CN106867577A - A kind of method for gasoline desulfurization - Google Patents

A kind of method for gasoline desulfurization Download PDF

Info

Publication number
CN106867577A
CN106867577A CN201710158467.2A CN201710158467A CN106867577A CN 106867577 A CN106867577 A CN 106867577A CN 201710158467 A CN201710158467 A CN 201710158467A CN 106867577 A CN106867577 A CN 106867577A
Authority
CN
China
Prior art keywords
zinc oxide
catalyst
zinc
alumina
complex carrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710158467.2A
Other languages
Chinese (zh)
Other versions
CN106867577B (en
Inventor
晁会霞
贾贞健
罗祥生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qinzhou University
Original Assignee
Qinzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qinzhou University filed Critical Qinzhou University
Priority to CN201710158467.2A priority Critical patent/CN106867577B/en
Publication of CN106867577A publication Critical patent/CN106867577A/en
Application granted granted Critical
Publication of CN106867577B publication Critical patent/CN106867577B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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, using fixed bed reactors, catalyst is load-type nickel cobaltmolybdate catalyst, and the carrier of catalyst is the complex carrier containing zinc oxide aluminum oxide.Gasoline hydrodesulfurizationmethod process conditions are gentle, and adaptable to different material, 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 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, the discharge of poisonous and harmful substance will be controlled strictly in vehicle exhaust System, thus it is more and more tighter as the oil quality requirement of engine fuel.Be this various countries to motor petrol specification such as oxygen content, steam Vapour pressure, benzene content, aromatic hydrocarbons total content, boiling point, olefin(e) centent and sulfur content etc. are proposed extremely harsh limitation index, to drop The discharge of low harmful substance.More than 80% is FCC gasoline in current China gasoline product, because the general sulfur content of FCC gasoline exists 100-500v%, or even also high-sulfur, olefin feedstock high oil, in more than 500mg/kg, olefin(e) centent is also above 40% for sulfur content. With content of olefin in gasoline is high, arene content low (being less than 20v%) the characteristics of.Selective hydrodesulfurization technology adds carrying out depth Hydrocarbon fraction saturation is inevitably caused during hydrogen desulfurization and octane number is reduced, this requires Hydrobon catalyst desulfurization Avoid loss of octane number excessive as far as possible simultaneously.
In existing Hydrobon catalyst, ZnO/A12O3It is its main active component, ZnO is in hydro-thermal spinel-type Composite oxides are the up-and-coming Inorganic Non-metallic Materials of a class, and the composite of zinc oxide and aluminum oxide is urged frequently as desulfurization Changing material is used to adsorb desulfurization and hydrodesulfurization field.The conventional preparation method of the domestic and international material includes that infusion process, machinery are mixed Legal, coprecipitation and peptisation.Wherein, because infusion process and mechanical mixing use alumina material as predecessor, lead to The specific surface area of adjustment alumina material is crossed, both approaches can prepare the composite of high specific surface area, but due to Aluminum oxide and zinc oxide interaction in composite is weaker, the loss of zinc oxide is easily produced during use, typically The two is promoted to form spinelle to avoid the loss of zinc oxide using the method for high-temperature roasting；And coprecipitation and peptisation are used 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 avoid the zinc oxide during use from being lost in, 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, and the auxiliary agent includes zinc The composite oxides of aluminate and dispersed zinc oxide and optionally at least one rare earth metal oxide, by Zinc-aluminium bedded substance with hydrotalcite-like compound is fired and prepared with the mixture of optional rare earth hydrous oxide, chemistry Formula is ZnAl2O4·(1-9)ZnO·(0-0.5)RE2O3；Its preparation method is that NaOH and soluble inorganic sodium salt are added dropwise To in the mixed solution of zinc salt, aluminium salt and rare earth ion, the pH value of solution is 8-11, and 1-4h is calcined 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, with reduction gasoline Sulfur content function simultaneously has excellent hydrothermal stability.To obtain gahnite structure, the material is needed in higher temperature roasting Burn, specific surface area is 120m to the maximum after roasting2/g。
CN201210178395.5 (CN103449503A) discloses a kind of preparation method of nano zinc aluminum spinelle, its system Preparation Method is that zinc salt is added to the water into dissolving, adds silicon source, is stirred 10-30 minutes, adds expanding agent, stirring, at 20-100 DEG C It is 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 calculate for 100%, 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 the 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, the invention is related to one kind ternary houghite to be presoma, is obtained by high-temperature roasting High-specific-surface mesoporous structure gahnite and zinc oxide, nickel oxide nano composite photocatalyst material for obtaining 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 Oxidation is received and is waited as raw material, and salting liquid and aqueous slkali are configured to respectively, under 80 DEG C simultaneously magnetic agitation, is mixed with constant flow pump； Reaction mixture is transferred in hydrothermal reaction kettle, in hydro-thermal process 5-10h at 130-180 DEG C；Suction filtration, wash, be drying to obtain before Body is driven, forerunner is put into Muffle furnace and is calcined 2-6 hours at 400-600 DEG C, obtain final product product, zinc, nickel, aluminium ion mol ratio are 1-3:1-3:1-3, specific surface area is more than 150m2/g.Need to carry out during the method synthesis of ternary houghite presoma Hydro-thermal process, and process time is more long.
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 the soluble-salt of silicon and heavy Shallow lake agent is added drop-wise in water simultaneously, is produced altogether under conditions of 40-75 DEG C and pH value 7.0-7.5 of temperature for controlling whole reaction system The zinc oxide precursor basic zinc carbonate of precipitation generation doping, by the roasting under the mixed atmosphere of hydrogen and argon gas, is obtained The super fine zinc oxide conductive powder material of doping is obtained, but material prepared by the method is be applied to conductive material, doping 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, the method with Zinc, magnesium and aluminium are active component, with 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 in the mixed solution of NaOH and sodium carbonate with the mixed solution of cerium salt, the coprecipitated product for obtaining is in 400-600 DEG C roasting 6-8h, zinc mangnesium-aluminium-cerium houghite is prepared by coprecipitation, and zinc, magnesium, three kinds of mol ratios of metal of aluminium are 1.0: 1.0-4.5:1.0-2.0, the sulfur transfer additive prepared using the material has 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 constitutes and is：ZnO：10%-40%, NiO：15%- 22%th, Al2O3：10%-17%, SiO2：5%-22%, the balance of 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, is that to use the soluble-salt and alkali of metal be raw material, and being reacted by fractional precipitation makes composition LDH laminates Metal ion precipitate respectively, and LDH is produced in second step precipitation process, specific surface area is 140-280m2/g.Relative to altogether Although the precipitation method, the invention is employed and precipitates twice, but the LDH material specific surface areas for preparing are higher, but the invention is reacted Time is more long, and the reaction time be given in embodiment is more than 10 hours.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, prepared Process needs two steps to precipitate respectively, and the reaction time is more long.《Reduce the conjunction of the 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 respectively, is added after being well mixed 16% sodium hydroxide solution, the pH value for adjusting solution is 8.6, after the sediment of generation is through aging 15min, adds a small amount of hydrogen Sodium hydroxide solution, regulation pH value is 9.0.Sediment is filtered through the repetition of more than 3 times, washing, to remove Na+.Finally will precipitation Thing dries 4h at 120 DEG C, and 2h is calcined 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 processes full cut FCC gasoline.The main chemical reactions of the method are de- Reaction of Salmon-Saxl.Therefore, compared with raw material, in addition to sulfur content is greatly reduced, density, boiling range and other properties are substantially not for the product of generation Become；Alkene slightly has reduction；Alkane is increased slightly；(RON+MON)/2 loss is less than 1.0 units.But the method can not be significantly Reduce the olefin(e) centent in gasoline products, the FCC gasoline higher for olefin(e) centent, it is impossible to solve the problems, such as alkene.US5411658 Disclosed gasoline modifying method is, first using traditional Hydrobon catalyst by FCC gasoline hydrofinishing after, then using containing β Zeolite catalyst carries out octane value recovering to the reaction effluent of hydrofinishing.But the raw material end point of distillation that the method is used is inclined Height, reaction temperature is too high makes aromatic hydrocarbons and alkene saturation more for hydrofinishing section, causes research octane number (RON) (RON) to lose larger, It is difficult to effectively recovery.Gasoline modifying method is disclosed in US5399258, and first paragraph is satisfied by hydrogenation desulfurization and denitrogenation, hydrogenation of olefins With it is rear, the intermediate product for obtaining is directly entered second segment and carries out octane value recovering reaction.The reaction temperature of first paragraph is higher, with Two sections of reaction temperature maintains an equal level.Because the reaction temperature of first paragraph is too high, final product is caused to produce a large amount of mercaptan sulfurs, temperature is got over Height, the mercaptan sulfur of generation is more.The method of deep desulfurization olefin hydrocarbon reduction of gasoline disclosed in CN1465666A is to cut gasoline stocks It is light, heavy distillat, through alkali refining removal of mercaptans, heavy distillat, hydrogen are urged with Hydrobon catalyst, octane value recovering successively for light fraction Agent contact, by desulfurization after light, heavy distillat be mixed to get gasoline products.The method can produce sulfur content less than 200 μ g/g, Gasoline products of the alkene less than 20v%.But there is the problems such as liquid yield is low, and spent lye is processed in the method. 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 aluminum oxide of 5-30 weight %, the zinc oxide of 30-70 weight %, 2-15 weight % Lead oxide, the molecular sieve with BEA structures of 1-20 weight % and/or the molecular sieve with FAU structures and 5-30 weights Measure the active metal of %；And at least partly the lead oxide forms the zinc lead that formula PbxZn1-xO is represented with the zinc oxide The form of solid solution is present, and wherein x meets 0 ＜ x≤0.12, and x represents atomic molar ratio；The active metal be cobalt, nickel, iron and At least one in 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.CN200810010248.0 discloses a kind of gasoline depth The method for spending desulfurating and reducing olefinic hydrocarbon, 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 inventive method can produce gasoline of the sulfur content less than 50 μ g/g and produce Product, can further produce gasoline products of the sulfur content less than 10 μ g/g, and olefin(e) centent is less than 20v%, while ensureing anti- Quick-fried figure penalties very little.The inventive method 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, and adaptable to different material, 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, comprises the following steps：
Using fixed bed reactors, presulfurization is carried out to catalyst with sulfurized oil, after presulfurization treatment terminates, switched to complete Cut FCC gasoline replacement Treatment；
After pre-vulcanization process terminates, reaction process condition is adjusted to, carries out FCC gasoline reaction；
The described catalyst is support type nickel-cobalt-molybdenum catalyst, and the carrier of catalyst is containing 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 described catalyst, comprises the following steps：
The soluble-salt of nickeliferous, cobalt and molybdenum is made into maceration extract, complex carrier of the dipping containing zinc oxide-alumina is dried, Roasting obtains catalyst；The described 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 is 60.0-85.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts 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 described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, is prepared containing gahnite Zinc oxide stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid is added The acid solution containing Sodium Polyacrylate after acidification, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping, Dried process, calcination process is obtained 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.
Described 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, described catalyst, 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 described complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 10.0-35.0wt%, alumina content is 65.0-90.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts 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 obtains catalyst, and 4-6 hours, 550-650 are preferably dried at 110-150 DEG C Roasting obtains Hydrobon catalyst in 6-8 hours at DEG C.
The described 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；Be further continued for be added dropwise another zinc salt it is molten Liquid；After zinc solution is dripped, 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；To contain aluminium mixed solution according to the above method and replace titration with zinc solution, until zinc solution whole completion of dropping, 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 be completed in 1-6h；After 80-95 DEG C of aging 2-8h, cooling washing dries 4-10h to neutrality at 80-140 DEG C, 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 described 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, add Sodium Polyacrylate, and dissolved Entirely, the acid solution containing Sodium Polyacrylate is obtained.The addition of described Sodium Polyacrylate is preferably the 0.6- of boehmite 12wt%.The Sodium Polyacrylate of acidified treatment, zinc oxide, alumina powder mixing are more uniform.
The addition of the sesbania powder is preferably the 0.2-7wt% of boehmite.
Described dried process, calcination process, preferably 110-150 DEG C dried process 4-8 hours, at 550 DEG C -700 DEG C roast Burn treatment 4.5-8 hours.
The complex carrier containing zinc oxide-alumina obtained using preparation method of the present invention, can also using potassium and Magnesium is modified to the complex carrier surface containing zinc oxide-alumina, and the concentration of potassium and magnesium is unsuitable too high, preferably configuration concentration Carrier surface is sprayed less than the potassium nitrate and magnesium nitrate aqueous solution when preparing complex carrier, carrier is preferably carried out as follows Surface is modified：Aqueous solution spray complex carrier containing zinc oxide-alumina of the configuration containing potassium nitrate and magnesium nitrate, through drying, roasting Burning obtains used additives potassium and magnesium carries out the modified zinc oxide-alumina complex carrier in surface, and control zinc oxide-alumina is compound to be carried Potassium oxide and content of magnesia are respectively in the range of 0.2-2.5wt% and 0.2-2.5wt% in body, and aoxidize carrier surface 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 advantages below：
1st, the hydrodesulfurizationprocess process of gasoline of the present invention, reaction condition is gentle, to the strong adaptability of different material；Make to urge Agent has hydrodesulfurization activity and selectivity higher, and loss of octane number is low, and desulfurization degree is high, good stability, 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, accordingly, it would be desirable 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, it is to avoid the precursor obtained using alkaline solution one step titration zinc-aluminium mixed solution needs high-temperature roasting The problem of fixed zinc oxide, decreases hydrothermal treatment process.The material has larger specific surface area, it is adaptable to be catalyzed material Material, is particularly well-suited to FCC catalyst sulfur prodegradant and hydrodesulfurization carrier material.
3rd, the present invention can also introduce phosphorus, potassium, magnesium and Sodium Polyacrylate, poly- third in zinc oxide-alumina complex carrier Olefin(e) acid sodium can be repaired and improve catalytic inner pore passage structure, and diffusion effect is good in catalyst.The carrier is prepared into hydrodesulfurization Catalyst, such as catalyst such as cobalt molybdenum or nickel molybdenum, can suppress alkene saturated activity, and catalyst desulfurizing rate is high, alkene saturation factor (HYD) it is low, with good hydrodesulfurization selectivity.
4th, the present invention obtain containing 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 times.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 Enter to 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.
Specific 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 by catalyst：Reagent of the present invention is commercially available prod.
Feedstock oil is FCC gasoline, and sulfur content is 408mg/kg, and RON is 93.0, and alkene is 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 To in 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 is all added, last time is added dropwise mixed solution containing aluminium and reaches 9.0 to pH, and titration time amounts to 3h. After 80 DEG C of aging 4h, cooling washing dries 3h to the mixture for arriving to neutrality 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。
Weigh phosphatase 11 .04g, potassium nitrate 1.03g respectively, magnesium nitrate 8.88g is dissolved completely in 60g distilled water to be made into and contains 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.By 40g, zinc oxide and 164.3g boehmites ground and mixed containing gahnite are uniform, add 6.0g sesbania powders, Sodium Polyacrylate acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, 125 DEG C of dried process 7 hours are roasted at 580 DEG C Burn treatment and obtain within 7 hours the complex carrier containing zinc oxide-alumina.Complex carrier specific surface area 276m2/g.Complex carrier includes Zinc oxide 25wt% containing gahnite, aluminum oxide is 71.9wt%, and 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 ammoniacal liquor regulation After pH value, then diluted with deionized water, be made into maceration extract complex carrier of the dipping containing zinc oxide-alumina, the catalyst for obtaining Precursor is calcined 6h after being dried at 120 DEG C at 600 DEG C, obtains catalyst 1.Catalyst 1 is mainly constituted：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
The zinc nitrate solution of amount same as Example 1, sodium metaaluminate and sodium carbonate liquor are well mixed by blending method, with reality Apply that the zinc-aluminium mol ratio of example 1 is identical, similarity condition is aging, washing, dry, roasting obtains the oxide material containing zinc-aluminium.Zinc oxide Content be 65%；Specific surface area is 141m2/g.Compared with comparative example 1, embodiment 1 is using pH swing methods zinc, the friendship of aluminum solutions For titration, zinc-aluminium stratified material can be obtained, under the conditions of two kinds of material zinc-aluminium mol ratio identicals, embodiment 1 is containing zinc-aluminium point The specific surface area of the zinc oxide stratified material of spar is higher.
Weigh phosphatase 11 .04g, potassium nitrate 1.03g respectively, magnesium nitrate 8.88g is dissolved completely in 60g distilled water to be made into and contains 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.By 40g, oxide material and 164.3g boehmites ground and mixed containing zinc-aluminium are uniform, add 6.0g sesbania powders, gather PAA acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, 125 DEG C of dried process 7 hours are calcined at 580 DEG C Treatment obtains carrier in 7 hours.37.7g nickel nitrates, 426.4g ammonium molybdates, 12.5g cobalt nitrates is taken to be added in 50ml distilled water, plus After entering ammoniacal liquor regulation pH value, then diluted with deionized water, be made into maceration extract impregnated carrier, the catalyst precursor for obtaining is 120 DEG C drying after 600 DEG C be calcined 6h, obtain comparative catalyst 1.
Catalyst 1 and comparative catalyst 1 are respectively charged into 10ml fixed bed reactors, hydrodesulfurization reaction is carried out.With Sulfurized oil carries out presulfurization to catalyst, and sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%；Vulcanization pressure Power is 2.7MPa, and hydrogen to oil volume ratio is 320, and sulfurized oil volume space velocity is 2.5h-1, vulcanization program is respectively at 210 DEG C, 260 DEG C Vulcanizing treatment 7h, then switch to full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, enters FCC gasoline anti- Should.Reaction process condition is：270 DEG C of temperature of reactor, reaction pressure 1.5MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 260. Sampling analysis after reaction about 60h, Hydrobon catalyst 1 and the product desulfurization degree of comparative catalyst 1 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%, HYD point Wei 9 and 16.The loss of octane number of Hydrobon catalyst 1 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, with good hydrodesulfurization selectivity.Reaction operation 400h, Hydrobon catalyst product desulfurization degree is 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 stable performance.
Embodiment 2
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1 Zinc oxide, pH value is 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 and is modified, and detailed process comprises 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 respectively, is dissolved completely in 30ml distilled water, 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. Obtaining used additives potassium and magnesium through drying, roasting carries out the modified zinc oxide-alumina complex carrier in surface.The complex carrier compares table Area 238m2/g。
Nickel nitrate, ammonium molybdate, cobalt nitrate are made into maceration extract, dipping used additives potassium and magnesium carry out the modified oxidation in surface Zinc-alumina composite carrier, specific steps are with embodiment 1.Dried 6 hours at 120 DEG C, be calcined 5 hours at 650 DEG C, obtained Hydrobon catalyst 2.Catalyst 2 is mainly constituted：Nickel oxide 3.2wt%, cobalt oxide 2.7wt%, molybdenum oxide 9.5wt%, use Auxiliary agent potassium and magnesium carry out the modified zinc oxide-alumina complex carrier 84.6wt% in surface.
Catalyst 2 is fitted into 10ml fixed bed reactors, hydrodesulfurization reaction is carried out.Catalyst is carried out with sulfurized oil Presulfurization, sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%；Sulfide stress is 2.7MPa, hydrogen oil volume Than being 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 to switch to Full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, enters FCC gasoline reaction.Reaction process condition is：Instead Answer 270 DEG C of device temperature, reaction pressure 1.5MPa, volume space velocity 3.0h-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.82% situation is not less than in desulfurization degree Under, alkene saturation factor (HYD) is only 8% or so, with good hydrodesulfurization selectivity.Reaction operation 400h, hydrodesulfurization Catalyst prod desulfurization degree is 82.5%, and loss of octane number is 0.3 unit, and HYD is 9.Produce on the complex carrier surface of catalyst More active sites load centres are born, catalyst desulfurizing activity, catalyst reaction stable performance is effectively improved.
Embodiment 3
The preparation method and step of the complex carrier containing zinc oxide-alumina are with embodiment 1.Prepare containing gahnite Zinc oxide, pH value is 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, and aluminum oxide is 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, complex carrier of the dipping containing zinc oxide-alumina, specific step Suddenly with embodiment 1.Dried 4 hours at 130 DEG C, be calcined 6 hours at 600 DEG C, obtain Hydrobon catalyst 3.Catalyst 3 is led Constitute：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, hydrodesulfurization reaction is carried out.Catalyst is carried out with sulfurized oil Presulfurization, sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%；Sulfide stress is 2.7MPa, hydrogen oil volume Than being 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 to switch to Full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, enters FCC gasoline reaction.Reaction process condition is：Instead Answer 295 DEG C of temperature, reaction pressure 2.5MPa, volume space velocity 2.4h-1, hydrogen to oil volume ratio 270:1.
Sampling analysis after reaction about 60h, Hydrobon catalyst product desulfurization degree is 81.5%, and loss of octane number 0.3 is Individual unit, alkene drop amount 2.2%, HYD is 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, with good hydrodesulfurization Selectivity.
Embodiment 4
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1 Zinc oxide, pH value is 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, and aluminum oxide is 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, are added ammoniacal liquor regulation pH value salt is impregnated after all dissolving and is contained The complex carrier of zinc oxide-alumina, specific steps are with embodiment 1.Dried 5 hours at 120 DEG C, 7 are calcined at 550 DEG C small When, obtain Hydrobon catalyst 4.Catalyst 4 is mainly constituted：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, hydrodesulfurization reaction is carried out.Catalyst is carried out with sulfurized oil Presulfurization, sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%；Sulfide stress is 2.7MPa, hydrogen oil volume Than being 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 to switch to Full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, enters FCC gasoline reaction.Reaction process condition is：Instead Answer 245 DEG C of temperature, reaction pressure 2.0MPa, volume space velocity 1.8h-1, hydrogen to oil volume ratio 230:1.
Sampling analysis after reaction about 60h, Hydrobon catalyst product desulfurization degree is 80.6%, and loss of octane number 0.3 is Individual unit, alkene drop amount 2.0%, HYD is 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, de- with good hydrogenation Sulphur selectivity.
Embodiment 5
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1 Zinc oxide, pH value is 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, and aluminum oxide is 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 comprises the following steps：Configuration contains potassium nitrate and magnesium nitrate aqueous solution, and spray zinc oxide-alumina is combined 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 modified zinc oxide-alumina complex carrier in surface.
Nickel nitrate, ammonium molybdate, cobalt nitrate are made into maceration extract, dipping used additives potassium and magnesium carry out the modified oxidation in surface Zinc-alumina composite carrier, specific steps are with embodiment 1.Dried 5 hours at 130 DEG C, be calcined 6 hours at 600 DEG C, obtained Hydrobon catalyst 5.Catalyst 5 is mainly constituted：Nickel oxide 4.1wt%, cobalt oxide 1.4wt%, molybdenum oxide 11.3wt%, contain The complex carrier 83.2wt% of zinc oxide-alumina.
Catalyst 5 is fitted into 10ml fixed bed reactors, hydrodesulfurization reaction is carried out.Catalyst is carried out with sulfurized oil Presulfurization, sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%；Sulfide stress is 2.7MPa, hydrogen oil volume Than being 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 to switch to Full cut FCC gasoline replacement Treatment 10h.Reaction process condition is adjusted to again, enters FCC gasoline reaction.Reaction process condition is：Instead Answer 260 DEG C of temperature, reaction pressure 2.2MPa, volume space velocity 2.6h-1, hydrogen to oil volume ratio 240:1.
Sampling analysis after reaction about 60h, Hydrobon catalyst product desulfurization degree is 84.3%, and loss of octane number 0.3 is Individual unit, alkene drop amount 1.5%, HYD is 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, with 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 10 for 1.5%, HYD.The complex carrier surface of catalyst produces more active sites load centres, effectively improves Catalyst desulfurizing activity, catalyst reaction stable performance.
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 Knowing those skilled in the art can make various corresponding changes and deformation, but these corresponding changes and deformation according to the present invention Protection scope of the present invention should all be belonged to.

Claims (10)

1. a kind of method for gasoline desulfurization, it is characterised in that comprise the following steps：
Using fixed bed reactors, presulfurization is carried out to catalyst with sulfurized oil, after presulfurization treatment terminates, switch to full cut FCC gasoline replacement Treatment；
After pre-vulcanization process terminates, reaction process condition is adjusted to, carries out FCC gasoline reaction；
Described 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 described catalyst, comprises the following steps：
Soluble-salt containing cobalt and molybdenum is made into maceration extract, complex carrier of the dipping containing zinc oxide-alumina is dried, be calcined To catalyst；The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum 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 to be respectively be 5.0-40.0wt%, alumina content is 60.0-95.0wt%, and adjuvant component phosphorus, potassium and magnesium contain Amount accounts for the percentage composition respectively P of carrier quality2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, Complex carrier specific surface area 200-300m2/g；
The described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, the oxygen containing gahnite is prepared Change zinc stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid acidifying is added The acid solution containing Sodium Polyacrylate after treatment, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping, dry Treatment, calcination process is obtained containing zinc oxide-alumina composite carrier.
2. a kind of method for gasoline desulfurization according to claim 1, it is characterised in that：Described fixed bed reaction Device, is fixed bed adiabatic reactor or fixed bed isothermal reactor.
3. a kind of method for gasoline desulfurization according to claim 1, it is characterised in that：Described 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 method for gasoline desulfurization according to claim 3, it is characterised in that：Described 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 method for gasoline desulfurization according to claim 1, it is characterised in that：
Described 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 described complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 10.0- 35.0wt%, alumina content is 65.0-90.0wt%, and the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contains 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 method for gasoline desulfurization according to claim 1, it is characterised in that：Described drying, is calcined It is that roasting obtains Hydrobon catalyst in 6-8 hours at 4-6 hours, 550-650 DEG C are dried at 110-150 DEG C to catalyst； Described dried process, calcination process, be 110-150 DEG C dried process 4-8 hours, calcination process 4.5-8 at 550 DEG C -700 DEG C Hour.
7. a kind of 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 is dripped, continue to be added dropwise containing aluminium Mixed solution, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；To contain aluminium mixed solution and zinc according to the above method Salting liquid is alternately titrated, until zinc solution whole completion of dropping, last time is added dropwise mixed solution containing aluminium, 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；It is aging at 80-95 DEG C After 2-8h, cooling washing dries 4-10h, 450-550 DEG C of roasting 4-10h at 80-140 DEG C to neutrality, obtains dispersed containing The zinc oxide stratified material of gahnite；The soluble zinc salt is zinc nitrate or zinc chloride.
8. a kind of method for gasoline desulfurization according to claim 1, it is characterised in that：Described 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, Sodium Polyacrylate is added, and dissolves complete, obtain the acid solution containing Sodium Polyacrylate.
9. a kind of method for gasoline desulfurization according to claim 1, it is characterised in that：Described 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 method for gasoline desulfurization according to claim 1, it is characterised in that：It is described containing 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：Aqueous solution spray complex carrier containing zinc oxide-alumina of the configuration containing potassium nitrate and magnesium nitrate, warp Dry, roasting obtains used additives potassium and magnesium carries out the modified zinc oxide-alumina complex carrier in surface, 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% in aluminium complex carrier, and make carrier The content of surface oxidation potassium and magnesia is 1.05-1.5 times of internal oxidation potassium and content of magnesia.
CN201710158467.2A 2017-03-17 2017-03-17 A kind of method for gasoline desulfurization Expired - Fee Related CN106867577B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710158467.2A CN106867577B (en) 2017-03-17 2017-03-17 A kind of method for gasoline desulfurization

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710158467.2A CN106867577B (en) 2017-03-17 2017-03-17 A kind of method for gasoline desulfurization

Publications (2)

Publication Number Publication Date
CN106867577A true CN106867577A (en) 2017-06-20
CN106867577B CN106867577B (en) 2018-04-20

Family

ID=59172462

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710158467.2A Expired - Fee Related CN106867577B (en) 2017-03-17 2017-03-17 A kind of method for gasoline desulfurization

Country Status (1)

Country Link
CN (1) CN106867577B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108404976A (en) * 2018-03-12 2018-08-17 济南大学 A kind of FCC gasoline desulfurization-hydrogenation method for modifying
CN109261161A (en) * 2018-10-14 2019-01-25 黄凤玉 A kind of catalyst and preparation method of FCC gasoline hydro-sweetening

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4920089A (en) * 1987-05-08 1990-04-24 Unilever Patent Holdings B.V. Hydrogenation catalyst
CN1043359C (en) * 1994-11-25 1999-05-12 中国石化齐鲁石油化工公司 Hydrodevulcanizing catalyst for hydro-carbons and preparation method thereof
CN101844088A (en) * 2010-04-14 2010-09-29 中国科学院大连化学物理研究所 Gasoline selective desulfurization catalyst
CN102335612B (en) * 2010-07-22 2013-07-31 中国石油天然气股份有限公司 Selective hydrodesulfurization catalyst and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108404976A (en) * 2018-03-12 2018-08-17 济南大学 A kind of FCC gasoline desulfurization-hydrogenation method for modifying
CN108404976B (en) * 2018-03-12 2020-11-17 济南大学 FCC gasoline desulfurization and hydrogenation modification method
CN109261161A (en) * 2018-10-14 2019-01-25 黄凤玉 A kind of catalyst and preparation method of FCC gasoline hydro-sweetening
CN109261161B (en) * 2018-10-14 2021-12-14 莆田城厢振达宸贸易有限公司 Catalyst for removing mercaptan from FCC gasoline by hydrogenation and preparation method thereof

Also Published As

Publication number Publication date
CN106867577B (en) 2018-04-20

Similar Documents

Publication Publication Date Title
CN106867576B (en) A kind of hydrodesulfurizationprocess process of gasoline
CN106635135B (en) A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline
CN102335612B (en) Selective hydrodesulfurization catalyst and preparation method thereof
CN106622204B (en) A kind of zinc oxide material and preparation method containing gahnite
RU2569682C2 (en) Composition and method for preparation of carrier and catalyst of deep hydrofining of hydrocarbon stock
CN102343276A (en) Catalyst for deep desulfuration and octane number increase for gasoline and preparation and application methods thereof
CN106179414B (en) A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof
CN102909027A (en) Preparation method of catalyst by ultralow-sulfur hydrofining
CN106867577B (en) A kind of method for gasoline desulfurization
CN102500403A (en) Liquefied gas hydrogenating, olefin content decreasing and desulfurizing catalyst and preparation method thereof
CN106955746A (en) A kind of complex carrier of the aluminum oxide containing zinc oxide and preparation method thereof
CN106833731B (en) A kind of hydro-dearsenic method of naphtha
CN100478423C (en) Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method
CN106807420A (en) A kind of catalyst and preparation method for petroleum naphtha hydrogenation dearsenification
CN107511143B (en) Regeneration method of adsorption desulfurizer
CN106881127A (en) A kind of catalyst and preparation method for gasoline desulfurization modification
CN102268285A (en) Pre-hydrotreatment method of reforming feedstocks
CN106622319B (en) A kind of zinc-aluminium stratified material and preparation method
CN106929091B (en) A kind of catalytic gasoline hydrogenation desulfurization method for modifying
CN106732632A (en) A kind of Hydrobon catalyst and preparation method
CN106732516A (en) A kind of zinc oxide aluminium complex carrier and preparation method containing auxiliary agent
CN106925309A (en) A kind of catalyst for gasoline hydrodesulfurizationmethod and preparation method thereof
CN102268284B (en) Hydrorefining method of middle and low distillate oil
CN102319572B (en) Hydrotreatment catalyst and preparation method thereof
CN107583659B (en) Catalyst for selective hydrodesulfurization and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180420

CF01 Termination of patent right due to non-payment of annual fee