CN106635135A - Hydrodesulfurization method of catalytic cracking gasoline - Google Patents

Hydrodesulfurization method of catalytic cracking gasoline Download PDF

Info

Publication number
CN106635135A
CN106635135A CN201611205747.6A CN201611205747A CN106635135A CN 106635135 A CN106635135 A CN 106635135A CN 201611205747 A CN201611205747 A CN 201611205747A CN 106635135 A CN106635135 A CN 106635135A
Authority
CN
China
Prior art keywords
zinc oxide
zinc
strontium
potassium
catalyst
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
CN201611205747.6A
Other languages
Chinese (zh)
Other versions
CN106635135B (en
Inventor
牟晓红
夏德强
周艳青
唐蓉萍
田苗
郑晓明
王守伟
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.)
Lanzhou Petrochemical College of Vocational Technology
Original Assignee
Lanzhou Petrochemical College of Vocational Technology
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 Lanzhou Petrochemical College of Vocational Technology filed Critical Lanzhou Petrochemical College of Vocational Technology
Priority to CN201611205747.6A priority Critical patent/CN106635135B/en
Publication of CN106635135A publication Critical patent/CN106635135A/en
Application granted granted Critical
Publication of CN106635135B publication Critical patent/CN106635135B/en
Active 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8873—Zinc, cadmium or mercury
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Abstract

The invention relates to a hydrodesulfurization method of catalytic cracking gasoline. A fixed bed reactor is adopted, wherein the catalyst is a supported cobalt-molybdate catalyst; and the hydrodesulfurization method comprises the following technologic conditions: the reaction temperature is 180-310 DEG C, the reaction pressure is 1.5-2.5MPa, the volume velocity is 1.5-3.5h<-1> and the volume ratio of hydrogen to oil is (180-400):1. The hydrodesulfurization method is mild in technologic conditions, high in adaptive capacity on different raw materials, low in octane value loss and high in desulfurization rate.

Description

A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline
Technical field
The present invention relates to a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline, more specifically using a kind of auxiliary agent that contains Zinc oxide-alumina composite is the FCC Hydrobon catalysts of carrier, takes off for catalytic gasoline selective hydrogenation Sulphur.
Background technology
Because the general sulfur content of catalytically cracked gasoline is in 100-500v%, or even also high-sulfur, high olefin feedstock are oily, and sulphur contains , in more than 500mg/kg, olefin(e) centent is also above 40% for amount.Selective hydrodesulfurization technology can not when deep hydrodesulfurizationof is carried out The meeting for avoiding causes hydrocarbon fraction saturation and reduces octane number, avoids as far as possible while this requires Hydrobon catalyst desulfurization Loss of octane number is excessive.
The composite of zinc oxide and aluminum oxide is used for hydrodesulfurization field frequently as desulfurization catalyst material.Spinel-type is answered It is the up-and-coming Inorganic Non-metallic Materials of a class to close oxide, and with a series of good characteristics high temperature is widely used in The fields such as material, catalyst and catalyst carrier.The composite of zinc oxide and aluminum oxide is used for frequently as desulfurization catalyst material Absorption desulfurization and hydrodesulfurization field.Both at home and abroad the conventional preparation method of the material includes infusion process, mechanical mixing, co-precipitation Method and peptisation.Wherein, because infusion process and mechanical mixing use alumina material as predecessor, by adjusting aluminum oxide The specific surface area of material, both approaches can prepare the composite of high specific surface area, but due in composite Aluminum oxide and zinc oxide interaction are weaker, and the loss of zinc oxide is easily produced during use, are typically with high-temperature roasting Method promote the two to form spinelle to avoid the loss of zinc oxide；And coprecipitation and peptisation are using the change containing aluminum and zinc Compound prepares zinc-aluminium precursor by precipitation or peptization, and aluminum and zinc produces stronger interaction in preparation process by reaction The zinc oxide during use can be avoided to be lost in, but the specific surface area that peptisation prepares material is minimum so as to as catalysis It is restricted during materials'use.
US5525210 discloses a kind of method of FCC gasoline desulfurization, and its main active component is to be carried on alumina support On L it is sour, such as zinc oxide, the method for being adopted is infusion process and coprecipitation, and wherein infusion process prepares material in 815 DEG C of roastings Specific surface area 142m afterwards2/ g, coprecipitation prepares material specific surface area 74m after 704 DEG C of roastings2/g.Two methods sintering temperature It is higher, prepare zinc-aluminium material specific surface area low.
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 homodisperse 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 to be added dropwise in NaOH and soluble inorganic sodium salt To in the mixed solution of zinc salt, aluminium salt and rare earth ion, the pH value of solution is 8-11, in 500-1000 DEG C of roasting 1-4h.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）Disclose a kind of Nano-Zinc The preparation method of aluminate, its preparation method is that zinc salt is added to the water into dissolving, adds silicon source, is stirred 10～30 minutes, plus Enter expanding agent, stir, it is aging 30～60 minutes at 20～100 DEG C, it is dried, 500～1200 DEG C of roastings；Feed molar proportioning is Zn : Al: water=1: 2: 16 ~ 35；Calculated with the quality of zinc oxide as 100%, the addition of expanding agent is 0.5～30%；Expanding agent is sugarcane One or more in sugar, glycerine, ammonium carbonate, ammonium hydrogen carbonate, polystyrene emulsion, polyethylene glycol.Synthesized zinc-aluminium point The specific surface area of spar is from 60 to 300m2/g.Zinc-aluminium proportioning that the method feeds intake is relatively low and preparation process addition expanding agent, only Gahnite is obtained, not comprising homodisperse zinc oxide.
CN201310625314.6 (CN103691441) discloses a kind of strong absorption, high visible degradation property photocatalysis The preparation method of material, it is presoma that the invention is related to one kind ternary houghite, the Gao Bibiao obtained by high-temperature roasting Face meso-hole 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 is using zinc nitrate, nickel nitrate, aluminum nitrate, sodium carbonate and sodium hydroxid etc. Raw material, is configured to respectively salting liquid and aqueous slkali, under 80 DEG C and magnetic agitation, is mixed with constant flow pump；Reaction mixture In being transferred to hydrothermal reaction kettle, hydro-thermal process 5-10h at 130-180 DEG C；Suction filtration, wash, be drying to obtain presoma, by forerunner The roasting 2-6 hours at 400-600 DEG C are put in Muffle furnace, product is obtained final 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 hydro-thermal process during the method synthesis of ternary houghite presoma, and And process time is longer.CN200310121344.X discloses a kind of preparation side of the Nano-class zinc oxide conductive powder body of adulterated al Method.The method be by the soluble-salt of zinc and doped chemical aluminium, gallium, indium, yttrium, scandium, tin, germanium, the soluble-salt of silicon salt-mixture Solution and precipitating reagent are added drop-wise in water simultaneously, in the condition of temperature 40-75 DEG C and pH value 7.0-7.5 for controlling whole reaction system It is lower to produce the zinc oxide precursor basic zinc carbonate that co-precipitation generates doping, by the roasting under the mixed atmosphere of hydrogen and argon gas Burn, the super fine zinc oxide conductive powder material for obtaining doping has been obtained, but material prepared by the method is to be applied to conduction material Material, the addition mole of doped chemical is only the 0.1-10% of zinc and doped chemical integral molar quantity.CN200510028233.3 is disclosed A kind of preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas, the method with zinc, magnesium and aluminium as active component, with cerium and vanadium For auxiliary agent, under the conditions of 60-80 DEG C, pH value 8-10, the mixed solution of zinc salt, magnesium salts, aluminium salt and cerium salt is added drop-wise to into hydroxide In the mixed solution of sodium and sodium carbonate, the coprecipitated product for obtaining prepares zinc in 400-600 DEG C of roasting 6-8h by coprecipitation Mangnesium-aluminium-cerium houghite, zinc, magnesium, the mol ratio of three kinds of metals of aluminium are 1.0:1.0-4.5:1.0-2.0, is prepared using the material Sulfur transfer additive has efficient SOx absorption and desorption performance and good mechanical strength.CN200910087590.5 discloses one Desulfurizing agent for reforming stock oil and preparation method thereof is planted, method for preparing catalyst is related to blending method, eutectic method and coprecipitation, it is special Levy is that its weight is consisted of：ZnO：10%-40%、NiO：15%-22%、Al2O3：10%-17%、SiO2：5%-22%, it is balance of not The impurity that can exempt from.CN201310089762.9（CN 103159238）Disclose a kind of nano-scale stratiform complex hydroxide and Its fractional precipitation preparation method, be the soluble-salt and alkali for adopting metal for raw material, by fractional precipitation reaction make composition LDH layer The metal ion of plate is precipitated respectively, and LDH is produced in second step precipitation process, and specific surface area is 140-280m2/g.Relative to Although coprecipitation, the invention employs and precipitates twice, but the LDH material specific surface areas for preparing are higher, but the invention is anti- Longer between seasonable, the reaction time be given in embodiment is more than 10 hours.The purpose of the invention is the stratiform for preparing Gao Bibiao Complex hydroxide（LDH）, layered double hydroxide structural formula complexity, may relate to various metals or it is combined, system Standby process needs two steps to precipitate respectively, and the reaction time is longer.《Reduce the research-zinc-aluminium point of sulfur content of catalytic cracking gasoline auxiliary agent The synthesis of spar and its cracking desulfurization performance》(author：Wang Peng；Sinopec Group,《Petroleum journal (oil Processing)》2 phases of volume 19 in 2003)：A kind of preparation method of gahnite is disclosed：By sodium aluminate solution and zinc nitrate solution By m (Al2O3The ratio of)/m (ZnO)=9, is added drop-wise in 40 DEG C of distilled water respectively with identical speed, is added again after being well mixed Enter 16% sodium hydroxide solution, the pH value for adjusting solution is 8.6, the sediment of generation is added a small amount of Jing after aging 15 min Sodium hydroxide solution, it is 9.0 to adjust pH value.The repetition that sediment Jing is more than 3 times is filtered, washing, to remove Na+.Finally will be heavy Starch is dried 4 h, the h of roasting 2 at 700 DEG C at 120 DEG C.The specific surface area of sample is substantially all in 160 m2/ g or so.
The content of the invention
The present invention provides a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline, hydrodesulfurization mild condition, to difference Raw material is adaptable, and loss of octane number is low, and desulfurization degree is high.
A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline, using fixed bed reactors；The catalyst is supported cobalt Molybdenum catalyst, the carrier of catalyst is the zinc oxide-alumina complex carrier containing auxiliary agent, and the composition of catalyst is with oxide mass Meter, including following component：Active component cobalt oxide 0.5-10 wt%, preferred 1.5-4.5 wt%, molybdenum oxide 0.5-12 wt%, it is excellent 1-8 wt% are selected, the zinc oxide-alumina complex carrier 78-94 wt % containing auxiliary agent.Hydrodesulfurization condition is：Reaction temperature 180-310 DEG C, preferred 200-280 DEG C, reaction pressure 1.5-2.5MPa, volume space velocity 1.4-3.5h-1, preferred 1.5-3.0h-1 , Hydrogen to oil volume ratio 180-400:1, preferred 200-300:1.
The catalytic gasoline hydrogenation sulfur method that the present invention is provided, its reactor can be fixed bed adiabatic reactor Can be fixed bed isothermal reactor, preferably fixed bed adiabatic reactor.
The Hydrobon catalyst preparation method comprises the steps：Soluble-salt containing cobalt and molybdenum is made into into dipping Liquid, adds ammoniacal liquor to adjust zinc oxide-alumina complex carrier of the dipping containing auxiliary agent after pH value makes salt all dissolve, in 110-150 Roasting 6-8 hours at 4-6 hours, 550-650 DEG C are dried at DEG C, Hydrobon catalyst is obtained.
Zinc oxide-alumina complex carrier containing auxiliary agent of the present invention, adjuvant component boron, potassium and strontium, zinc oxide is to contain The zinc oxide stratified material of gahnite.Soluble salt solutions containing aluminium and zinc-containing solution are alternately dripped through non-constant pH It is fixed, prepare the zinc oxide stratified material containing gahnite, the zinc oxide stratified material again with boehmite, adjuvant component The kneadings such as the soluble-salt of boron, potassium and strontium, obtain the zinc oxide-alumina complex carrier containing auxiliary agent.It is mainly used in FCC catalyst Sulfur prodegradant and FCC hydrodesulfurization carriers.
Zinc oxide-alumina complex carrier containing auxiliary agent of the present invention, complex carrier includes the oxygen containing gahnite Change zinc, aluminum oxide, adjuvant component boron, potassium and strontium, the composition of complex carrier is with oxidation material gauge：Oxidation containing gahnite Zn content be 5-40 wt%, preferred 10-30 wt%, alumina content be 65-85 wt%, preferred 70-80 wt%, adjuvant component Boron, potassium and content of strontium are respectively B2O30.5-1.5 wt %, K2O 0.3-2.5 wt %, SrO 0.2-2.5 wt %.It is compound to carry Surface area per unit volume accumulates 220-300m2/g。
Zinc oxide-alumina complex carrier preparation method containing auxiliary agent of the present invention is as follows：
Soluble salt solutions containing aluminium and zinc-containing solution are alternately titrated through non-constant pH, the oxygen containing gahnite is prepared Change zinc stratified material；Zinc oxide containing gahnite and boehmite are well mixed, sesbania powder, nitric acid acidifying is added The acid solution containing Sodium Polyacrylate after process, the addition of Sodium Polyacrylate is 0.5～10wt% of boehmite, and The aqueous solution of boric acid, potassium nitrate and strontium nitrate etc., kneading, after shaping, 110-140 DEG C of dried process 5-9 hour, 550 DEG C -750 Calcination process 5-7 hour obtains the zinc oxide-alumina complex carrier containing auxiliary agent at DEG C.The addition of the sesbania powder is thin to intend 0.2～6wt% of diaspore.
Acidification process is carried out to Sodium Polyacrylate as follows：Deionized water is heated to into 30～95 DEG C, then by nitric acid In being dissolved into deionized water, Sodium Polyacrylate is added, and dissolve complete, obtain the acid solution containing Sodium Polyacrylate.Through acid Change the Sodium Polyacrylate for processing, its is uniformly dispersed more preferably, zinc oxide, alumina powder mixing are more uniform, are effectively improved oxygen Change the problem that alumina particles are easily reunited, after extrusion-shaping-drying-roasting, diameter of particle is more uniform, good forming effect.
Zinc oxide containing gahnite of the present invention, in terms of oxide, the content of zinc oxide is 60-90%, preferably 65-75%；Specific surface area is 160-220m2/ g, the preferred 190-220 m of specific surface area2/g.The content of zinc oxide is being controlled in 65- When 80%, specific surface area 170-200m2/g；When the content of zinc oxide is controlled in 70-80%, specific surface area 190-220 m2/g。
The present invention provides a kind of preparation method of the zinc oxide stratified material containing gahnite, comprises the steps：Will Soluble Zn salting liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, sodium metaaluminate and sodium carbonate is 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 said 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 complete in 1.0-6h.After 80-95 DEG C of aging 2-8h, cooling washing is dried 4-10h to neutrality at 80-140 DEG C, 450-550 DEG C of roasting 4-10h, obtains the homodisperse zinc oxide stratified material containing gahnite.
Soluble zinc salt of the present invention is zinc nitrate or zinc chloride.
Boron, potassium, strontium and Sodium Polyacrylate are introduced in zinc oxide-alumina complex carrier, the carrier is prepared into containing cobalt molybdenum Hydrobon catalyst, is conducive to adjusting the acidity of Hydrobon catalyst, and catalytic inner pore passage structure is improved in finishing, can Reduce the polymerization of alkene in feedstock oil, suppress catalytic inner coking deactivation, carbon deposition rate is low, improve adding for Hydrobon catalyst Stabilized hydrogen.Macromolecule polyacrylic acid sodium can be adjusted at thousand grades according to the difference of the degree of polymerization, molecular weight between millions Section so that aluminum oxide macropore diameter can be adjusted according to molecular size range.Sodium Polyacrylate has ball of string structure so that carry In vivo the foramen magnum-mesoporous duct in portion has connectivity, rather than blind bore structure.
Zinc oxide-alumina complex carrier preparation method containing auxiliary agent of the present invention, after obtaining complex carrier, preferred profit Surface modification is carried out to the zinc oxide-alumina complex carrier containing auxiliary agent with potassium and strontium, detailed process comprises the steps：Configuration The aqueous solution containing potassium nitrate and strontium nitrate is used as maceration extract zinc oxide-alumina complex carrier of the dipping containing auxiliary agent, drying, roasting Burning obtains used additives potassium and strontium carries out the zinc oxide-alumina complex carrier of surface modification.Control zinc oxide-alumina is compound to be carried Body potassium oxide and content of strontium are respectively in the range of 0.3-2.5 wt % and 0.2-2.5 wt %.
Zinc oxide stratified material of the present invention containing gahnite or the zinc oxide material containing gahnite, can be abbreviated It is the zinc oxide containing gahnite or zinc oxide.Compared with prior art, the zinc oxide containing gahnite of the invention is By non-constant pH, alternately prepared by titration, i.e., under non-constant pH value condition, the friendship of the sodium carbonate liquor containing aluminium and zinc-containing solution Prepare for titration, accordingly, it would be desirable to zinc-containing solution is divided into into 2-4 parts, the sodium carbonate liquor containing aluminium is strong alkali solution, containing the strong of zinc Sour weak base salting liquid is acid solution, and the multiple alternately titration between aluminium zinc solution makes pH value swing between soda acid, is conducive to Aluminium zinc precursor thing can orderly accumulation be layer structure, the direct low-temperature bakes of Jing can be uniformly dispersed and specific surface area Can be in 150-220m2The zinc oxide material containing gahnite regulated and controled between/g, it is to avoid using alkaline solution one step drop Determining the precursor that zinc-aluminium mixed solution obtains needs high-temperature roasting to fix the problem of zinc oxide, decreases hydrothermal treatment process. The material has larger specific surface area, it is adaptable to catalysis material, is particularly well-suited to FCC catalyst sulfur prodegradant and hydrogenation is de- Sulfur-donor material.
The surface of zinc oxide-alumina complex carrier of the present invention containing auxiliary agent makes carrier table Jing after potassium and strontium modification The content that the potassium in face and the concentration of strontium form concentration difference, carrier surface potassium and strontium with the concentration of carrier inside potassium and strontium is higher than carrier The molar content or mass content of the content of internal potassium and strontium, i.e., outside potassium and strontium can be the 1.2- of the content of internal potassium and strontium 2.5 again.Can so make carrier surface tend to equally distributed state, reduce the acidity of carrier surface, the carrier is prepared into and adds Hydrogen desulphurization catalyst, it is possible to increase the specific surface area of Hydrobon catalyst, suppresses Hydrobon catalyst surface coking deactivation, Improve the decentralization and tack on carrier such as hydrodesulphurizatiocatalyst catalyst activity component cobalt molybdenum, active component cobalt molybdenum etc. and be difficult stream Lose, such effectively solving makes the problem of activity decrease, good catalyst activity because of the loss such as active component cobalt molybdenum.Potassium and strontium it is dense Degree is unsuitable too high, and the potassium nitrate and strontium nitrate aqueous solution when preferably configuration concentration slightly below or slightly above prepares complex carrier enters Row carrier surface is modified.
The hydrodesulfurizationprocess process of catalytically cracked gasoline of the present invention, reaction condition is gentle, the strong adaptability to different material；Make Catalyst has higher hydrodesulfurization activity and selectivity, and loss of octane number is low, and desulfurization degree is high, good stability, is conducive to dress Put long period steady running.
Description of the drawings
Fig. 1 is the XRD phenograms of the zinc oxide material sample containing gahnite prepared by embodiment 1.The XRD spectrums of sample Containing the XRD characteristic peaks of two kinds of thing phases of gahnite and zinc oxide in figure, illustrate that the material is the oxygen containing gahnite Change Zinc material.
Specific embodiment
By the following examples the hydrodesulfurizationprocess process of catalytically cracked gasoline of the present invention is carried out further with comparative example Describe in detail.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.
Catalytically cracked gasoline is Lanzhou Petrochemical oil plant catalytically cracked gasoline, and sulfur content is 300 mg/kg, and RON is 91.5, Alkene is 40% vol.
Embodiment 1
1.2kg zinc nitrates are dissolved in 6L water and are made into zinc-containing solution, 0.24kg sodium metaaluminates and 0.30kg sodium carbonate are dissolved It is made into containing aluminum solutions in 4L water.Zinc-containing solution is divided into into 3 parts, every part of 2L.2L zinc-containing solutions are taken, temperature is kept for 80 DEG C, to Mixed solution containing aluminium is wherein added dropwise and reaches 9.0 to pH value；Stop that mixed solution containing aluminium is added dropwise, then 2L zinc-containing solutions are added dropwise to mixing In system, continue dropwise addition mixed solution containing aluminium and reach 9.0 to pH value；Mixed solution containing aluminium and zinc-containing solution are alternately titrated, until Zinc-containing solution is all added, and last time is added dropwise mixed solution containing aluminium and reaches 9.0 to pH, and titration time amounts to 3h.What is obtained is mixed After 80 DEG C of aging 4h, cooling washing is dried 3h to compound to neutrality in 135 DEG C of air atmospheres, in 500 DEG C of roasting 9h, obtains The homodisperse zinc oxide stratified material containing gahnite, in terms of oxide, the content of zinc oxide is 65%；Specific surface area For 196m2/g。
Boric acid 1.18g, potassium nitrate 1.7g are weighed respectively, and strontium nitrate 1.51g is dissolved completely in be made in 56g distilled water and contains Boron, potassium, the aqueous solution of strontium.5.6g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.4g mass concentrations are 65% Acid.Zinc oxide of the 30g containing gahnite and 112.6g boehmites ground and mixed is uniform, 6.0g sesbania powders are added, Sodium Polyacrylate acid solution, boracic, potassium, the aqueous solution of strontium, kneading, after shaping, 135 DEG C of dried process 6 hours are roasted at 550 DEG C Burn to process and obtain within 6 hours the zinc oxide-alumina complex carrier containing auxiliary agent.Complex carrier specific surface area 268m2/g.Complex carrier Including the wt% of zinc oxide 27 containing gahnite, aluminum oxide is 71 wt%, and adjuvant component boron, potassium and content of strontium are respectively B2O3 0.6 wt %, K2The wt % of O 0.7, SrO 0.7 wt %.
Take 15.66g ammonium molybdates, 13.44g cobalt nitrates to be added in 20ml distilled water, adding ammoniacal liquor to adjust pH value makes salt complete After portion's dissolving, then deionized water dilution, maceration extract zinc oxide-alumina complex carrier of the dipping containing auxiliary agent is made into, obtain Catalyst precursor, in 600 DEG C of roasting 5h, obtains catalyst 1 after 110 DEG C of drying.Catalyst 1 is mainly constituted：Cobalt oxide 3 Wt%, molybdenum oxide 10wt%, the zinc oxide-alumina complex carrier 87wt % containing auxiliary agent.
Catalyst 1 is fitted in 10ml fixed bed reactors, carries out evaluating catalyst reaction performance.With sulfurized oil to catalysis Agent carries out presulfurization, and sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%；Sulfide stress is 2.8MPa, hydrogen Oil volume ratio is 300, and sulfurized oil volume space velocity is 3.0h-1, sulfuration program is respectively in 220 DEG C, 280 DEG C of vulcanizing treatments 6h.Sulphur After change process terminates, full cut FCC gasoline replacement Treatment 8h is switched to, after pre-vulcanization process terminates, be adjusted to reaction process Condition, enters catalytically cracked gasoline reaction.
Hydrodesulfurization condition is：260 DEG C of reaction temperature, reaction pressure 1.6MPa, volume space velocity 2.2h-1, hydrogen oil body Product compares 240:1.Sample analysis after reaction about 60h, the reactor product property of catalyst 1 is as follows：Product desulfurization degree 80.3%, alkene drop Amount 3.0%, loss of octane number is 0.6 unit.Hydrobon catalyst loss of octane number is low, and desulfurization degree is high, catalyst activity It is good.
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 embodiment 1 zinc-aluminium mol ratio is identical, and similarity condition is aging, washs, be dried, roasting obtains the oxide material containing zinc-aluminium.Zinc oxide contains Measure as 65%；Specific surface area is 141m2/g.Compared with comparative example 1, embodiment 1 is using pH swing method zinc, the alternating drop of aluminum solutions It is fixed, zinc-aluminium stratified material can be obtained, under the conditions of bi-material zinc-aluminium mol ratio identical, embodiment 1 contains gahnite Zinc oxide stratified material specific surface area it is higher.
Boric acid 1.18g, potassium nitrate 1.7g are weighed respectively, and strontium nitrate 1.51g is dissolved completely in be made in 56g distilled water and contains The aqueous solution of boron, potassium strontium.5.6g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.4g mass concentrations are 65% Acid.Oxide materials of the 30g containing zinc-aluminium and 112.6g boehmites ground and mixed is uniform, 6.0g sesbania powders are added, gather PAA acid solution, boracic, potassium, the aqueous solution of strontium, kneading, after shaping, 135 DEG C of dried process 6 hours, roasting at 550 DEG C Process obtains carrier in 6 hours.15.66g ammonium molybdate 13.44g are taken, cobalt nitrate is added in 20ml distilled water, add ammoniacal liquor to adjust After pH value makes salt all dissolve, then deionized water dilution, maceration extract impregnated carrier is made into, the catalyst precursor for obtaining exists In 600 DEG C of roasting 5h after 110 DEG C of drying, comparative catalyst 1 is obtained.
Comparative catalyst 1 is fitted in 10ml fixed bed reactors, carries out evaluating catalyst reaction performance.With sulfurized oil pair The catalyst carries out presulfurization, and sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%；Sulfide stress is 2.8MPa, hydrogen to oil volume ratio is 300, and sulfurized oil volume space velocity is 3.0h-1, sulfuration program is for respectively in 220 DEG C, 280 DEG C of sulfurations Process 6h.After vulcanizing treatment terminates, full cut FCC gasoline replacement Treatment 8h is switched to, after pre-vulcanization process terminates, be adjusted to Reaction process condition, enters catalytically cracked gasoline reaction.
Hydrodesulfurization condition is：260 DEG C of reaction temperature, reaction pressure 1.6MPa, volume space velocity 2.2h-1, hydrogen oil body Product compares 240:1.Sample analysis after reaction about 60h, the reactor product property of comparative catalyst 1 is as follows：Product desulfurization degree 71.5%, alkene Hydrocarbon drop amount 4.2%, loss of octane number is 0.9 unit.
Embodiment 2
The preparation method and step of the zinc oxide-alumina complex carrier containing auxiliary agent is 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.It is different It is to obtain after complex carrier, surface modification, concrete mistake is carried out to the zinc oxide-alumina complex carrier containing auxiliary agent using potassium and strontium Journey comprises the steps：Configuration, as maceration extract, weighs respectively potassium nitrate 3.0g, strontium nitrate containing potassium nitrate and the strontium nitrate aqueous solution 3.0g, in being dissolved completely in 30ml distilled water, then deionized water dilution, it is made into maceration extract oxide impregnation zinc-alumina composite Carrier, drying, roasting obtain used additives potassium and strontium and carry out the zinc oxide-alumina complex carrier of surface modification.The compound load Surface area per unit volume accumulates 233m2/g。
Ammonium molybdate, cobalt nitrate are made into into maceration extract, adding ammoniacal liquor to adjust pH value makes salt impregnate used additives potassium after all dissolving With the zinc oxide-alumina complex carrier that strontium carries out surface modification, concrete steps are with embodiment 1.It is dried 5 hours at 120 DEG C, Roasting 7 hours at 550 DEG C, obtain Hydrobon catalyst 2.Catalyst 2 is mainly constituted：The wt% of cobalt oxide 3, molybdenum oxide 7wt%, Used additives potassium and strontium carry out the zinc oxide-alumina complex carrier 90wt % of surface modification.
Catalyst 2 is fitted in 10ml fixed bed reactors, carries out evaluating catalyst reaction performance.With sulfurized oil to catalysis Agent carries out presulfurization, and pre-vulcanization process is with embodiment 1.Hydrodesulfurization condition is：230 DEG C of temperature of reactor, reaction pressure 1.4MPa, volume space velocity 2.5h-1, hydrogen to oil volume ratio 250:1.Sample analysis after reaction about 60h, catalyst reaction product property is such as Under：Product desulfurization degree 81.0%, alkene drop amount 2.0%, loss of octane number is 0.3 unit.Hydrobon catalyst octane number is damaged Lose low, desulfurization degree height, good catalyst activity.
Embodiment 3
The preparation method and step of the zinc oxide-alumina complex carrier containing auxiliary agent is 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%；Specific surface Product is 214m2/g。
Complex carrier includes the zinc oxide 17wt% containing gahnite, and alumina content is 80 wt%, adjuvant component boron, Potassium and content of strontium are respectively B2O31.2 wt %, K2The wt % of O 0.9, SrO 0.9 wt %.Complex carrier specific surface area 259m2/ g。
Ammonium molybdate, cobalt nitrate are made into into maceration extract, adding ammoniacal liquor to adjust pH value makes salt impregnate used additives potassium after all dissolving With the zinc oxide-alumina complex carrier that strontium carries out surface modification, concrete steps are with embodiment 1.It is dried 4 hours at 130 DEG C, Roasting 6 hours at 600 DEG C, obtain Hydrobon catalyst 3.Catalyst 3 is mainly constituted：The wt% of cobalt oxide 2.5, molybdenum oxide 8wt%, the zinc oxide-alumina complex carrier 89.5wt % containing auxiliary agent.
Catalyst 3 is fitted in 10ml fixed bed reactors, carries out evaluating catalyst reaction performance.With sulfurized oil to catalysis Agent carries out presulfurization, and pre-vulcanization process is with embodiment 1.Hydrodesulfurization condition is：280 DEG C of reaction temperature, reaction pressure 2.2MPa, volume space velocity 2.7h-1, hydrogen to oil volume ratio 280:1.Sample analysis after reaction about 60h, catalyst reaction product property is such as Under：Product desulfurization degree 82.4%, alkene drop amount 3.8%, loss of octane number is 0.5 unit.Hydrobon catalyst octane number is damaged Lose low, desulfurization degree height, good catalyst activity.
Embodiment 4
The preparation method and step of the zinc oxide-alumina complex carrier containing auxiliary agent is 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%；Specific surface Product is 213m2/g。
Complex carrier includes the wt% of zinc oxide 31 containing gahnite, and alumina content is 66 wt%, adjuvant component boron, Potassium and content of strontium are respectively B2O30.9 wt %, K2The wt % of O 1.0, SrO 1.1wt %.Complex carrier specific surface area 242m2/ g。
Ammonium molybdate, cobalt nitrate are made into into maceration extract, adding ammoniacal liquor to adjust pH value makes salt impregnate used additives potassium after all dissolving With the zinc oxide-alumina complex carrier that strontium carries out surface modification, concrete steps are with embodiment 1.It is dried 5 hours at 120 DEG C, Roasting 7 hours at 550 DEG C, obtain Hydrobon catalyst 4.Catalyst 4 is mainly constituted：The wt% of cobalt oxide 2.5, molybdenum oxide 6.5wt%, the zinc oxide-alumina complex carrier 91wt % containing auxiliary agent.
Catalyst 4 is fitted in 10ml fixed bed reactors, carries out evaluating catalyst reaction performance.With sulfurized oil to catalysis Agent carries out presulfurization, and pre-vulcanization process is with embodiment 1.Hydrodesulfurization condition is：250 DEG C of reaction temperature, reaction pressure 1.8MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio 220:1.Sample analysis after reaction about 60h, catalyst reaction product property is such as Under：Product desulfurization degree 80.2%, alkene drop amount 3.2%, loss of octane number is 0.5 unit.Hydrobon catalyst octane number is damaged Lose low, desulfurization degree height, good catalyst activity.
Embodiment 5
The preparation method and step of the zinc oxide-alumina complex carrier containing auxiliary agent is 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%；Specific surface Product is 191m2/g。
Complex carrier includes the wt% of zinc oxide 23 containing gahnite, and alumina content is 75 wt%, auxiliary agent
Component boron, potassium and content of strontium are respectively B2O30.8 wt %, K2The wt % of O 0.7, SrO 0.5wt %.Complex carrier compares table Area 284m2/g。
Except that obtaining after complex carrier, the zinc oxide-alumina complex carrier containing auxiliary agent is entered using potassium and strontium Row surface modification, detailed process comprises the steps：Configuration, as maceration extract, is weighed respectively containing potassium nitrate and the strontium nitrate aqueous solution Potassium nitrate 2.1g, strontium nitrate 2.2g are dissolved completely in 50g distilled water the aqueous solution being made into containing potassium and strontium, oxide impregnation zinc-oxygen Change aluminium complex carrier, drying, roasting obtain used additives potassium and strontium and carry out the zinc oxide-alumina complex carrier of surface modification.
Ammonium molybdate, cobalt nitrate are made into into maceration extract, adding ammoniacal liquor to adjust pH value makes salt impregnate used additives potassium after all dissolving With the zinc oxide-alumina complex carrier that strontium carries out surface modification, concrete steps are with embodiment 1.It is dried 5 hours at 130 DEG C, Roasting 6 hours at 600 DEG C, obtain Hydrobon catalyst 5.Catalyst 5 is mainly constituted：The wt% of cobalt oxide 3, molybdenum oxide 9wt%, Zinc oxide-alumina complex carrier 88wt % containing auxiliary agent.
Catalyst 5 is fitted in 10ml fixed bed reactors, carries out evaluating catalyst reaction performance.With sulfurized oil to catalysis Agent carries out presulfurization, and pre-vulcanization process is with embodiment 1.Hydrodesulfurization condition is：300 DEG C of reaction temperature, reaction pressure 2.0MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 300:1.Sample analysis after reaction about 60h, catalyst reaction product property is such as Under：Product desulfurization degree 83.8%, alkene drop amount 3.0%, loss of octane number is 0.3 unit.Hydrobon catalyst octane number is damaged Lose low, desulfurization degree height, good catalyst activity.
In order to investigate the stability of catalyst, catalyst 1,2 and 5 is respectively charged in 10ml fixed bed reactors, is carried out Evaluate catalyst reaction performance.Presulfurization is carried out to catalyst with sulfurized oil, pre-vulcanization process is with embodiment 1.Hydrodesulfurization work Skill condition is：230 DEG C of temperature of reactor, reaction pressure 1.4MPa, volume space velocity 2.5h-1, hydrogen to oil volume ratio 250：1.Reaction fortune Row 400h sample analysis, Hydrobon catalyst 1,2 and 5 product desulfurization degrees are respectively 77%, 80% and 82%, loss of octane number point Not Wei 0.4 unit, 0.2 unit and 0.1 unit, carbon deposition rate is respectively 3.1,2.2 and 2.0, and catalyst reaction performance is steady Fixed, active component is not easily runed off, and carbon deposition rate is low, illustrates that catalyst HDS has good stability.
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 (9)

1. a kind of hydrodesulfurizationprocess process of catalytically cracked gasoline, it is characterised in that adopt fixed bed reactors；The catalyst is Supported cobalt molybdenum catalyst, the carrier of catalyst is the zinc oxide-alumina complex carrier containing auxiliary agent, and the composition of catalyst is with oxygen Compound quality meter, including following component：Active component cobalt oxide 0.5-10 wt%, molybdenum oxide 0.5-12 wt%, the oxygen containing auxiliary agent Change zinc-alumina composite carrier 78-94 wt %；Hydrodesulfurization condition is：Reaction temperature 180-310 DEG C, reaction pressure 1.5-2.5MPa, volume space velocity 1.5-3.5h-1, hydrogen to oil volume ratio 180-400:1.
2. hydrodesulfurizationprocess process according to claim 1, it is characterised in that the active component cobalt oxide 1.5-4.5 Wt%, molybdenum oxide 1-8 wt%；The zinc oxide-alumina complex carrier containing auxiliary agent include containing gahnite zinc oxide, Aluminum oxide, adjuvant component boron, potassium and strontium, the composition of complex carrier is with oxidation material gauge：Zinc oxide containing gahnite contains Measure as 5-40 wt%, alumina content is 65-85 wt%, the content of adjuvant component boron, potassium and strontium is respectively B2O3 0.5-1.5 Wt %, K2O 0.3-2.5 wt %, SrO 0.2-2.5 wt %；Reaction temperature 200-280 DEG C, volume space velocity 1.4-3.0h-1, hydrogen Oil volume compares 200-300:1.
3. hydrodesulfurizationprocess process according to claim 1, it is characterised in that the preparation method of the catalyst includes as follows Step：Soluble-salt containing cobalt and molybdenum is made into into maceration extract, dipping is containing auxiliary agent after adding ammoniacal liquor regulation pH value salt is all dissolved Zinc oxide-alumina complex carrier, roasting 6-8 hours at 4-6 hours, 550-650 DEG C are dried at 110-150 DEG C, obtain Hydrobon catalyst.
4. hydrodesulfurizationprocess process according to claim 1, it is characterised in that the preparation method of the complex carrier include as Lower step：Soluble salt solutions containing aluminium and zinc-containing solution are alternately titrated through non-constant pH, is prepared containing gahnite Zinc oxide stratified material；Zinc oxide containing gahnite and boehmite are well mixed, sesbania powder, nitric acid is added The acid solution containing Sodium Polyacrylate after acidification, and the aqueous solution of boric acid, potassium nitrate and strontium nitrate, kneading, after shaping, 110-140 DEG C of dried process 5-9 hour, calcination process 5-7 hour obtains the zinc oxide-oxidation containing auxiliary agent at 550 DEG C -750 DEG C Aluminium complex carrier.
5. hydrodesulfurizationprocess process according to claim 2, it is characterised in that the zinc oxide material containing gahnite Preparation method comprise the steps：Soluble Zn salting liquid is divided into into 2-4 parts, under the conditions of 40-80 DEG C, in a zinc solution In the mixed solution containing aluminium of middle addition sodium metaaluminate and sodium carbonate, dropwise addition is stopped when pH value reaches 8.5-9.5 and mixes molten containing aluminium Liquid；It is further continued for that another zinc solution is added dropwise；After zinc solution is dripped, continue that mixed solution containing aluminium is added dropwise, when pH value reaches Stop that mixed solution containing aluminium is added dropwise during 8.5-9.5；To contain aluminium mixed solution according to said method and replace titration with zinc solution, until Zinc solution whole completion of dropping, last time is added dropwise mixed solution containing aluminium, when pH value reaches 8.5-9.5, non-constant pH value Alternating titration process terminate, control titration process complete in 1.0-6h；After 80-95 DEG C of aging 2-8h, cooling washing is extremely Neutrality, 4-10h, 450-550 DEG C of roasting 4-10h are dried at 80-140 DEG C, obtain the homodisperse oxidation containing gahnite Zinc stratified material.
6. hydrodesulfurizationprocess process according to claim 1, it is characterised in that the zinc oxide-alumina containing auxiliary agent is answered The content of carrier surface potassium and strontium is closed higher than complex carrier inside potassium and the content of strontium.
7. hydrodesulfurizationprocess process according to claim 6, it is characterised in that the zinc oxide-alumina containing auxiliary agent is answered The content of conjunction carrier surface potassium and strontium is 1.2-2.5 times of carrier inside potassium and content of strontium.
8. hydrodesulfurizationprocess process according to claim 4, it is characterised in that the nitric acid acidification Sodium Polyacrylate Process is as follows：Deionized water is heated to into 30～95 DEG C, then nitric acid is dissolved in deionized water, add polyacrylic acid Sodium, and dissolve complete, obtain the acid solution containing Sodium Polyacrylate.
9. the hydrodesulfurizationprocess process according to any one of claim 6 or 7, it is characterised in that the preparation of the complex carrier Method comprises the steps：Soluble salt solutions containing aluminium and zinc-containing solution are alternately titrated through non-constant pH, is prepared and is contained The zinc oxide stratified material of gahnite；Zinc oxide containing gahnite and boehmite are well mixed, are added The acid solution containing Sodium Polyacrylate after sesbania powder, nitric acid acidification, and the aqueous solution of boric acid, potassium nitrate and strontium nitrate, Kneading, after shaping, 110-140 DEG C of dried process 5-9 hour, calcination process 5-7 hour is obtained containing auxiliary agent at 550 DEG C -750 DEG C Zinc oxide-alumina complex carrier, recycles potassium and strontium to carry out surface to the zinc oxide-alumina complex carrier containing auxiliary agent and repaiies Decorations, detailed process comprises the steps：Configuration is containing potassium nitrate and the strontium nitrate aqueous solution as maceration extract oxidation of the dipping containing auxiliary agent Zinc-alumina composite carrier, drying, roasting obtain used additives potassium and strontium and carry out the zinc oxide-oxygen containing auxiliary agent of surface modification Change aluminium complex carrier.
CN201611205747.6A 2016-12-23 2016-12-23 A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline Active CN106635135B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611205747.6A CN106635135B (en) 2016-12-23 2016-12-23 A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611205747.6A CN106635135B (en) 2016-12-23 2016-12-23 A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline

Publications (2)

Publication Number Publication Date
CN106635135A true CN106635135A (en) 2017-05-10
CN106635135B CN106635135B (en) 2018-08-14

Family

ID=58827834

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611205747.6A Active CN106635135B (en) 2016-12-23 2016-12-23 A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline

Country Status (1)

Country Link
CN (1) CN106635135B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109423326A (en) * 2017-08-31 2019-03-05 中国石油天然气股份有限公司 A kind of hydrodesulfurizationprocess process of FCC gasoline
CN109423324A (en) * 2017-08-31 2019-03-05 中国石油天然气股份有限公司 A kind of method of FCC gasoline removal of mercaptans
CN109423325A (en) * 2017-08-31 2019-03-05 中国石油天然气股份有限公司 A kind of desulfuration processing method of catalytically cracked gasoline
CN109420504A (en) * 2017-08-31 2019-03-05 中国石油天然气股份有限公司 A kind of catalytic cracking gasoline hydrodesulfurization catalyst and preparation method
CN110935460A (en) * 2018-09-21 2020-03-31 中国石油天然气股份有限公司 High-selectivity hydrodesulfurization catalyst and preparation method thereof
CN115216352A (en) * 2021-04-15 2022-10-21 中国石油化工股份有限公司 Method for producing polypropylene raw material by liquefied petroleum gas desulfurization

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1123310A (en) * 1994-11-25 1996-05-29 中国石化齐鲁石油化工公司 Hydrodevulcanizing catalyst for hydro-carbons and preparation method thereof
CN1458236A (en) * 2002-05-15 2003-11-26 中国石油化工股份有限公司 Process for preparing demetalizing and desulfurizing catalyst of heavy oil hydrogenation
CN102166521A (en) * 2010-02-25 2011-08-31 中国石油天然气股份有限公司 Preparation method of hydrofining catalyst
CN103449503A (en) * 2012-06-01 2013-12-18 中国石油天然气股份有限公司 Method for preparing nanometer gahnite
CN104437578A (en) * 2013-09-16 2015-03-25 中国石油化工股份有限公司 Hydrodesulfurization catalyst, preparation method and applications thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1123310A (en) * 1994-11-25 1996-05-29 中国石化齐鲁石油化工公司 Hydrodevulcanizing catalyst for hydro-carbons and preparation method thereof
CN1458236A (en) * 2002-05-15 2003-11-26 中国石油化工股份有限公司 Process for preparing demetalizing and desulfurizing catalyst of heavy oil hydrogenation
CN102166521A (en) * 2010-02-25 2011-08-31 中国石油天然气股份有限公司 Preparation method of hydrofining catalyst
CN103449503A (en) * 2012-06-01 2013-12-18 中国石油天然气股份有限公司 Method for preparing nanometer gahnite
CN104437578A (en) * 2013-09-16 2015-03-25 中国石油化工股份有限公司 Hydrodesulfurization catalyst, preparation method and applications thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109423326A (en) * 2017-08-31 2019-03-05 中国石油天然气股份有限公司 A kind of hydrodesulfurizationprocess process of FCC gasoline
CN109423324A (en) * 2017-08-31 2019-03-05 中国石油天然气股份有限公司 A kind of method of FCC gasoline removal of mercaptans
CN109423325A (en) * 2017-08-31 2019-03-05 中国石油天然气股份有限公司 A kind of desulfuration processing method of catalytically cracked gasoline
CN109420504A (en) * 2017-08-31 2019-03-05 中国石油天然气股份有限公司 A kind of catalytic cracking gasoline hydrodesulfurization catalyst and preparation method
CN109423324B (en) * 2017-08-31 2021-01-29 中国石油天然气股份有限公司 Method for removing mercaptan from FCC gasoline
CN109423325B (en) * 2017-08-31 2021-01-29 中国石油天然气股份有限公司 Desulfurization treatment method for catalytically cracked gasoline
CN109423326B (en) * 2017-08-31 2021-07-30 中国石油天然气股份有限公司 Hydrodesulfurization method of FCC gasoline
CN109420504B (en) * 2017-08-31 2021-08-27 中国石油天然气股份有限公司 Catalytic gasoline hydrodesulfurization catalyst and preparation method thereof
CN110935460A (en) * 2018-09-21 2020-03-31 中国石油天然气股份有限公司 High-selectivity hydrodesulfurization catalyst and preparation method thereof
CN115216352A (en) * 2021-04-15 2022-10-21 中国石油化工股份有限公司 Method for producing polypropylene raw material by liquefied petroleum gas desulfurization
CN115216352B (en) * 2021-04-15 2024-02-09 中国石油化工股份有限公司 Method for producing polypropylene raw material by desulfurizing liquefied petroleum gas

Also Published As

Publication number Publication date
CN106635135B (en) 2018-08-14

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
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
CN106179381B (en) The preparation method of Hydrobon catalyst
CN106179414B (en) A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof
CN106955746A (en) A kind of complex carrier of the aluminum oxide containing zinc oxide and preparation method thereof
CN106867577B (en) A kind of method for gasoline desulfurization
CN106807420A (en) A kind of catalyst and preparation method for petroleum naphtha hydrogenation dearsenification
CN106732632A (en) A kind of Hydrobon catalyst and preparation method
CN1766047A (en) Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method
CN106622319B (en) A kind of zinc-aluminium stratified material and preparation method
CN106732516A (en) A kind of zinc oxide aluminium complex carrier and preparation method containing auxiliary agent
CN106833731A (en) A kind of hydro-dearsenic method of naphtha
CN106179382B (en) A kind of preparation method of body phase hydrotreating catalyst
CN107511143A (en) A kind of renovation process of adsorption desulfurizing agent
CN101590416A (en) Molybdenum-nickel hydrogenation catalyst and preparation method thereof
CN106881127A (en) A kind of catalyst and preparation method for gasoline desulfurization modification
CN106929091B (en) A kind of catalytic gasoline hydrogenation desulfurization method for modifying
CN106179388A (en) A kind of preparation method of hydrotreating catalyst
CN106925309A (en) A kind of catalyst for gasoline hydrodesulfurizationmethod and preparation method thereof
CN107511128B (en) Pretreatment method of adsorption desulfurizer
CN105289681B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN106925338A (en) Carry sulfur type hydrodesulfurizationmodification modification catalyst and preparation method
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