CN106732516A - A kind of zinc oxide aluminium complex carrier and preparation method containing auxiliary agent - Google Patents
A kind of zinc oxide aluminium complex carrier and preparation method containing auxiliary agent Download PDFInfo
- Publication number
- CN106732516A CN106732516A CN201611205777.7A CN201611205777A CN106732516A CN 106732516 A CN106732516 A CN 106732516A CN 201611205777 A CN201611205777 A CN 201611205777A CN 106732516 A CN106732516 A CN 106732516A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- complex carrier
- zinc
- strontium
- potassium
- 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.)
- Pending
Links
Classifications
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of 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
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of zinc oxide aluminium complex carrier containing auxiliary agent and preparation method, complex carrier includes the zinc oxide containing gahnite, aluminum oxide, adjuvant component boron, potassium and strontium, and the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 5 40 wt%, and alumina content is 65 85 wt%, and adjuvant component boron, potassium and content of strontium are respectively B2O30.5 1.5 wt %, K2The 0.2 2.5 wt % of wt %, SrO of O 0.3 2.5.The complex carrier zinc-aluminium is uniformly dispersed, specific surface area is high.
Description
Technical field
The present invention relates to a kind of zinc oxide-alumina complex carrier containing auxiliary agent and preparation method.The complex carrier can use
In FCC catalyst sulfur prodegradant and FCC hydrodesulfurization carriers.
Background technology
Spinelle type composite oxides are the up-and-coming Inorganic Non-metallic Materials of a class, with a series of good characteristics
And it is widely used in high-temperature material, the field such as catalyst and catalyst carrier.The composite of zinc oxide and aluminum oxide is often made
For desulfurization catalyst material is used to adsorb desulfurization and hydrodesulfurization field.The conventional preparation method of the domestic and international material includes dipping
Method, mechanical mixing, coprecipitation and peptisation.Wherein, because infusion process and mechanical mixing use alumina material conduct
Predecessor, by adjusting the specific surface area of alumina material, both approaches can prepare the composite of high specific surface area,
But because the aluminum oxide in composite and zinc oxide interaction are weaker, the stream of zinc oxide is easily produced during use
Lose, the method for being typically with high-temperature roasting promotes the two to form spinelle to avoid the loss of zinc oxide；And coprecipitation and
Peptisation prepares zinc-aluminium precursor using the compound containing aluminum and zinc by precipitation or peptization, and aluminum and zinc passes through in preparation process
The stronger interaction of reaction generation can avoid the zinc oxide during use from being lost in, but peptisation prepares the ratio table of material
Area is minimum, it is restricted when being used as catalysis material.
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
It is an object of the invention to provide a kind of zinc oxide-alumina complex carrier containing auxiliary agent.By the solubility containing aluminium
Salting liquid and zinc-containing solution are alternately titrated by non-constant pH, prepare the zinc oxide stratified material containing gahnite, the oxygen
Change zinc stratified material again with the kneading such as the soluble-salt of boehmite, adjuvant component boron, potassium and strontium, obtain the oxidation containing auxiliary agent
Zinc-alumina composite carrier.The complex carrier zinc-aluminium is uniformly dispersed, specific surface area is high, is mainly used in FCC catalyst sulfur prodegradant
With FCC hydrodesulfurization carriers.
The present invention provides a kind of zinc oxide-alumina complex carrier containing auxiliary agent, and complex carrier includes containing gahnite
Zinc oxide, aluminum oxide, adjuvant component boron, potassium and strontium, the composition of complex carrier is with oxidation material gauge：Containing gahnite
Zinc oxide content is 5-40 wt%, and preferably 10-30 wt%, alumina content is 65-85 wt%, preferably 70-80 wt%, auxiliary agent group
Boron, potassium and content of strontium is divided to be respectively B2O30.5-1.5 wt %, K2O 0.3-2.5 wt %, SrO 0.2-2.5 wt %.It is compound
Carrier specific surface area 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
Mixed solution containing aluminium, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；Be further continued for be added dropwise another zinc salt it is molten
Liquid；After zinc solution is dripped, continue that mixed solution containing aluminium is added dropwise, stop being added dropwise containing aluminium mixing when pH value reaches 8.5-9.5
Solution；To contain aluminium mixed solution according to the above method and replace titration with zinc solution, until zinc solution whole completion of dropping, finally
Mixed solution containing aluminium is once added dropwise, when pH value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, control drop
Determine process to be completed in 1.0-6h.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 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 hydrodesulfurization
Catalyst, such as cobaltmolybdate catalyst, are conducive to adjusting the acidity of Hydrobon catalyst, and catalytic inner duct knot is improved in finishing
Structure, can reduce the polymerization of alkene in feedstock oil, suppress catalytic inner coking deactivation, and carbon deposition rate is low, improves hydrodesulfurization and urges
The stabilized hydrogenation of agent.Macromolecule polyacrylic acid sodium can arrive ten million according to the difference of the degree of polymerization, molecular weight at thousand grades
Adjusted between level so that aluminum oxide macropore diameter can be adjusted according to molecular size range.Sodium Polyacrylate has ball of string knot
Structure so that the foramen magnum-mesoporous duct of carrier inside 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
The aqueous solution containing potassium nitrate and strontium nitrate through drying, is roasted as maceration extract zinc oxide-alumina complex carrier of the dipping containing auxiliary agent
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 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.
Through potassium and strontium modification, the zinc oxide-alumina complex carrier containing auxiliary agent can be with for carrier surface of the present invention
As the hydrodesulfurization for being used for gasoline after the carrier loaded active component of Hydrobon catalyst.
Present invention also offers a kind of Hydrobon catalyst, the composition of the catalyst with oxidation material gauge, including such as
Lower component：Active component cobalt oxide 0.5-10 wt%, preferably 1.5-4.5 wt%, preferably molybdenum oxide 0.5-12 wt%, 1-8 wt%,
Zinc oxide-alumina complex carrier 78-94 wt % containing auxiliary agent.Hydrobon catalyst loss of octane number is low, and desulfurization degree is high.
Hydrobon catalyst preparation method comprises the following steps：Soluble-salt containing cobalt and molybdenum is made into maceration extract, plus
Entering ammoniacal liquor regulation pH value makes salt impregnate the zinc oxide-alumina complex carrier containing auxiliary agent after all dissolving, and is done at 110-150 DEG C
It is dry 4-6 hours, it is calcined 6-8 hours at 550-650 DEG C, obtain Hydrobon catalyst.
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
Contain zinc oxide-alumina complex carrier and its preparation side of auxiliary agent to the present invention with comparative example by the following examples
Method and application are described in further 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 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 zinc oxide-alumina complex carrier containing auxiliary agent, it is characterised in that complex carrier is included containing gahnite
Zinc oxide, aluminum oxide, adjuvant component boron, potassium and strontium, the composition of complex carrier is with oxidation material gauge：Oxygen containing gahnite
Change Zn content is 5-40 wt%, and alumina content is 65-85 wt%, and adjuvant component boron, potassium and content of strontium are respectively B2O3 0.5-
1.5 wt %, K2O 0.3-2.5 wt %, SrO 0.2-2.5 wt %.
2. complex carrier according to claim 1, it is characterised in that the zinc oxide content containing gahnite is 10-30
Wt%, alumina content is 70-80 wt%.
3. the preparation method of complex carrier described in a kind of claim 1, it is characterised in that comprise the following steps：Will be solvable containing aluminium
Property salting liquid and zinc-containing solution by non-constant pH alternately titrate, prepare the zinc oxide stratified material containing gahnite；Will
Zinc oxide and boehmite containing gahnite be well mixed, add after sesbania powder, nitric acid acidification containing poly- third
The acid solution of olefin(e) acid sodium, and boric acid, potassium nitrate and strontium nitrate etc. the aqueous solution, kneading, after shaping, at 110-140 DEG C of drying
Reason 5-9 hours, obtains the zinc oxide-alumina complex carrier containing auxiliary agent for calcination process 5-7 hours at 550 DEG C -750 DEG C.
4. complex carrier according to claim 1, it is characterised in that the zinc oxide containing gahnite, to aoxidize
Thing meter, the content of zinc oxide is 65-80%；Specific surface area is 170-200m2/g。
5. complex carrier according to claim 1, it is characterised in that the system of the zinc oxide material containing gahnite
Preparation Method comprises the following steps：Soluble Zn salting liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, is added in a zinc solution
Enter the mixed solution containing aluminium of sodium metaaluminate and sodium carbonate, stop that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；Followed by
It is continuous 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 8.5-9.5
When stop be added dropwise mixed solution containing aluminium；To contain aluminium mixed solution according to the above method and replace titration with zinc solution, until zinc salt is molten
Liquid whole completion of dropping, last time is added dropwise mixed solution containing aluminium, when pH value reaches 8.5-9.5, the alternating of non-constant pH value
Titration process terminates, and control titration process is completed in 1.0-6h, after 80-95 DEG C of aging 2-8h, cooling washing to neutrality,
80-140 DEG C dries 4-10h, 450-550 DEG C of roasting 4-10h, obtains the dispersed zinc oxide stratiform material containing gahnite
Material.
6. complex carrier according to claim 1, it is characterised in that the content of complex carrier surface potassium and strontium is higher than
The content of complex carrier inside potassium and strontium.
7. complex carrier according to claim 6, it is characterised in that the content of the carrier surface potassium and strontium is in carrier
1.2-2.5 times of portion's potassium and content of strontium.
8. the preparation method of complex carrier according to claim 3, it is characterised in that the nitric acid acidification polyacrylic acid
The process of sodium is as follows：Deionized water is heated to 30~95 DEG C, then nitric acid is dissolved into deionized water, add polypropylene
Sour sodium, and dissolve complete, obtain the acid solution containing Sodium Polyacrylate.
9. the preparation method of complex carrier described in a kind of any one of claim 6 or 7, it is characterised in that comprise the following steps：Will
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, prepare the zinc oxide film containing gahnite
Shape material；Zinc oxide and boehmite containing gahnite are well mixed, after adding sesbania powder, nitric acid acidification
The acid solution containing Sodium Polyacrylate, 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 the compound load of the zinc oxide-alumina containing auxiliary agent
Body；Recycling potassium and strontium carries out surface modification to the zinc oxide-alumina complex carrier containing auxiliary agent, and detailed process includes following step
Suddenly：The aqueous solution of the configuration containing potassium nitrate and strontium nitrate is used as maceration extract zinc oxide-alumina complex carrier of the dipping containing auxiliary agent, warp
Dry, roasting obtains used additives potassium and strontium and carries out the zinc oxide-alumina complex carrier containing auxiliary agent of surface modification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611205777.7A CN106732516A (en) | 2016-12-23 | 2016-12-23 | A kind of zinc oxide aluminium complex carrier and preparation method containing auxiliary agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611205777.7A CN106732516A (en) | 2016-12-23 | 2016-12-23 | A kind of zinc oxide aluminium complex carrier and preparation method containing auxiliary agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106732516A true CN106732516A (en) | 2017-05-31 |
Family
ID=58919866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611205777.7A Pending CN106732516A (en) | 2016-12-23 | 2016-12-23 | A kind of zinc oxide aluminium complex carrier and preparation method containing auxiliary agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106732516A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113750950A (en) * | 2020-06-05 | 2021-12-07 | 中国石油化工股份有限公司 | Purifying agent for removing carbonyl metal compound and preparation method and application thereof |
Citations (8)
| 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 | Hydrocarbon hydrodesulfurization catalyst and preparation method thereof |
| CN1356377A (en) * | 2000-12-01 | 2002-07-03 | 中国石化集团齐鲁石油化工公司 | Catalyst for selectively hydrodesulfurizing gasoline and its preparing process |
| 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 |
| CN102515247A (en) * | 2011-12-09 | 2012-06-27 | 浙江工业大学 | Zinc-aluminum binary hydrotalcite and application thereof as photocatalytic material used for degrading methyl violet |
| CN103721693A (en) * | 2012-10-10 | 2014-04-16 | 中国石油化工股份有限公司 | Titanium oxide-aluminum oxide compound as well as preparation method and application thereof |
| CN104549475A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking gasoline desulfurization catalyst composition |
| CN104986785A (en) * | 2015-06-17 | 2015-10-21 | 中国石油天然气集团公司 | Large-specific-surface-area mesoporous divalent metal aluminum base spinel and preparing method and application thereof |
| CN105749922A (en) * | 2014-12-17 | 2016-07-13 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrotreating catalyst and heavy oil hydrotreating catalyst prepared by preparation method and use of heavy oil hydrotreating catalyst |
-
2016
- 2016-12-23 CN CN201611205777.7A patent/CN106732516A/en active Pending
Patent Citations (8)
| 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 | Hydrocarbon hydrodesulfurization catalyst and preparation method thereof |
| CN1356377A (en) * | 2000-12-01 | 2002-07-03 | 中国石化集团齐鲁石油化工公司 | Catalyst for selectively hydrodesulfurizing gasoline and its preparing process |
| 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 |
| CN102515247A (en) * | 2011-12-09 | 2012-06-27 | 浙江工业大学 | Zinc-aluminum binary hydrotalcite and application thereof as photocatalytic material used for degrading methyl violet |
| CN103721693A (en) * | 2012-10-10 | 2014-04-16 | 中国石油化工股份有限公司 | Titanium oxide-aluminum oxide compound as well as preparation method and application thereof |
| CN104549475A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking gasoline desulfurization catalyst composition |
| CN105749922A (en) * | 2014-12-17 | 2016-07-13 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrotreating catalyst and heavy oil hydrotreating catalyst prepared by preparation method and use of heavy oil hydrotreating catalyst |
| CN104986785A (en) * | 2015-06-17 | 2015-10-21 | 中国石油天然气集团公司 | Large-specific-surface-area mesoporous divalent metal aluminum base spinel and preparing method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113750950A (en) * | 2020-06-05 | 2021-12-07 | 中国石油化工股份有限公司 | Purifying agent for removing carbonyl metal compound and preparation method and application thereof |
| CN113750950B (en) * | 2020-06-05 | 2024-03-26 | 中国石油化工股份有限公司 | Purifying agent for removing carbonyl metal compound and preparation method and application thereof |
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) | Zinc oxide material containing zinc-aluminum spinel and preparation method thereof | |
| CN106179382B (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| 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 | |
| CN105289632B (en) | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil | |
| CN106955746A (en) | A kind of complex carrier of the aluminum oxide containing zinc oxide and preparation method thereof | |
| CN106732516A (en) | A kind of zinc oxide aluminium complex carrier and preparation method containing auxiliary agent | |
| CN106881127A (en) | A kind of catalyst and preparation method for gasoline desulfurization modification | |
| CN106867577B (en) | A kind of method for gasoline desulfurization | |
| CN106732632A (en) | A kind of Hydrobon catalyst and preparation method | |
| CN106807420A (en) | A kind of catalyst and preparation method for petroleum naphtha hydrogenation dearsenification | |
| CN106622319B (en) | Zinc-aluminum layered material and preparation method thereof | |
| CN106929091B (en) | Catalytic gasoline hydrodesulfurization modification method | |
| CN110038581A (en) | A method of preparing Hydrobon catalyst | |
| CN106925309A (en) | A kind of catalyst for gasoline hydrodesulfurizationmethod and preparation method thereof | |
| CN106925338B (en) | Sulfur-carrying type hydrodesulfurization modification catalyst and preparation method thereof | |
| CN107511128B (en) | Pretreatment method of adsorption desulfurizer | |
| CN107511127B (en) | Desulfurization treatment method for catalytically cracked gasoline | |
| CN107583659B (en) | Catalyst for selective hydrodesulfurization and preparation method thereof | |
| CN106179480A (en) | A kind of Hydrobon catalyst compositions and preparation method thereof | |
| CN106179389B (en) | Hydrobon catalyst and preparation method thereof | |
| CN106925337A (en) | Hydrodesulfurization modification catalyst 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |