum journal (PETROLEUM PROCESSING)》 2 phases of volume 19 in 2003)：A kind of preparation method of gahnite is disclosed：Sodium aluminate solution and zinc nitrate solution are pressed into m (Al2O3The ratio of)/m (ZnO)=9, is added drop-wise in 40 DEG C of distilled water with identical speed, added after mixing respectively 16% sodium hydroxide solution, the pH value for adjusting solution is 8.6, and the sediment of generation adds a small amount of hydrogen after aging 15min Sodium hydroxide solution, it is 9.0 to adjust pH value.Sediment is filtered through the repetition of more than 3 times, washing, to remove Na+.Finally will precipitation Thing dry 4h at 120 DEG C, 2h is roasted at 700 DEG C.The specific surface area of sample is substantially all in 160m2/ g or so.
The main purpose of gasoline hydrogenation modifying method is exactly Olefin decrease desulfurization, and octane number is not lost.US6482314 and US7182918 discloses a kind of method using absorption desulfurization and handles full cut FCC gasoline.The main chemical reactions of this method are de- Reaction of Salmon-Saxl.Therefore, the product of generation is compared with raw material, and in addition to sulfur content is greatly reduced, density, boiling range and other properties are substantially not Become；Alkene is slightly reduced；Alkane is increased slightly；(RON+MON)/2 loss is less than 1.0 units.But this method cannot be significantly The olefin(e) centent in gasoline products is reduced, for the higher FCC gasoline of olefin(e) centent, can not solve the problems, such as alkene.US5411658 Disclosed gasoline modifying method is first then to be used after FCC gasoline hydrofinishing using traditional Hydrobon catalyst and contain β Zeolite catalyst carries out octane value recovering to the reaction effluent of hydrofinishing.But the raw material end point of distillation is inclined used in this method Height, hydrofinishing section reaction temperature is excessive to make aromatic hydrocarbons and alkene saturation more, causes research octane number (RON) (RON) loss larger, It is difficult to effectively recover.Gasoline modifying method is disclosed in US5399258, and first segment is satisfied by hydrogenation desulfurization and denitrogenation, hydrogenation of olefins With it is rear, obtained intermediate product be directly entered second segment carry out octane value recovering reaction.The reaction temperature of first segment is higher, with Two sections of reaction temperature maintains an equal level.Since the reaction temperature of first segment is excessive, final product is caused to produce a large amount of mercaptan sulfurs, temperature is got over Height, the mercaptan sulfur of generation are more.The method of deep desulfurization olefin hydrocarbon reduction of gasoline disclosed in CN1465666A is to cut gasoline stocks For light, heavy distillat, light fraction is urged with Hydrobon catalyst, octane value recovering successively through alkali refining removal of mercaptans, heavy distillat, hydrogen Agent contacts, and light, the heavy distillat after desulfurization are mixed to get gasoline products.This method can produce sulfur content and be less than 200 μ g/g, Alkene is less than the gasoline products of 20v%.But this method is low there are liquid yield, spent lye processing the problems such as. CN201310461917.7 discloses a kind of desulphurization catalyst, on the basis of the gross weight of the desulphurization catalyst, the desulfurization catalyst Agent contains the laminated clay column of 5-30 weight %, the aluminium oxide of 5-30 weight %, the zinc oxide of 30-70 weight %, 2-15 weight % Lead oxide, 1-20 weight % the molecular sieve with BEA structures and/or the molecular sieve with FAU structures and 5-30 weight Measure the active metal of %；And zinc lead of at least partly described lead oxide to be represented with zinc oxide formation general formula PbxZn1-xO The form of solid solution exists, and wherein x meets that 0 ＜ x≤0.12, x represents atomic molar ratio；The active metal for cobalt, nickel, iron and At least one of manganese.Present invention also offers a kind of method of the preparation method and desulfurization of hydrocarbon oil of desulphurization catalyst.The present invention The desulphurization catalyst of offer has more preferable desulphurizing activated and activity stability.It is deep that CN200810010248.0 discloses a kind of gasoline The method of desulfurating and reducing olefinic hydrocarbon is spent, gasoline stocks and hydrogen are contacted with hydrogenation absorbing desulfurization catalyst, alkene aromatized catalyst, Remove the sulphur in gasoline and reduce the olefin(e) centent of product.The method of the present invention can produce gasoline of the sulfur content less than 50 μ g/g and produce Product, can further produce the gasoline products that sulfur content is less than 10 μ g/g, and olefin(e) centent is less than 20v%, while ensure anti- Quick-fried figure penalties very little.The method of the present invention can be used for FCC gasoline, catalytic cracking gasoline, coker gasoline, drippolene, hot tearing Change the deep desulfurization olefin hydrocarbon reduction process of gasoline or above-mentioned blend gasoline raw material.
The content of the invention
The present invention provides a kind of method for gasoline desulfurization, and gasoline products are produced for FCC gasoline hydrodesulfurization.Hydrogenation Desulfurization process conditions are gentle, adaptable to different material, and loss of octane number is low, and desulfurization degree is high, are adapted to high sulfur content, alkene Content deep desulfurization of gasoline.
A kind of method for gasoline desulfurization of the present invention, includes the following steps：
Using fixed bed reactors, presulfurization is carried out to catalyst with sulfurized oil, presulfurization after treatment, is switched to complete Cut FCC gasoline replacement Treatment；
After treating pre-vulcanization process, reaction process condition is adjusted to, carries out FCC gasoline reaction；
The catalyst is support type nickel-cobalt-molybdenum catalyst, and the carrier of catalyst is to contain zinc oxide-alumina Complex carrier, the composition of catalyst is with oxidation material gauge, including following component：Active component nickel oxide 0.5-6wt%, oxygen Change cobalt 0.3-5.5wt%, molybdenum oxide 6-12wt%, the complex carrier 75-92wt% containing zinc oxide-alumina；
The preparation method of the catalyst, includes the following steps：
The soluble-salt of nickeliferous, cobalt and molybdenum is made into maceration extract, impregnates the complex carrier containing zinc oxide-alumina, it is dry, Roasting obtains catalyst；The complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, oxidation Aluminium, adjuvant component phosphorus, potassium and magnesium, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 6.0-38.0wt%, alumina content 60.0-85.0wt%, the content of adjuvant component phosphorus, potassium and magnesium account for the hundred of carrier quality Point content is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, complex carrier specific surface area 200-300m2/g；
The complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure obtain：
Soluble salt solutions containing aluminium and zinc-containing solution are alternately titrated by non-constant pH, are prepared containing gahnite Zinc oxide stratified material；Zinc oxide containing gahnite and boehmite are uniformly mixed, add sesbania powder, nitric acid The acid solution containing Sodium Polyacrylate after acidification, and the aqueous solution of phosphoric acid, potassium nitrate and magnesium nitrate, kneading, after shaping, Drying process, calcination process obtain containing zinc oxide-alumina composite carrier.
Fixed bed reactors of the present invention, are fixed bed adiabatic reactor or fixed bed isothermal reactor, preferably solid Fixed bed adiabatic reactor.
The gasoline desulfurization modifying process condition is：180-320 DEG C of reaction temperature, reaction pressure 1.5-2.8MPa, body Product air speed 1.2-3.2h-1, hydrogen to oil volume ratio 150-320:1, preferably 180-280:1.
200-280 DEG C of preferable reaction temperature, reaction pressure 1.8-2.5MPa, volume space velocity 1.5-2.8h-1, hydrogen to oil volume ratio 180-280:1。
Preferably, the catalyst, it is composed of the following components：Complex carrier 80- containing zinc oxide-alumina 90wt%, active component nickel oxide 0.5-6wt%, cobalt oxide 0.5-4.5wt%, molybdenum oxide 7.0-11.0wt%.
Preferably, the composition of the complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 10.0-35.0wt%, alumina content 65.0-90.0wt%, the content of adjuvant component phosphorus, potassium and magnesium account for the hundred of carrier quality Point content is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, complex carrier specific surface area 200-300m2/g。
Drying of the present invention, roasting obtain catalyst, when drying 4-6 is small preferably at 110-150 DEG C, 550-650 Hydrobon catalyst is obtained when roasting 6-8 is small at DEG C.
The zinc oxide stratified material prepared containing gahnite, is preferably prepared by the following preparation method：Will Soluble Zn salting liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, and sodium metaaluminate and sodium carbonate are added in a zinc solution Mixed solution containing aluminium, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；It is further continued for another zinc salt is added dropwise molten Liquid；After zinc solution drips, continue that mixed solution containing aluminium is added dropwise, stop being added dropwise containing aluminium mixing when pH value reaches 8.5-9.5 Solution；It will contain aluminium mixed solution according to the above method and replace titration with zinc solution, until zinc solution is all added dropwise, finally Mixed solution containing aluminium is once added dropwise, when pH value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, control drop Determine process to complete in 1-6h；After 80-95 DEG C of aging 2-8h, cooling washing is to neutrality, in 80-140 DEG C of dry 4-10h, 450-550 DEG C of roasting 4-10h, obtains the dispersed zinc oxide stratified material containing gahnite.
The soluble zinc salt is zinc nitrate or zinc chloride.
The acid solution containing Sodium Polyacrylate after the nitric acid acidification, is preferably prepared by the following preparation method： Deionized water is heated to 30-90 DEG C, then nitric acid is dissolved into deionized water, adds Sodium Polyacrylate, and dissolved Entirely, the acid solution containing Sodium Polyacrylate is obtained.The addition of the Sodium Polyacrylate is preferably the 0.6- of boehmite 12wt%.The Sodium Polyacrylate of acidified processing, zinc oxide, alumina powder mixing are more uniform.
The addition of the sesbania powder is preferably the 0.2-7wt% of boehmite.
The drying process, calcination process, when preferably 110-150 DEG C of drying process 4-8 is small, roasts at 550 DEG C -700 DEG C When burning processing 4.5-8 is small.
The complex carrier containing zinc oxide-alumina obtained using preparation method of the present invention, can also utilize potassium and Magnesium is modified the complex carrier surface containing zinc oxide-alumina, and the concentration of potassium and magnesium is unsuitable excessive, preferably configuration concentration Carrier surface is sprayed less than potassium nitrate when preparing complex carrier and magnesium nitrate aqueous solution, preferably carries out carrier as follows Surface is modified：Configuration sprays the complex carrier containing zinc oxide-alumina containing the aqueous solution of potassium nitrate and magnesium nitrate, through drying, roasting Burn and obtain the zinc oxide-alumina complex carrier of used additives potassium and magnesium progress surface modification, control the compound load of zinc oxide-alumina Potassium oxide and content of magnesia are respectively in the range of 0.2-2.5wt% and 0.2-2.5wt%, and aoxidize carrier surface in body The content of potassium and magnesia is 1.05-1.5 times of external oxidation potassium and content of magnesia.
Compared with prior art, the present invention has the following advantages：
1st, the hydrodesulfurizationprocess process of gasoline of the present invention, reaction condition is gentle, to the adaptable of different material；Make to urge Agent has higher hydrodesulfurization activity and selectivity, and loss of octane number is low, and desulfurization degree is high, and stability is good, is conducive to device Long period steady running, is adapted to high sulfur content, olefin-content gasoline deep desulfuration.
2nd, the zinc oxide containing gahnite of the invention is that alternately prepared by titration by non-constant pH, i.e., in non-constant pH Prepared by the alternating titration of sodium carbonate liquor and zinc-containing solution under the conditions of value, containing aluminium, therefore, it is necessary to zinc-containing solution is divided into number Part, the sodium carbonate liquor containing aluminium is strong alkali solution, and the strong acid weak base salting liquid containing zinc is acid solution, between aluminium zinc solution Repeatedly alternately titration pH value is swung between soda acid, be conducive to aluminium zinc precursor thing can orderly accumulation be layer structure, through straight Connect that low-temperature bake can be uniformly dispersed and specific surface area can be in 150-220m2The point containing zinc-aluminium regulated and controled between/g is brilliant The zinc oxide material of stone, avoiding the precursor obtained using one step of alkaline solution titration zinc-aluminium mixed solution needs high-temperature roasting The problem of fixed zinc oxide, decrease hydrothermal treatment process.The material has larger specific surface area, suitable for being catalyzed material Material, especially suitable for FCC catalyst sulfur prodegradant and hydrodesulfurization carrier material.
3rd, the present invention can also introduce phosphorus, potassium, magnesium and Sodium Polyacrylate in zinc oxide-alumina complex carrier, and poly- third Olefin(e) acid sodium, which can be repaired, improves catalytic inner pore passage structure, and diffusion effect is good in catalyst.The carrier is prepared into hydrodesulfurization Catalyst, such as the catalyst such as cobalt molybdenum or nickel molybdenum, can suppress alkene saturated activity, catalyst desulfurizing rate is high, alkene saturation factor (HYD) it is low, there is good hydrodesulfurization selectivity.
What the 4th, the present invention obtained contains zinc oxide-alumina composite carrier, using potassium and magnesium to being answered containing zinc oxide-alumina Close carrier surface to be modified, and make the content of carrier surface potassium oxide and magnesia be internal oxidation potassium and content of magnesia 1.05-1.5 again.Complex carrier surface is modified by the way of spray, is capable of the portion on effective peptization complex carrier surface Divide micropore, so advantageously reduce the micropore ratio on complex carrier surface, improve complex carrier surface Jie-macropore ratio, promote Complex carrier surface produces more active sites load centres, effectively improves catalyst desulfurizing activity.Carrier surface is changed Into that should not use dipping method, impregnated carrier surface can make large quantity of moisture enter carrier, and intensity is deteriorated, and does not reach raising carrier surface The purpose of Jie-macropore ratio.
5th, through potassium and magnesium-modified effect, the complex carrier containing zinc oxide-alumina can be made carrier surface of the present invention To be used for the hydrodesulfurization of gasoline after the carrier loaded active component of Hydrobon catalyst.
Embodiment
Catalyst of the present invention and its preparation method and application is carried out with comparative example by the following examples further detailed Describe in detail bright.But these embodiments are not regarded as limiting of the invention.
Analysis method and standard：Sulfur content in oil products is analyzed：SH/T 0689-2000
Prepare primary raw material source used in catalyst：Reagent of the present invention is commercial product.
Feedstock oil is FCC gasoline, sulfur content 408mg/kg, RON 93.0, alkene 42.5%vol.
Embodiment 1
1.2kg zinc nitrates are dissolved in 6L water and are made into zinc-containing solution, by 0.24kg sodium metaaluminates and 0.30kg sodium carbonate It is dissolved in 4L water and is made into containing aluminum solutions.Zinc-containing solution is divided into 3 parts, every part of 2L.2L zinc-containing solutions are taken, temperature keeps 80 DEG C, mixed solution containing aluminium to pH value is added dropwise thereto and reaches 9.0；Stop that mixed solution containing aluminium is added dropwise, then 2L zinc-containing solutions are added dropwise Into hybrid system, continue dropwise addition mixed solution containing aluminium to pH value and reach 9.0；Mixed solution containing aluminium and zinc-containing solution alternately drip Fixed, until zinc-containing solution all adds, last time is added dropwise mixed solution containing aluminium and reaches 9.0 to pH, and titration time amounts to 3h. The mixture arrived is after 80 DEG C of aging 4h, cooling washing to neutrality, the dry 3h in 135 DEG C of air atmospheres, in 500 DEG C of roastings 9h, obtains the dispersed zinc oxide stratified material containing gahnite, and in terms of oxide, the content of zinc oxide is 65%； Specific surface area is 196m2/g。
Phosphatase 11 .04g, potassium nitrate 1.03g are weighed respectively, and magnesium nitrate 8.88g, which is dissolved completely in be made into 60g distilled water, to be contained Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65% Acid.Zinc oxide of the 40g containing gahnite and 164.3g boehmite ground and mixeds is uniform, 6.0g sesbania powders are added, Sodium Polyacrylate acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, when 125 DEG C of drying process 7 are small, roasts at 580 DEG C Burning processing 7 obtains the complex carrier containing zinc oxide-alumina when small.Complex carrier specific surface area 276m2/g.Complex carrier includes Zinc oxide 25wt% containing gahnite, aluminium oxide 71.9wt%, adjuvant component phosphorus, potassium, content of magnesium are respectively P2O5 0.4wt%, K2O 1.2wt%, MgO 1.5wt%.
Take 37.7g nickel nitrates, 426.4g ammonium molybdates, 12.5g cobalt nitrates to be added in 40ml distilled water, add ammonium hydroxide and adjust After pH value, then diluted with deionized water, be made into complex carrier of the maceration extract dipping containing zinc oxide-alumina, obtained catalyst Precursor roasts 6h after 120 DEG C of drying at 600 DEG C, obtains catalyst 1.Catalyst 1 mainly forms：Nickel oxide 4.9wt%, oxygen Change cobalt 3.6wt%, molybdenum oxide 10.8wt%, the complex carrier 80.7wt% containing zinc oxide-alumina.
Comparative example 1
Zinc nitrate solution, sodium metaaluminate and the sodium carbonate liquor of amount same as Example 1 are uniformly mixed by blending method, with reality Apply that 1 zinc-aluminium molar ratio of example is identical, and similarity condition aging, washing, drying, roasting obtain the oxide material containing zinc-aluminium.Zinc oxide Content be 65%；Specific surface area is 141m2/g.Compared with comparative example 1, embodiment 1 uses the friendship of pH swing methods zinc, aluminum solutions For titration, zinc-aluminium stratified material can be obtained, in two kinds of material zinc-aluminium molar ratios under the same conditions, embodiment 1 is containing zinc-aluminium point The specific surface area of the zinc oxide stratified material of spar is higher.
Phosphatase 11 .04g, potassium nitrate 1.03g are weighed respectively, and magnesium nitrate 8.88g, which is dissolved completely in be made into 60g distilled water, to be contained Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65% Acid.Oxide materials of the 40g containing zinc-aluminium and 164.3g boehmite ground and mixeds is uniform, 6.0g sesbania powders are added, are gathered Sodium acrylate acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, when 125 DEG C of drying process 7 are small, roasts at 580 DEG C Handle 7 it is small when obtain carrier.Take 37.7g nickel nitrates, 426.4g ammonium molybdates, 12.5g cobalt nitrates to be added in 50ml distilled water, add Enter after ammonium hydroxide adjusts pH value, then diluted with deionized water, be made into maceration extract impregnated carrier, obtained catalyst precursor is 120 DEG C drying after 600 DEG C roast 6h, obtain comparative catalyst 1.
Catalyst 1 and comparative catalyst 1 are respectively charged into 10ml fixed bed reactors, carry out hydrodesulfurization reaction.With Sulfurized oil carries out presulfurization to catalyst, and sulfurized oil is direct steaming gasoline, vulcanizing agent CS2, its concentration is 1.0wt%；Vulcanization pressure Power is 2.7MPa, and hydrogen to oil volume ratio 320, sulfurized oil volume space velocity is 2.5h-1, vulcanization program is respectively at 210 DEG C, 260 DEG C Vulcanizing treatment 7h, then it is switched to full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, it is anti-into FCC gasoline Should.Reaction process condition is：270 DEG C, reaction pressure 1.5MPa, volume space velocity 3.0h of temperature of reactor-1, hydrogen to oil volume ratio 260. Sampling analysis after reaction about 60h, Hydrobon catalyst 1 and 1 product desulfurization degree of comparative catalyst are respectively 81.1% He 73.7%, loss of octane number is respectively 0.4 unit and 2.0 units, and alkene drop amount is respectively 2.7% and 3.1%, and HYD divides Wei 9 and 16.1 loss of octane number of Hydrobon catalyst is very low, and desulfurization degree is high, good catalyst activity.It is not less than in desulfurization degree In the case of 81%, alkene saturation factor (HYD) is only 9% or so, has good hydrodesulfurization selectivity.Reaction operation 400h, Hydrobon catalyst product desulfurization degree are 80.9%, and loss of octane number is 0.4 unit, and alkene drop amount is 2.9%, HYD is 10.The complex carrier surface of catalyst produces more active sites load centres, effectively improves catalyst desulfurizing work Property, catalyst reaction performance is stablized.
Embodiment 2
The preparation method and step of complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1 Zinc oxide, pH value are adjusted to 8.7.In terms of oxide, the content of zinc oxide is 70%；Specific surface area is 191m2/g.Complex carrier Component and content with embodiment 1, except that after obtaining complex carrier, using potassium and magnesium to containing zinc oxide-alumina Complex carrier carries out surface modification, and detailed process includes the following steps：Configuration is containing potassium nitrate and magnesium nitrate aqueous solution as spray Liquid, weighs potassium nitrate 1.2g, magnesium nitrate 10.7g, is dissolved completely in 30ml distilled water respectively, then is diluted with deionized water, spray Drench the complex carrier of zinc oxide-alumina so that the content of carrier outside potassium and magnesium is 1.1 times of the content of internal potassium and magnesium. Used additives potassium is obtained through drying, roasting and magnesium carries out the zinc oxide-alumina complex carrier of surface modification.The complex carrier compares table Area 238m2/g。
Nickel nitrate, ammonium molybdate, cobalt nitrate are made into maceration extract, used additives potassium is impregnated and magnesium carries out the oxidation of surface modification Zinc-alumina composite carrier, specific steps are the same as embodiment 1.When drying 6 is small at 120 DEG C, when roasting 5 is small at 650 DEG C, obtain Hydrobon catalyst 2.Catalyst 2 mainly forms：Nickel oxide 3.2wt%, cobalt oxide 2.7wt%, molybdenum oxide 9.5wt%, is used Auxiliary agent potassium and magnesium carry out the zinc oxide-alumina complex carrier 84.6wt% of surface modification.
Catalyst 2 is fitted into 10ml fixed bed reactors, carries out hydrodesulfurization reaction.Catalyst is carried out with sulfurized oil Presulfurization, sulfurized oil are direct steaming gasoline, vulcanizing agent CS2, its concentration is 1.0wt%；Sulfide stress is 2.7MPa, hydrogen oil volume Than for 320, sulfurized oil volume space velocity is 2.5h-1, vulcanization program is respectively in 210 DEG C, 260 DEG C of vulcanizing treatment 7h, then be switched to Full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, is reacted into FCC gasoline.Reaction process condition is：Instead Answer 270 DEG C, reaction pressure 1.5MPa, volume space velocity 3.0h of device temperature-1, hydrogen to oil volume ratio 260.Sampling analysis after reaction about 60h, Hydrobon catalyst product desulfurization degree is 82.6%, and loss of octane number 1.8 is a unit, and alkene drop amount is for 1.8%, HYD 8.Hydrobon catalyst loss of octane number is very low, and desulfurization degree is high, good catalyst activity.It is not less than 82% situation in desulfurization degree Under, alkene saturation factor (HYD) is only 8% or so, has good hydrodesulfurization selectivity.Reaction operation 400h, hydrodesulfurization Catalyst prod desulfurization degree is 82.5%, and loss of octane number is 0.3 unit, HYD 9.The complex carrier surface production of catalyst More active sites load centres are born, effectively improve catalyst desulfurizing activity, catalyst reaction performance is stablized.
Embodiment 3
The preparation method and step of complex carrier containing zinc oxide-alumina are the same as embodiment 1.Prepare containing gahnite Zinc oxide, pH value are adjusted to 9.3.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 63%；Compare table Area is 214m2/g。
Complex carrier includes the zinc oxide 18.3wt% containing gahnite, aluminium oxide 79wt%, adjuvant component phosphorus, Potassium, content of magnesium are respectively P2O50.9wt%, K2O 0.8wt%, MgO 1.0wt%.Complex carrier specific surface area 242m2/g。
Nickel nitrate, ammonium molybdate, cobalt nitrate are made into maceration extract, impregnate the complex carrier containing zinc oxide-alumina, specific step Suddenly with embodiment 1.When drying 4 is small at 130 DEG C, when roasting 6 is small at 600 DEG C, Hydrobon catalyst 3 is obtained.Catalyst 3 is led Form：Nickel oxide 1.4wt%, cobalt oxide 5.1wt%, molybdenum oxide 8.4wt%, the complex carrier containing zinc oxide-alumina 85.1wt%.
Catalyst 3 is fitted into 10ml fixed bed reactors, carries out hydrodesulfurization reaction.Catalyst is carried out with sulfurized oil Presulfurization, sulfurized oil are direct steaming gasoline, vulcanizing agent CS2, its concentration is 1.0wt%；Sulfide stress is 2.7MPa, hydrogen oil volume Than for 320, sulfurized oil volume space velocity is 2.5h-1, vulcanization program is respectively in 210 DEG C, 260 DEG C of vulcanizing treatment 7h, then be switched to Full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, is reacted into FCC gasoline.Reaction process condition is：Instead Answer 295 DEG C, reaction pressure 2.5MPa, volume space velocity 2.4h of temperature-1, hydrogen to oil volume ratio 270:1.
Sampling analysis after reaction about 60h, Hydrobon catalyst product desulfurization degree are 81.5%, and loss of octane number 0.3 is A unit, alkene drop amount 2.2%, HYD 11.Hydrobon catalyst loss of octane number is very low, and desulfurization degree is high, catalyst activity It is good.In the case where desulfurization degree is not less than 81%, alkene saturation factor (HYD) is only 11% or so, has good hydrodesulfurization Selectivity.
Embodiment 4
The preparation method and step of complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1 Zinc oxide, pH value are adjusted to 8.6.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 75%；Compare table Area is 213m2/g。
Complex carrier includes the zinc oxide 22.9wt% containing gahnite, aluminium oxide 75wt%, adjuvant component phosphorus, Potassium, content of magnesium are respectively P2O51.1wt%, K2O 0.4wt%, MgO 0.6wt%.Complex carrier specific surface area 256m2/g。
Nickel nitrate, ammonium molybdate, cobalt nitrate are made into maceration extract, ammonium hydroxide is added and adjusts pH value and salt is all impregnated after dissolving and contain The complex carrier of zinc oxide-alumina, specific steps are the same as embodiment 1.When drying 5 is small at 120 DEG C, roasting 7 is small at 550 DEG C When, obtain Hydrobon catalyst 4.Catalyst 4 mainly forms：Nickel oxide 2.5wt%, cobalt oxide 4.2wt%, molybdenum oxide 7.9wt%, the complex carrier 85.4wt% containing zinc oxide-alumina.
Catalyst 4 is fitted into 10ml fixed bed reactors, carries out hydrodesulfurization reaction.Catalyst is carried out with sulfurized oil Presulfurization, sulfurized oil are direct steaming gasoline, vulcanizing agent CS2, its concentration is 1.0wt%；Sulfide stress is 2.7MPa, hydrogen oil volume Than for 320, sulfurized oil volume space velocity is 2.5h-1, vulcanization program is respectively in 210 DEG C, 260 DEG C of vulcanizing treatment 7h, then be switched to Full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, is reacted into FCC gasoline.Reaction process condition is：Instead Answer 245 DEG C, reaction pressure 2.0MPa, volume space velocity 1.8h of temperature-1, hydrogen to oil volume ratio 230:1.
Sampling analysis after reaction about 60h, Hydrobon catalyst product desulfurization degree are 80.6%, and loss of octane number 0.3 is A unit, alkene drop amount 2.0%, HYD 10.Hydrobon catalyst loss of octane number is very low, and desulfurization degree is high, catalyst activity It is good.In the case where desulfurization degree is not less than 80.6%, alkene saturation factor (HYD) is only 10% or so, and there is good hydrogenation to take off Sulphur selectivity.
Embodiment 5
The preparation method and step of complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1 Zinc oxide, pH value are adjusted to 8.7.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 67%；Compare table Area is 191m2/g。
Complex carrier includes the zinc oxide 30wt% containing gahnite, aluminium oxide 68wt%, adjuvant component phosphorus, potassium, Content of magnesium is respectively P2O50.6wt%, K2O 1.0wt%, MgO 0.4wt%.Complex carrier specific surface area 279m2/g。
Except that after obtaining complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium Face is modified, and detailed process includes the following steps：Configuration contains potassium nitrate and magnesium nitrate aqueous solution, and spray zinc oxide-alumina is compound Carrier so that the content of carrier outside potassium and magnesium is 1.5 times of the content of internal potassium and magnesium.Used additives are obtained through drying, roasting Potassium and magnesium carry out the zinc oxide-alumina complex carrier of surface modification.
Nickel nitrate, ammonium molybdate, cobalt nitrate are made into maceration extract, used additives potassium is impregnated and magnesium carries out the oxidation of surface modification Zinc-alumina composite carrier, specific steps are the same as embodiment 1.When drying 5 is small at 130 DEG C, when roasting 6 is small at 600 DEG C, obtain Hydrobon catalyst 5.Catalyst 5 mainly forms：Nickel oxide 4.1wt%, cobalt oxide 1.4wt%, molybdenum oxide 11.3wt%, contains The complex carrier 83.2wt% of zinc oxide-alumina.
Catalyst 5 is fitted into 10ml fixed bed reactors, carries out hydrodesulfurization reaction.Catalyst is carried out with sulfurized oil Presulfurization, sulfurized oil are direct steaming gasoline, vulcanizing agent CS2, its concentration is 1.0wt%；Sulfide stress is 2.7MPa, hydrogen oil volume Than for 320, sulfurized oil volume space velocity is 2.5h-1, vulcanization program is respectively in 210 DEG C, 260 DEG C of vulcanizing treatment 7h, then be switched to Full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, is reacted into FCC gasoline.Reaction process condition is：Instead Answer 260 DEG C, reaction pressure 2.2MPa, volume space velocity 2.6h of temperature-1, hydrogen to oil volume ratio 240:1.
Sampling analysis after reaction about 60h, Hydrobon catalyst product desulfurization degree are 84.3%, and loss of octane number 0.3 is A unit, alkene drop amount 1.5%, HYD 9.Hydrobon catalyst loss of octane number is very low, and desulfurization degree is high, catalyst activity It is good.In the case where desulfurization degree is not less than 84.3%, alkene saturation factor (HYD) is only 9% or so, has good hydrodesulfurization Selectivity.Reaction operation 400h, Hydrobon catalyst product desulfurization degree is 84.1%, and loss of octane number is 0.4 unit, alkene Hydrocarbon drop amount is 1.5%, HYD 10.The complex carrier surface of catalyst produces more active sites load centres, effectively improves Catalyst desulfurizing activity, catalyst reaction performance are stablized.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art Protection scope of the present invention should all be belonged to.

Claims (10)

  1. A kind of 1. method for gasoline desulfurization, it is characterised in that include the following steps：
    Using fixed bed reactors, presulfurization is carried out to catalyst with sulfurized oil, presulfurization after treatment, is switched to full cut FCC gasoline replacement Treatment；
    After treating pre-vulcanization process, reaction process condition is adjusted to, carries out FCC gasoline reaction；
    The catalyst is load-type nickel cobaltmolybdate catalyst, and the carrier of catalyst is the complex carrier containing zinc oxide-alumina, The composition of catalyst is with oxidation material gauge, including following component：Active component nickel oxide 0.5-6wt%, cobalt oxide 0.3- 5.5wt%, molybdenum oxide 6-12wt%, the complex carrier 75-92wt% containing zinc oxide-alumina；
    The preparation method of the catalyst, includes the following steps：
    Soluble-salt containing cobalt and molybdenum is made into maceration extract, impregnates the complex carrier containing zinc oxide-alumina, it is dry, roast To catalyst；The complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminium oxide, auxiliary agent Component phosphorus, potassium and magnesium, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite accounts for carrier quality Percentage be 5.0-40.0wt%, alumina content 60.0-95.0wt%, adjuvant component phosphorus, potassium and magnesium contain The percentage composition that amount accounts for carrier quality is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, Complex carrier specific surface area 200-300m2/g；
    The complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure obtain：
    Soluble salt solutions containing aluminium and zinc-containing solution are alternately titrated by non-constant pH, prepare the oxygen containing gahnite Change zinc stratified material；Zinc oxide containing gahnite and boehmite are uniformly mixed, add sesbania powder, nitric acid acidifying The acid solution containing Sodium Polyacrylate after processing, and the aqueous solution of phosphoric acid, potassium nitrate and magnesium nitrate, kneading are dry after shaping Processing, calcination process obtain containing zinc oxide-alumina composite carrier；
    Alternately prepared by titration by the non-constant pH, i.e. the sodium carbonate liquor under non-constant pH value condition, containing aluminium and molten containing zinc It is prepared by the alternating titration of liquid.
  2. A kind of 2. method for gasoline desulfurization according to claim 1, it is characterised in that：The fixed bed reaction Device, is fixed bed adiabatic reactor or fixed bed isothermal reactor.
  3. A kind of 3. method for gasoline desulfurization according to claim 1, it is characterised in that：The FCC gasoline reaction, Its process conditions is：180-320 DEG C of reaction temperature, reaction pressure 1.5-2.8MPa, volume space velocity 1.2-3.2h-1, hydrogen oil volume Compare 150-320:1.
  4. A kind of 4. method for gasoline desulfurization according to claim 3, it is characterised in that：The FCC gasoline reaction, Its process conditions is：200-280 DEG C of reaction temperature, reaction pressure 1.8-2.5MPa, volume space velocity 1.5-2.8h-1, hydrogen oil volume Compare 180-280:1.
  5. A kind of 5. method for gasoline desulfurization according to claim 1, it is characterised in that：
    The catalyst, it is composed of the following components：Active component nickel oxide 0.5-6wt%, cobalt oxide 0.5-4.5wt%, oxygen Change molybdenum 7-11wt%, the complex carrier 75-92wt% containing zinc oxide-alumina；
    The composition of the complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 10.0- 35.0wt%, alumina content 65.0-90.0wt%, the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contain Amount is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, complex carrier specific surface area 200- 300m2/g。
  6. A kind of 6. method for gasoline desulfurization according to claim 1, it is characterised in that：The drying, roasts To catalyst, when being that drying 4-6 is small at 110-150 DEG C, Hydrobon catalyst is obtained when roasting 6-8 is small at 550-650 DEG C； The drying process, calcination process, when being 110-150 DEG C of drying process 4-8 small, calcination process 4.5-8 at 550 DEG C -700 DEG C Hour.
  7. A kind of 7. method for gasoline desulfurization according to claim 1, it is characterised in that：Described prepares containing zinc-aluminium The zinc oxide stratified material of spinelle, is to be prepared by the following preparation method：Soluble Zn salting liquid is divided into 2-4 parts, 40-80 Under the conditions of DEG C, the mixed solution containing aluminium of sodium metaaluminate and sodium carbonate is added in a zinc solution, when pH value reaches 8.5-9.5 When stop be added dropwise mixed solution containing aluminium；It is further continued for that another zinc solution is added dropwise；After zinc solution drips, continue dropwise addition and contain aluminium Mixed solution, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；It will contain aluminium mixed solution and zinc according to the above method Salting liquid alternately titrates, until zinc solution is all added dropwise, mixed solution containing aluminium is added dropwise in last time, when pH value reaches During 8.5-9.5, the alternating titration process of non-constant pH value terminates, and control titration process is completed in 1-6h；In 80-95 DEG C of aging After 2-8h, cooling washing to neutrality, in 80-140 DEG C of dry 4-10h, 450-550 DEG C of roasting 4-10h, obtains dispersed contain The zinc oxide stratified material of gahnite；The soluble zinc salt is zinc nitrate or zinc chloride.
  8. A kind of 8. method for gasoline desulfurization according to claim 1, it is characterised in that：The nitric acid acidification The acid solution containing Sodium Polyacrylate afterwards, is to be prepared by the following preparation method：Deionized water is heated to 30-90 DEG C, then Nitric acid is dissolved into deionized water, adds Sodium Polyacrylate, and is dissolved completely, obtains the acid solution containing Sodium Polyacrylate.
  9. A kind of 9. method for gasoline desulfurization according to claim 1, it is characterised in that：The Sodium Polyacrylate Addition is the 0.6-12wt% of boehmite；The addition of the sesbania powder is the 0.2-7wt% of boehmite.
  10. A kind of 10. method for gasoline desulfurization according to claim 1, it is characterised in that：Described contains zinc oxide-oxygen Change the complex carrier of aluminium, the complex carrier surface containing zinc oxide-alumina is modified using potassium and magnesium, as follows Carry out carrier surface modification：Configuration sprays the complex carrier containing zinc oxide-alumina, warp containing the aqueous solution of potassium nitrate and magnesium nitrate Dry, roasting obtains used additives potassium and magnesium carries out the zinc oxide-alumina complex carrier of surface modification, controls zinc oxide-oxidation Potassium oxide and content of magnesia are respectively in the range of 0.2-2.5wt% and 0.2-2.5wt%, and make carrier in aluminium complex carrier The content of surface oxidation potassium and magnesia is 1.05-1.5 times of internal oxidation potassium and content of magnesia.
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