CN106732632A - A kind of Hydrobon catalyst and preparation method - Google Patents

A kind of Hydrobon catalyst and preparation method Download PDF

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Publication number
CN106732632A
CN106732632A CN201611205786.6A CN201611205786A CN106732632A CN 106732632 A CN106732632 A CN 106732632A CN 201611205786 A CN201611205786 A CN 201611205786A CN 106732632 A CN106732632 A CN 106732632A
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China
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zinc oxide
zinc
strontium
complex carrier
potassium
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Inventor
牟晓红
周艳青
夏德强
唐蓉萍
田苗
郑晓明
王守伟
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Lanzhou Petrochemical College of Vocational Technology
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Lanzhou Petrochemical College of Vocational Technology
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    • 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
    • B01J23/882—Molybdenum and cobalt
    • 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
    • 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
    • C10G2300/70—Catalyst aspects

Abstract

The present invention relates to a kind of Hydrobon catalyst and preparation method, the composition of catalyst is with oxidation material gauge, including following component：The wt% of active component cobalt oxide 0.5 10, the wt% of molybdenum oxide 0.5 12, the wt % of zinc oxide aluminium complex carrier 78 94 containing auxiliary agent.Hydrobon catalyst loss of octane number is low, and desulfurization degree is high.

Description

A kind of Hydrobon catalyst and preparation method
Technical field
It is more specifically a kind of with the oxidation containing auxiliary agent the present invention relates to a kind of Hydrobon catalyst and preparation method Zinc-alumina composite material is the FCC Hydrobon catalysts and preparation method of carrier.
Background technology
Because the general sulfur content of catalytically cracked gasoline is in 100-500v%, or even also high-sulfur, olefin feedstock high 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, and this requires to be tried one's best while Hydrobon catalyst desulfurization and is avoided 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 high temperature is widely used in a series of good characteristics 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.The conventional preparation method of the domestic and international 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, stronger by the reacting generation interaction in preparation process of aluminum and zinc by precipitation or peptization The zinc oxide during use can be avoided to be lost in, but the specific surface area that peptisation prepares material is minimum, makes it 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 acid, such as zinc oxide, the method for being used 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 specific surface area 74m after material is calcined at 704 DEG C2/g.Two methods sintering temperature It is higher, prepare zinc-aluminium material specific surface area relatively 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 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）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, dry, 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.The zinc-aluminium proportioning that the method feeds intake is relatively low and preparation process adds expanding agent, only Gahnite is obtained, not comprising dispersed zinc oxide.
CN201310625314.6 (CN103691441) discloses a kind of strong absorption, high visible degradation property photocatalysis The preparation method of material, the invention is related to one kind ternary houghite to be presoma, 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 salting liquid and aqueous slkali respectively, under 80 DEG C and magnetic agitation, is mixed with constant flow pump；Reaction mixture It is transferred in hydrothermal reaction kettle, in hydro-thermal process 5-10h at 130-180 DEG C；Suction filtration, wash, be drying to obtain presoma, by forerunner It is put into Muffle furnace and is calcined 2-6 hour at 400-600 DEG C, obtain final product product, zinc, nickel, aluminium ion mol ratio is 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 more long.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 40-75 DEG C and pH value 7.0-7.5 of temperature for controlling whole reaction system The lower zinc oxide precursor basic zinc carbonate for producing co-precipitation generation to adulterate, 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 It is 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 hydroxide In the mixed solution of sodium and sodium carbonate, the coprecipitated product for obtaining is calcined 6-8h at 400-600 DEG C, and zinc is prepared by coprecipitation Mangnesium-aluminium-cerium houghite, zinc, magnesium, three kinds of mol ratios of metal 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 composition is：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, is that to use the soluble-salt and alkali of metal be raw material, and being reacted by fractional precipitation makes composition LDH layers 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- More long 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 more long.《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 with identical speed respectively, is added again after being well mixed Enter 16% sodium hydroxide solution, the pH value for adjusting solution is 8.6, after the sediment of generation is through aging 15 min, add a small amount of 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 be heavy Starch dries 4 h at 120 DEG C, and 2 h are calcined at 700 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 Hydrobon catalyst and preparation method, and the carrier of Hydrobon catalyst is containing auxiliary agent Zinc oxide-alumina complex carrier, active component includes cobalt oxide and molybdenum oxide.The complex carrier zinc-aluminium is uniformly dispersed, compares table Area is high.Hydrobon catalyst loss of octane number is low, and desulfurization degree is high.
The composition of catalyst of the present invention is with oxidation material gauge, including following component：Active component cobalt oxide 0.5- 10 wt%, preferably 1.5-4.5 wt%, molybdenum oxide 0.5-12 wt%, preferably 1-8 wt%, the zinc oxide-alumina containing auxiliary agent are combined Carrier 78-94 wt %.
The Hydrobon catalyst preparation method comprises the following steps：Soluble-salt containing cobalt and molybdenum is made into dipping Liquid, zinc oxide-alumina complex carrier of the dipping containing auxiliary agent after adding ammoniacal liquor regulation pH value to make salt all dissolve, in 110-150 Dried at DEG C and be calcined 6-8 hours at 4-6 hours, 550-650 DEG C, obtain Hydrobon catalyst.
Zinc oxide-alumina complex carrier containing auxiliary agent of the present invention, adjuvant component is boron, potassium and strontium, and zinc oxide is Zinc oxide stratified material containing gahnite.Soluble salt solutions and zinc-containing solution containing aluminium are alternately dripped by 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 is 5-40 wt%, and preferably 10-30 wt%, alumina content is 65-85 wt%, preferably 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 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, 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 dried process 5-9 hours, 550 DEG C -750 Obtain within calcination process 5-7 hours at DEG C the zinc oxide-alumina complex carrier containing auxiliary agent.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 30~95 DEG C, then by nitric acid It is dissolved into deionized water, adds Sodium Polyacrylate, and dissolve complete, obtains the acid solution containing Sodium Polyacrylate.Through peracid Change the Sodium Polyacrylate for the treatment of, 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, by 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 controlling the content of zinc oxide 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 following steps：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 In mixed solution containing aluminium, stop 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 1.0-6h.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.
Soluble zinc salt of the present invention can be 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 The foramen magnum-mesoporous duct in internal portion has connectivity, rather than blind bore structure.
Zinc oxide-alumina complex carrier preparation method containing auxiliary agent of the present invention, it is preferably sharp after obtaining complex carrier Surface modification is carried out to the zinc oxide-alumina complex carrier containing auxiliary agent with potassium and strontium, detailed process comprises the following steps：Configuration Containing potassium nitrate and the strontium nitrate aqueous solution as maceration extract zinc oxide-alumina complex carrier of the dipping containing auxiliary agent, through drying, roasting Obtaining used additives potassium and strontium carries out the zinc oxide-alumina complex carrier of surface modification.Control zinc oxide-alumina complex carrier 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 zinc oxide or zinc oxide containing gahnite.Compared with prior art, the zinc oxide containing gahnite of the invention is By non-constant pH, alternately prepared by titration, i.e., the friendship of sodium carbonate liquor and zinc-containing solution under non-constant pH value condition, containing aluminium Prepared for titration, accordingly, it would be desirable to zinc-containing solution is divided 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 be swung between soda acid, is conducive to Aluminium zinc precursor thing can orderly accumulation be layer structure, be that can be uniformly dispersed and specific surface area through direct low-temperature bake Can be in 150-220m2The zinc oxide material containing gahnite regulated and controled between/g, it is to avoid using the step of alkaline solution one 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.
After the surface of zinc oxide-alumina complex carrier of the present invention containing auxiliary agent is through potassium and strontium modification, make carrier table The content of the concentration formation concentration difference of the potassium in face and the concentration of strontium and carrier inside potassium and strontium, carrier surface 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 times.Carrier surface is tended 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, so effectively solve the problems, such as to make activity decrease because active component cobalt molybdenum etc. is lost in, good catalyst activity.Potassium and strontium it is dense Degree is unsuitable too high, and the potassium nitrate and the strontium nitrate aqueous solution when preferably configuration concentration is slightly below or slightly above prepares complex carrier enter Row carrier surface is modified.
Brief 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
Traveling one is entered to Hydrobon catalyst of the present invention and preparation method and application with comparative example by the following examples The detailed description of step.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 3 parts, every part of 2L.2L zinc-containing solutions are taken, temperature is kept for 80 DEG C, to Mixed solution containing aluminium to pH value is wherein added dropwise and reaches 9.0；Stop that mixed solution containing aluminium is added dropwise, then 2L zinc-containing solutions to mixing are added dropwise In system, continue dropwise addition mixed solution containing aluminium to pH value and reach 9.0；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 dries 3h to compound to neutrality in 135 DEG C of air atmospheres, and 9h is calcined at 500 DEG C, obtains The dispersed zinc oxide stratified material containing gahnite, in terms of oxide, the content of zinc oxide is 65%；Specific surface area It is 196m2/g。
Weigh boric acid 1.18g, potassium nitrate 1.7g respectively, strontium nitrate 1.51g is dissolved completely in 56g distilled water to be made into 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.By 30g, zinc oxide and 112.6g boehmites ground and mixed containing gahnite are uniform, add 6.0g sesbania powders, 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 treatment 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 0.7 wt % of wt %, SrO of O 0.7.
Take 15.66g ammonium molybdates, 13.44g cobalt nitrates to be added in 20ml distilled water, add ammoniacal liquor regulation pH value to make salt complete After portion's dissolving, then diluted with deionized water, be made into maceration extract zinc oxide-alumina complex carrier of the dipping containing auxiliary agent, obtained Catalyst precursor is calcined 5h after being dried at 110 DEG C at 600 DEG C, obtains catalyst 1.Catalyst 1 is mainly constituted：Cobalt oxide 3 Wt%, molybdenum oxide 10wt%, the zinc oxide-alumina complex carrier 87wt % containing auxiliary agent.
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, dry, roasting obtains the oxide material containing zinc-aluminium.Zinc oxide contains Measure is 65%；Specific surface area is 141m2/g.Compared with comparative example 1, embodiment 1 is using pH swing methods zinc, the alternating drop of aluminum solutions It is fixed, zinc-aluminium stratified material can be obtained, under the conditions of two kinds of material zinc-aluminium mol ratio identicals, embodiment 1 contains gahnite Zinc oxide stratified material specific surface area it is higher.
Weigh boric acid 1.18g, potassium nitrate 1.7g respectively, strontium nitrate 1.51g is dissolved completely in 56g distilled water to be made into 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.By 30g, oxide material and 112.6g boehmites ground and mixed containing zinc-aluminium are uniform, add 6.0g sesbania powders, gather PAA acid solution, boracic, the aqueous solution of potassium strontium, kneading, after shaping, 135 DEG C of dried process 6 hours, at 550 DEG C at roasting Reason obtains carrier in 6 hours.15.66g ammonium molybdate 13.44g are taken, cobalt nitrate is added in 20ml distilled water, add ammoniacal liquor regulation pH After value makes salt all dissolve, then diluted with deionized water, be made into maceration extract impregnated carrier, the catalyst precursor for obtaining is 110 DEG C drying after 600 DEG C be calcined 5h, obtain comparative catalyst 1.
Embodiment 2
The preparation method and step of the zinc oxide-alumina complex carrier containing auxiliary agent 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.It is different It is after obtaining complex carrier, surface modification, specific mistake to be carried out to the zinc oxide-alumina complex carrier containing auxiliary agent using potassium and strontium Journey comprises the following steps：Configuration, as maceration extract, weighs potassium nitrate 3.0g, strontium nitrate respectively containing potassium nitrate and the strontium nitrate aqueous solution 3.0g, is dissolved completely in 30ml distilled water, then is diluted with deionized water, is made into maceration extract oxide impregnation zinc-alumina composite Carrier, obtains used additives potassium and strontium and carries out the zinc oxide-alumina complex carrier of surface modification through drying, roasting.The compound load Surface area per unit volume accumulates 233m2/g。
Ammonium molybdate, cobalt nitrate are made into maceration extract, add ammoniacal liquor regulation pH value salt is impregnated used additives potassium after all dissolving With the zinc oxide-alumina complex carrier that strontium carries out surface modification, specific steps are with embodiment 1.Dried 5 hours at 120 DEG C, It is calcined 7 hours at 550 DEG C, obtains Hydrobon catalyst 2.Catalyst 2 is mainly constituted：Cobalt oxide 3 wt%, molybdenum oxide 7wt%, Used additives potassium and strontium carry out the zinc oxide-alumina complex carrier 90wt % of surface modification.
Embodiment 3
The preparation method and step of the zinc oxide-alumina complex carrier containing auxiliary agent 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%；Specific surface Product is 214m2/g。
Complex carrier include containing gahnite zinc oxide 17wt%, alumina content be 80 wt%, adjuvant component boron, Potassium and content of strontium are respectively B2O31.2 wt %, K2The 0.9 wt % of wt %, SrO of O 0.9.Complex carrier specific surface area 259m2/ g。
Ammonium molybdate, cobalt nitrate are made into maceration extract, add ammoniacal liquor regulation pH value salt is impregnated used additives potassium after all dissolving With the zinc oxide-alumina complex carrier that strontium carries out surface modification, specific steps are with embodiment 1.Dried 4 hours at 130 DEG C, It is calcined 6 hours at 600 DEG C, obtains 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.
Embodiment 4
The preparation method and step of the zinc oxide-alumina complex carrier containing auxiliary agent 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%；Specific surface Product is 213m2/g。
Complex carrier include containing gahnite the wt% of zinc oxide 31, alumina content be 66 wt%, adjuvant component boron, Potassium and content of strontium are respectively B2O30.9 wt %, K2Wt %, the SrO 1.1wt % of O 1.0.Complex carrier specific surface area 242m2/ g。
Ammonium molybdate, cobalt nitrate are made into maceration extract, add ammoniacal liquor regulation pH value salt is impregnated used additives potassium after all dissolving With the zinc oxide-alumina complex carrier that strontium carries out surface modification, specific steps are with embodiment 1.Dried 5 hours at 120 DEG C, It is calcined 7 hours at 550 DEG C, obtains 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.
Embodiment 5
The preparation method and step of the zinc oxide-alumina complex carrier containing auxiliary agent 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%；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 %, K2Wt %, the SrO 0.5wt % of O 0.7.Complex carrier compares table Area 284m2/g。
Except that after obtaining complex carrier, being entered to the zinc oxide-alumina complex carrier containing auxiliary agent using potassium and strontium Row surface modification, detailed process comprises the following 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 made into the aqueous solution containing potassium and strontium, oxide impregnation zinc-oxygen in being dissolved completely in 50g distilled water Change aluminium complex carrier, obtain used additives potassium and strontium and carry out the zinc oxide-alumina complex carrier of surface modification through drying, roasting.
Ammonium molybdate, cobalt nitrate are made into maceration extract, add ammoniacal liquor regulation pH value salt is impregnated used additives potassium after all dissolving With the zinc oxide-alumina complex carrier that strontium carries out surface modification, specific steps are with embodiment 1.Dried 5 hours at 130 DEG C, It is calcined 6 hours at 600 DEG C, obtains Hydrobon catalyst 5.Catalyst 5 is mainly constituted：Cobalt oxide 3 wt%, molybdenum oxide 9wt%, Zinc oxide-alumina complex carrier 88wt % containing auxiliary agent.
Catalyst 1-5, comparative catalyst 1 are respectively charged into 10ml fixed bed reactors, evaluation catalyst reaction is carried out Performance.Presulfurization is carried out to catalyst with sulfurized oil, sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%； Sulfide stress is 2.8MPa, and hydrogen to oil volume ratio is 300, and sulfurized oil volume space velocity is 3.0h-1, vulcanization program for respectively 220 DEG C, 280 DEG C of vulcanizing treatment 6h.After vulcanizing treatment terminates, full cut FCC gasoline replacement Treatment 8h is switched to, treat that pre-vulcanization process terminates Afterwards, reaction process condition is adjusted to, enters catalytically cracked gasoline reaction.Reaction process 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.Sampling analysis after reaction about 60h, catalyst and contrast medium react Product property is shown in Table 1.As can be seen from Table 1, Hydrobon catalyst loss of octane number is low, and desulfurization degree is high, good catalyst activity. Study on the stability is carried out to catalyst 1,2,5, reaction runs 400h, and Hydrobon catalyst 1,2 and 5 product desulfurization degrees are respectively 77%th, 80% and 82%, loss of octane number is respectively 0.4 unit, 0.2 unit and 0.1 unit, carbon deposition rate is respectively 3.1, 2.2 and 2.0, catalyst reaction stable performance, active component is not easily runed off, and carbon deposition rate is low, illustrates catalyst HDS stabilization Property is good.
The catalyst of table 1 and contrast medium reactor product property
Certainly, the present invention can also have other various embodiments, in the case of without departing substantially from spirit of the invention and its essence, be familiar with this The technical staff in field can make various corresponding changes and deformation according to the present invention, but these corresponding changes and deformation all should Belong to protection scope of the present invention.

Claims (9)

1. a kind of Hydrobon catalyst, it is characterised in that the composition of catalyst is with oxidation material gauge, including following component： Active component cobalt oxide 0.5-10 wt%, molybdenum oxide 0.5-12 wt%, the zinc oxide-alumina complex carrier 78-94 containing auxiliary agent wt %。
2. Hydrobon catalyst 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 It is 5-40 wt% to measure, and alumina content is 65-85 wt%, and 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 %.
3. the preparation method of Hydrobon catalyst described in a kind of claim 1, it is characterised in that comprise the following steps：Cobalt will be contained Maceration extract is made into the soluble-salt of molybdenum, zinc oxide-oxygen of the dipping containing auxiliary agent after adding ammoniacal liquor regulation pH value to make salt all dissolve Change aluminium complex carrier, roasting 6-8 hours at 4-6 hour, 550-650 DEG C is dried at 110-150 DEG C, obtain hydrodesulfurization catalytic Agent.
4. Hydrobon catalyst according to claim 1, it is characterised in that the preparation method of the complex carrier includes Following steps：Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, the point containing zinc-aluminium is prepared brilliant The zinc oxide stratified material of stone；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitre is added The acid solution containing Sodium Polyacrylate after sour acidification, and boric acid, potassium nitrate and strontium nitrate the aqueous solution, kneading, shaping Afterwards, 110-140 DEG C dried process 5-9 hours, obtains the zinc oxide-oxygen containing auxiliary agent for calcination process 5-7 hours at 550 DEG C -750 DEG C Change aluminium complex carrier.
5. Hydrobon catalyst according to claim 2, it is characterised in that the zinc oxide material containing gahnite The preparation method of material comprises the following steps：Soluble Zn salting liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, it is molten in a zinc salt Added in liquid in the mixed solution containing aluminium of sodium metaaluminate and sodium carbonate, stop being added dropwise containing aluminium mixing when pH value reaches 8.5-9.5 Solution；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 Mixed solution containing aluminium is added dropwise to stopping during 8.5-9.5；To contain aluminium mixed solution according to the above method and replace titration with zinc solution, directly To 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 The alternating titration process of value terminates, and control titration process is completed in 1.0-6h, after 80-95 DEG C of aging 2-8h, cooling washing To neutral, 4-10h, 450-550 DEG C of roasting 4-10h are dried at 80-140 DEG C, obtain the dispersed oxygen containing gahnite Change zinc stratified material.
6. Hydrobon catalyst according to claim 1, it is characterised in that the zinc oxide-alumina containing auxiliary agent The content of complex carrier surface potassium and strontium is higher than complex carrier inside potassium and the content of strontium.
7. Hydrobon catalyst according to claim 6, it is characterised in that the zinc oxide-alumina containing auxiliary agent The content of complex carrier surface potassium and strontium is 1.2-2.5 times of carrier inside potassium and content of strontium.
8. Hydrobon catalyst according to claim 4, it is characterised in that the nitric acid acidification Sodium Polyacrylate Process it is as follows：Deionized water is heated to 30~95 DEG C, then nitric acid is dissolved into deionized water, add polyacrylic acid Sodium, and dissolve complete, obtain the acid solution containing Sodium Polyacrylate.
9. the Hydrobon catalyst according to any one of claim 6 or 7, it is characterised in that the preparation of the complex carrier Method comprises the following steps：Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, is prepared and is contained The zinc oxide stratified material of gahnite；Zinc oxide and boehmite containing gahnite are well mixed, are added The acid solution containing Sodium Polyacrylate after sesbania powder, nitric acid acidification, and boric acid, potassium nitrate and strontium nitrate the aqueous solution, Kneading, after shaping, 110-140 DEG C dried process 5-9 hours, obtain within calcination process 5-7 hours at 550 DEG C -750 DEG C containing auxiliary agent Zinc oxide-alumina complex carrier, recycles potassium and strontium to carry out surface to the zinc oxide-alumina complex carrier containing auxiliary agent and repair Decorations, detailed process comprises the following steps：The aqueous solution of the configuration containing potassium nitrate and strontium nitrate is used as maceration extract oxygen of the dipping containing auxiliary agent Change zinc-alumina composite carrier, obtain used additives potassium through drying, roasting and strontium carry out the zinc oxide containing auxiliary agent of surface modification- Alumina composite carrier.
CN201611205786.6A 2016-12-23 2016-12-23 A kind of Hydrobon catalyst and preparation method Pending CN106732632A (en)

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Application publication date: 20170531