CN107983405A - A kind of preparation method of hydrogenation catalyst - Google Patents

A kind of preparation method of hydrogenation catalyst Download PDF

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Publication number
CN107983405A
CN107983405A CN201610950056.2A CN201610950056A CN107983405A CN 107983405 A CN107983405 A CN 107983405A CN 201610950056 A CN201610950056 A CN 201610950056A CN 107983405 A CN107983405 A CN 107983405A
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hydrogenation catalyst
carrier
water absorption
high water
acid
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CN107983405B (en
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董松涛
陈元君
李明丰
胡志海
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • 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

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

Abstract

The disclosure provides a kind of preparation method of hydrogenation catalyst, and this method includes：Extrusion molding is carried out after carrier precursor is mixed with high water absorption compound and water, obtains carrier precursor wet bar；Wherein, the water absorbent rate of the high water absorption compound is 250 1500, and the particle diameter of the high water absorption compound is less than 100 microns；Resulting vehicle precursor wet bar is dried and roasted successively, obtains shaping carrier；By gained shaping carrier supported active metals element.Hydrogenation catalyst metal deposition capability prepared by disclosure preparation method is big and deposit depth is deep.

Description

A kind of preparation method of hydrogenation catalyst
Technical field
A kind of this disclosure relates to preparation method of hydrogenation catalyst.
Background technology
In recent years, in world wide crude oil heaviness and in poor quality tendency it is increasingly apparent, at the same time, liquid-fuel oil with And reformation, the demand of steam crack material are but continuously increased.This promotes heavy distillate processing technology to be developed rapidly, and Catalyst is wherein mostly important and crucial factor.
The catalyst converted for mink cell focus or macromolecular, has larger aperture and enough holes except catalyst is required Outside holding, the pore-size distribution of catalyst mesoporous is also required to concentrate.
Due to for mink cell focus or the catalyst of the conversion of macromolecular generally by by the activity with catalytic action What component load obtained on porous support, therefore preparation has larger aperture and pore volume, and there is higher aperture collection The key of the catalyst of moderate is to provide with big aperture and with the porous carrier of higher aperture concentration degree.
Caused by the characteristic of aluminium oxide in itself, no image of Buddha molecular sieve forms regular crystalline structure like that, therefore aoxidizes Alumina supporter and part silica-alumina material, magnalium material etc. are difficult to form homogeneous pore passage structure.But also just because of oxidation This stacking provisions of aluminium, allow alumina support to be likely to form macropore or bigger serface, but have macropore and big ratio at the same time Surface area is relatively difficult.
If the performance for weighing catalyst need by specific surface area, pore volume and can a few hole apertures are unified considers, one A empirical equation that can be for reference is (crude oil depth process catalyst, Sinopec publishing house, Beijing, 1995, P231)：
R=K+0.0589S+13.2V+0.0012R
Wherein r is desulfurization degree, %；
S is specific surface area, m2/g；
V is pore volume, mL/g；
R is aperture, nm；
But it only can not completely reflect the duct degree of mobility of carrier from K values, it is also difficult to and response data combines Get up.
Since the pore structure of catalyst can have shadow in terms of specific surface area, pore volume and three, aperture to catalyst performance Ring, and for different reactions, the influence of three aspects will be different.
It is generally believed that specific surface area can provide greatly more active areas, more activated centres are produced；Pore volume Greatly, ensure there are enough deposition volumes, the carbon distribution of catalyst even occur, the activity of catalyst still can maintain one Higher level；And whether aperture is directly related to reactant and can be in contact with activated centre and reactant and product Diffusion velocity etc..Some hydrogenation reactions contrast surface area, i.e., activated centre number is sensitive, and some reactions are same to aperture and pore volume When with special requirement, such as while residual oil hydrocatalyst requires the catalyst to have larger aperture, it is also desirable to catalyst Pore volume with suitable size.
In order to improve the characteristic of pore structure to improve catalyst performance, individually, or the mode of two parameters is improved at the same time It is more, it is common to there is mode to have：Combustible port-creating method and mixed powder extrusion method.
Combustible port-creating method as：
Chinese patent literature CN1768947A proposes a kind of preparation method of macroporous aluminium oxide, is that preparation method is to prepare During using powder such as crops stem shells as expanding agent, addition be aluminium oxide 10~20wt%.Compared with prior art, should Method prepare alumina support have the characteristics that aperture greatly, pore distribution concentration, high mechanical strength.
Chinese patent literature CN102861615A proposes a kind of method for preparing macropore alumina supporter, comprises the following steps that： Weigh a certain amount of boehmite dry glue powder, carbon powder, extrusion aid to be uniformly mixed, then add and expand containing peptizing agent and chemistry The aqueous solution of hole agent, resulting material is uniformly mixed, extruded moulding, and alumina support is made through drying, roasting in molding materials, its In, the carbon powder passes through ammonium salt aqueous solution impregnation.
Chinese patent literature CN101214454A proposes a kind of preparation method of the macroporous aluminium oxide with diplopore distribution, tool Body step is：First aluminium oxide, pore creating material, solid silicon are mixed, in the ball mill ball-milling treatment；By the mixture after processing with molten After the aqueous solution that solution has cationic surfactant, extrusion aid and peptizing agent etc. is kneaded into plastic, it is placed in water vapour atmosphere Processing；Again by obtained molding it is dry, roast to obtain final alumina support.The pore creating material is carbon black, cellulose and shallow lake One kind or its mixture in powder.
Mixed powder extrusion method has：
Chinese patent literature CN1597117A proposes a kind of preparation method of alumina support, and this method is by under aluminium oxide Heel (i.e. γ-Al2O3) be ground into powder, then with carbon powder and nitrogenous aqueous slkali or the ammonium salt alkaline water that can be volatilized completely Solution kneading, adds aluminum hydroxide solid elastomer powder, and kneading is into plastic；After being molded, dry, roast, alumina support is made. In the carrying alumina production procedure, make peptizing agent without using inorganic acid or organic acid.
Chinese patent literature CN101322949A proposes a kind of carrying alumina preparation, which uses carbon Boehmite powder prepared by boehmite powder and aluminum sulfate method prepared by change method is by weight 1: 0.1~5 mixing as system The predecessor of standby alumina support, peptizing agent is made with Compound-acid, and zirconium, titanium, silicon, alkali metal, alkaline earth gold are added in kneading process The materials such as category, rare earth metal and carbon black, are then molded, are dry, alumina support is made in roasting.
Chinese patent literature CN103212449A proposes a kind of hydrofining catalyst carrier and preparation method thereof, and method is After modification infusorial earth, alumina powder, adhesive and expanding agent are mixed, carrier is made after kneaded and formed, dry, roasting；Its Feature is, modification infusorial earth be by diatomite after soda-dip, acid solution neutralize, then through washing, press filtration and be made, its surface Greatly reduce with intrapore impurity level, be conducive to the load of active component.
Chinese patent literature CN1103009A proposes a kind of preparation method with double-hole alumina support, it is by two Kind aluminium hydrate powder of different nature adds carbon black and surfactant, by kneading extruded moulding, drying, finally oxygenous Required double-hole alumina support is made in roasting in stream.
Chinese patent literature CN101433863A proposes a kind of composite oxide carrier and preparation method thereof, and method is by oxygen Change precursor and the aqueous slkali co-precipitation of aluminium, silica and zirconium oxide, addition surfactant improves pore structure and acid-base property, Obtained sediment is washed, filtering, high-temperature roasting obtain composite oxide powder, then extruded moulding to obtain the final product.
Chinese patent CN1768945A proposes a kind of siliceous and alumina support of titanium and preparation method thereof, modified aluminas Auxiliary agents of silicon in carrier introduces during aluminium hydroxide plastic, makes specific surface area, aperture and the pore volume of aluminium oxide significantly Improve；After cemented into bundles, the pH value for adjusting mixed serum with acid reagent and alkaline reagent respectively is multiple, so as to get hydrogen-oxygen Change aluminium pore size distribution more to concentrate；Auxiliary agent titanium is added after plastic, before aging.
In addition to the method for both the above mainstream, also have：Improve the calcination temperature of carrier；Water steaming is passed through in roasting process The methods of gas, but these patents inevitably also change the thing phase of alumina support while carrier aperture is improved Structure, so as to influence the characteristic of active component, adversely affects catalyst performance.
The content of the invention
The purpose of the disclosure is to provide a kind of preparation method of hydrogenation catalyst, using prepared by disclosure preparation method Hydrogenation catalyst metal deposition capability is big and deposit depth is deep.
To achieve these goals, the disclosure provides a kind of preparation method of hydrogenation catalyst, and this method includes：By carrier Precursor carries out extrusion molding after being mixed with high water absorption compound and water, obtains carrier precursor wet bar；Wherein, the high water absorption The water absorbent rate of compound is 250-1500, and the particle diameter of the high water absorption compound is less than 100 microns；By resulting vehicle precursor Wet bar is dried and roasts successively, obtains shaping carrier；By gained shaping carrier supported active metals element.
Preferably, the high water absorption compound is at least one in carbohydrate, starch, cellulose and high molecular polymer Kind.
Preferably, the high water absorption compound is resin；The resin be selected from starch resinoid, cellulosic resin, At least one of polyacrylate resinoid, polyvinyl alcohol resin and polyoxyethylene resinoid.
Preferably, using the weight ratio of the carrier precursor of dry basis, high water absorption compound and water as 100：(0.1- 5)：(25-1600).
Preferably, using the weight ratio of the carrier precursor of dry basis, high water absorption compound and water as 100：(0.2- 2)：(50-1000).
Preferably, the preparation method of the hydrogenation catalyst further includes：By carrier precursor, high water absorption compound and water with The extrusion molding is carried out again after peptizing agent mixing；Wherein, the peptizing agent is aqueous hydrochloric acid solution and/or aqueous solution of nitric acid, institute The concentration for stating peptizing agent is 0.5-5 weights %.
Preferably, the carrier precursor is boehmite.
Preferably, the condition of the drying includes：Temperature is 80-200 DEG C, when the time is 1-12 small；The bar of the roasting Part includes：Temperature is 350-800 DEG C, and when the time is 1-10 small, calcination atmosphere is oxygen-containing atmosphere.
Preferably, the step of load includes：By shaping carrier use containing at least one group VIII metal can The solution of soluble metal compound and the soluble metal compound of at least one vib metals is impregnated, and is then carried out Dry and roasting.
Preferably, the soluble metal compound of the group VIII metal be the nitrate selected from nickel, it is acetate, solvable At least one of acid carbonate, chloride and soluble complexes, the soluble metal compound of the vib metals are Selected from molybdic acid, para-molybdic acid, molybdate, paramolybdate, wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates, metatungstate and ethyl At least one of metatungstate.
Preferably, the duct performance index of the hydrogenation catalyst is 12-20；Wherein, the duct performance index uses Formulas I is calculated, and the Formulas I is：TI=0.1S/ [1+5ABS (1-V)]+logR；Wherein, TI is the duct performance index, TI is dimensionless number；S is the specific surface area of the hydrogenation catalyst, and unit is rice2/ gram；V is the hole of the hydrogenation catalyst Volume, unit are ml/g；R be the hydrogenation catalyst can a few hole apertures, unit for angstrom；The ABS is absolute value letter Number.
Preferably, the duct performance index is 13-16.
Preferably, the specific surface area of the hydrogenation catalyst is 120-350 meters2/ gram, pore volume for 0.4-1.25 milliliters/ Gram, can a few hole apertures be 10-1000 angstroms.
The disclosure is conducive to improve hydrogenation at the same time and urges by adding high water absorption compound in hydrogenation catalyst preparation process The specific surface area and pore volume of agent, at the same make hydrogenation catalyst can a few hole apertures more concentrate.
Method of disclosure prepare hydrogenation catalyst be conducive to improve macromolecular reaction performance, coke laydown performance and add The metal deposition capability and deposit depth of hydrogen catalyst.
In addition, in order to produce the pore volume of identical hydrogenation catalyst, method of disclosure uses the weight of high water absorption compound Measure to divide it using the hundreds to thousands of the weight of the non-high water absorption compound expanding agent such as conventional activated carbon, cellulose and starch One, the manufacturing cost of hydrogenation catalyst is greatly reduced, and carbon emission is reduced, realize the requirement of green low-carbon production.
Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the disclosure is described in detail below.It is it should be appreciated that described herein specific Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
Butt weight described in the disclosure refers to the result that sample measures after 650 DEG C of roasting 3h.
The disclosure provides a kind of preparation method of hydrogenation catalyst, and this method includes：By carrier precursor and high water absorption Extrusion molding is carried out after compound and water mixing, obtains carrier precursor wet bar；Wherein, the water absorbent rate of the high water absorption compound For 250-1500, the particle diameter of the high water absorption compound is less than 100 microns；Resulting vehicle precursor wet bar is dried successively And roasting, obtain shaping carrier；By gained shaping carrier supported active metals element.
High water absorption compound is a kind of new high molecular material, it can absorb the water of own wt hundred times to thousand times Point, it is nontoxic, harmless, pollution-free；Water absorbing capacity extra-heavy, water holding capacity is extra-high, and absorb water point cannot be squeezed by simple physical method Go out, and water, water suction can be released repeatedly.The disclosure to high water absorption compound composition do not have concrete restriction, such as can be selected from At least one of carbohydrate, starch, cellulose and high molecular polymer, are preferably resin；The resin is selected from starch tree At least one of fat, cellulosic resin, polyacrylate resinoid, polyvinyl alcohol resin and polyoxyethylene resinoid, Preferably polyacrylate resinoid.High water absorption compound can be Synthetic artifact or natural product and natural product Modified product, can be organic matter or inorganic matter.
The disclosure added in shaping carrier preparation process high water absorption compound can both make high water absorption compound absorb water after To support carrier precursor wet bar, making high water absorption compound, burning-off produces more pore volumes after baking, can also prevent for expansion The problems such as excessive caused carrier of local temperature caused by the conventional expanding agent such as activated carbon sinters is produced when only roasting, is carried The pore-size distribution reservation of body precursor is better, a kind of embodiment, with the carrier precursor of dry basis, high suction The weight ratio of hydrate and water is 100：(0.1-5)：(25-1600), is preferably 100：(0.2-2)：(50-1000).Carrier The butt weight of precursor obtains after can carrier precursor be roasted, for example, at 500~800 DEG C roasting 2~5 it is small when After weigh.
Similar to the preparation method of conventional hydrogenation catalyst, the preparation method of the hydrogenation catalyst can also include：Will Carrier precursor, high water absorption compound and water carry out the extrusion molding again after being mixed with peptizing agent；Wherein, the peptizing agent is Aqueous hydrochloric acid solution and/or aqueous solution of nitric acid, the concentration of the peptizing agent is 0.5-5 weights %.Preparation method can also be included in crowded Go out and appropriate extrusion aid and/or adhesive, then extrusion molding are added when being molded.
Other extrusion aids extruded moulding together with peptizing agent, extrusion aid, peptizing agent can also be added in carrier forming process Species and dosage device to hole concentration degree influence it is bigger, select appropriate extrusion aid to change the pore structure of carrier.Extrusion aid Species include but not limited to organic carboxyl acid, polyalcohol, organic amine, surfactant and high-molecular compound etc..
Organic carboxyl acid refers to the compound with carboxyl, includes but not limited to：Formic acid, acetic acid, ethanedioic acid, propionic acid, the third two Acid, butyric acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, benzenpropanoic acid etc., other are unrequited to can be found in《Lan Shi Chemical manual》The second edition, 1.26-1.27.
Surfactant refers to, with fixed hydrophilic lipophilic group, align in the surface energy of solution, and can make table The material that face tension force is remarkably decreased.Including：1st, anion surfactant, such as stearic acid, neopelex etc.； 2nd, cationic surfactant, such as quaternary ammonium compound；3rd, zwitterionic surfactant, such as lecithin, amino acid pattern, glycine betaine Type etc.；4th, nonionic surfactant, such as fatty glyceride, polyalcohol, including fatty acid sorbitan (sapn), polysorbate (tween), polyoxyethylene-type and Pluronic F68s etc..
Polyalcohol refers to the organic compound for containing multiple hydroxyls in molecular structure, includes but not limited to ethylene glycol, the third three Alcohol, butanediol etc..
Organic amine can include monoethanolamine, diethanol amine, triethanolamine, N methyldiethanol amine, urea etc..
High-molecular compound, also known as high polymer, refer to those by numerous atoms or atomic group mainly with Covalent bonding together Compound of the relative molecular weight formed more than 10,000.Organic high molecular compound can be divided into natural organic high-molecular chemical combination Thing (such as starch, cellulose, protein, natural rubber, butadiene rubber) and synthetic organic polymer compound (such as polyethylene, Polyvinyl chloride, phenolic resin etc.), their relative molecular mass can from tens of thousands of until millions of or bigger, but they Chemical composition and structure is fairly simple, is often arranged in a repetitive fashion by countless (n) structure junior unit, the disclosure The property of high polymer is not limited.
The silica gel that the carrier precursor that the disclosure is mentioned can include silica or hydrated silica is key component, silicon Powder；Molecular sieve or zeolite, carbon material；Mg-based material using magnesia or hydrated magnesium as key component；With titanium oxide or each Kind hydrous titanium oxide thing is mutually the titanium base material of key component；It can also include what is formed by any combination between above material Catalysis material.
The component of the carrier precursor of the disclosure can be bi component oxide, such as aluminium oxide-silicon oxide, aluminium oxide-oxygen Change titanium, alumina-silica magnesium, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, oxygen SiClx-titanium oxide, titania-zirconia etc., can also add the third component, to the 3rd of addition the on the basis of bi-component Kind component does not do any restrictions.More multicomponent can be added on the basis of bi-component or three components, to the component of addition also not Do any restrictions.
In the carrier precursor of the disclosure, can also there is molecular sieve or a zeolite component, the disclosure to the type of molecular sieve and Property does not do any restriction.Molecular sieve can be X-type, Y types, beta types, ZSM-5 and the similar molecular sieve with ten-ring, And http:All molecular sieve types and structure mentioned in //www.iza-structure.org/databases/ websites. In addition to the molecular sieve of primary structure, further include but be not limited to modified molecular screen, such as Modified Zeolite Y, modified BETA molecules Sieve, or modified ZSM-5 molecular sieve etc..
The Modified Zeolite Y that the disclosure is mentioned refers to, by the processing to NaY molecular sieve, changes total group of molecular sieve Into the mode formed with skeleton.Composition change method enters including ion-exchange reduction Na contents or exchange other elements and divides In son sieve, these elements include the elements such as rare earth element, transition metal and Ca, Mg, it is therefore an objective to increase the stability of molecular sieve Or the acidity of molecular sieve is adjusted.Change skeleton composition, it is common to have high temperature hydro-thermal method, organic coordination reaction method, high temperature Gas-phase reaction method, ammonium fluosilicate liquid phase reactor method etc., it is therefore an objective to change framework si-al ratio, improved generally by framework dealumination Framework si-al ratio.
The dealuminzation mode of Y type molecular sieve includes：Heat or hydrothermal dealumination, chemical dealuminization, two methods are combined.Wherein hydro-thermal Facture use is wider, also substantial amounts of commercial Application, is currently used a kind of most method.Hydro-thermal process method goes out earliest Present middle nineteen sixties, generally in vapor or from the presence of the vapor produced, roast NH4Y, so that by skeleton Aluminium extracting becomes non-framework aluminum, and framework si-al ratio improves, lattice constant and ion exchange capacity are reduced.The temperature of change processing, Time and steam partial pressure can adjust the size of degree of dealumination and lattice constant.Can also multiple hydro-thermal process, structure cell is normal Number is reduced toHereinafter, due to after dealuminzation the defects of is to be filled by silicon, improves heat endurance, and people are referred to as USY, USY is widely used on industrial hydrogenation catalyst.
Chemical dealuminization method includes：EDTA complexing dealuminzations method, SiCl4Gas phase same order elements dealuminzation method, (NH4)2SiF6Liquid phase is same Crystalline substance substitution dealuminzation method and organic acid (such as oxalic acid, citric acid) liquid complexing dealuminzation method.Hydro-thermal and chemical dealuminization are combined method：One As be hydrothermal dealumination first, then chemical dealuminization method sloughs non-framework aluminum, while dealuminzation, also removes in molecular sieve system and remains Remaining Na+。
Since the method for modifying of Y type molecular sieve is numerous, the disclosure does not do any limit to the method for modifying of Modified Zeolite Y It is fixed, also the physico-chemical property of Modified Zeolite Y is not limited in any way.
Preferably, the lattice constant of Modified Zeolite Y existsBetween, the preparation of molecular sieve There is hydrothermal treatment step in journey.
The lattice constant of most preferred modified molecular screen existsBetween.In the preparation process of molecular sieve There are hydro-thermal process and chemical dealuminization step.
Hydrogenation catalyst is used to prepare, in addition to hydrogenation active component, it is also necessary to add other coagents, the disclosure Species and dosage to other coagents do not do any restriction.If being used for non-hydrogenation catalyst, can there is no hydrogenation component, Can also there is no addO-on therapy.
The disclosure is in addition to non-amorphous mesoporous acidic material and Modified Zeolite Y, to other acid materials of addition Material does not do any restrictions.The acid material can be selected from the zeolite for being commonly used for active component of cracking catalyst in the prior art One or more in type molecular sieve, non-zeolite molecular sieve, the disclosure do not appoint the species and dosage of used molecular sieve What is limited.For example, in ZRP, Y zeolite, modenite, ZSM-5, MCM-41, Ω, ZSM-12, MCM-22 zeolite molecular sieve One or more.It is preferred that the one or more in Y zeolites, modenite, ZSM-5.The molecular sieve can be commercially available Commodity, can also use routine techniques to prepare.
The carrier precursor can be made into various easily operated moldings, such as microballoon, spherical, tablet depending on different requirements Or bar shaped etc..Shaping can carry out according to a conventional method, for example, for the complex carrier of a kind of molecular sieve and inorganic refractory oxides, Can be the molecular sieve is mixed with the heat-resistant inorganic oxide or its precursor, extruded moulding and roast method system It is standby.Wherein, the precursor of the heat-resistant inorganic oxide can form the compound of the heat-resistant inorganic oxide after referring to roasting, logical Refer to hydroxide, hydrous oxide, containing its oxide, hydroxide gel and colloidal sol in one or more.Example Such as, the precursor of aluminium oxide can be selected from the one or more in various hydrated aluminas and Aluminum sol.
A kind of preferred embodiment, the shaping carrier contain selected from aluminium oxide, silica, magnesia, titanium oxide, At least one of zirconium oxide, carbon and zeolite, are counted by alumina weight and on the basis of the butt weight of shaping carrier, it is described into Alumina content is preferably 95-100 weights % in type carrier.Carrier precursor refers to：Oneself in itself, or adds certain other group Can be as the material of catalyst after point.Carrier precursor can be one-component or the mixture of various ingredients.Carry Can be one-component in body precursor, such as (hydration) aluminium oxide, (hydration) silica, magnesia, titanium oxide, zirconium oxide, carbon Component, and any combination between them.Can be crystalline state or amorphous state.Wherein crystalline state includes but unlimited In molecular sieve or zeolite component.The disclosure does not appoint the composition and property of molecular sieve or zeolite included in carrier precursor What is limited, and includes but not limited to y-type zeolite, BETA zeolites, ZSM-5 and other contain the molecular sieve of ten-ring.Except sial type Outside molecular sieve, other non-Si-Al molecular sieves are further included.Shaping carrier can become catalyst, this public affairs after active component is added Open and any restrictions are not done to the composition and property of active component.
It is preferred that the carrier precursor is boehmite, such as Shandong boehmite, Chang Ling boehmite etc..
Dry and roasting is well-known to those skilled in the art, for example, the condition of the drying can include：Temperature is 80-200 DEG C, when the time is 1-12 small；The temperature of the roasting can be 350-800 DEG C, be preferably 450-650 DEG C, during roasting Between when can be 1-10 small, when being preferably 2-8 small, the atmosphere in roasting process is arbitrary, can contain vapor, can also Be free of, can be oxygen-containing atmosphere, such as air atmosphere or nitrogen, argon gas or other gases or gas Any combination of various ratios is preferably oxygen-containing atmosphere with burning-off high water absorption compound.
It is well known to those skilled in the art by the method that active metallic element is loaded on shaping carrier according to the disclosure , such as the aqueous solution of the compound containing active metallic element can be contacted with the shaping carrier, drying simultaneously roasts.Will The method that the aqueous solution of compound containing active metallic element is contacted with shaping carrier is preferably with containing hydrogenation active component The aqueous solution of compound impregnate the shaping carrier.The temperature of the dipping is not particularly limited in the disclosure, can be leaching The attainable various temperature of stain liquid institute.The time of dipping is not particularly limited, as long as the upper aequum of shaping carrier load can be made The compound containing hydrogenation active component, for example, the temperature of dipping can be 5-150 DEG C, dip time can be When 0.5-12 is small.The temperature of the drying can be 80-350 DEG C, be preferably 100-300 DEG C, more preferably 105-250 ℃；When the dry time can be 0.5-24 small, when being preferably 1-24 small, when more preferably 2-12 is small.The temperature of roasting It can be 350-600 DEG C, be preferably 400-550 DEG C；When the time of roasting can be 1-10 small, when being preferably 2-8 small.
The compound containing active metallic element can be it is conventional be used to prepare hydrogenation catalyst containing active The compound of metallic element, such as the soluble metal compound and at least one of at least one group VIII metal can be included The soluble metal compound of vib metals.
The species of the soluble metal compound of the group VIII metal is known to those skilled in the art, e.g., can With one kind in the nitrate selected from group VIII metal, acetate, soluble carbonate salt, chloride and soluble complexes or It is several.Under preferable case, the soluble metal compound of the group VIII metal is the nitrate, acetate, solubility of nickel One or more in carbonate, chloride and soluble complexes.
The species of the soluble compound of the vib metals is known to those skilled in the art, under preferable case, The soluble compound of the vib metals include in molybdic acid, para-molybdic acid, molybdate and paramolybdate it is one or more of with And the one or more in wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates, metatungstate and ethyl metatungstate.
The duct performance index for using the hydrogenation catalyst of method of disclosure preparation can be 12-20；Wherein, the duct Performance index is calculated using Formulas I, and the Formulas I is：TI=0.1S/ [1+5ABS (1-V)]+logR；Wherein, TI is the hole Road performance index, TI are dimensionless number；S is the specific surface area of the hydrogenation catalyst, and unit is rice2/ gram；V adds to be described The pore volume of hydrogen catalyst, unit are ml/g；R be the hydrogenation catalyst can a few hole apertures, unit for angstrom；The ABS For ABS function.
For macromolecular raw material oil hydrogenation catalysts, aperture, pore volume and specific surface area etc. are extremely important, but this is several A index is to be mutually related, and the incidence formula of a routine is：
K × pore volume=specific surface area × aperture；
The general values of K are 30000-40000；
Wherein pore volume Unit/mL/g, specific surface area unit are m2/ g, aperture unit are
The size of K values reflects the arrangement mode of elementary cell in carrier.
For the characteristic of accurate description hydrogenation catalyst, the disclosure defines a new index-duct performance index TI (Transportation Index), calculation is：
TI=0.1S/ [1+5ABS (1-V)]+logR.
The duct performance index of hydrogenation catalyst is high, on the one hand will be by optimizing the working condition of carrier precursor, control The microstructure of carrier precursor, on the other hand will use suitable molding mode and condition of molding, to keep to greatest extent With the duct of extension hydrogenation catalyst.
According to the disclosure, in order to further meet hydrogenation reaction needs, the specific surface area of the hydrogenation catalyst can be 120-350 meters2/ gram, it is preferably 210-350 meters2/ gram, pore volume can be 0.4-1.25 mls/g, be preferably 0.9-1.25 millis Rise/gram, can a few hole apertures can be 10-1000 angstroms, be preferably 100-150 angstroms.
According to the disclosure, the active metallic element can be included selected from group VIII metallic element and group vib metal member At least one of element, the group VIII metallic element can be with iron, cobalt and nickel, and the group vib metallic element can be chromium, molybdenum And tungsten, for example, the active metallic element can include tungsten and nickel, including or do not include molybdenum；Add in terms of oxide and with described On the basis of the butt weight of hydrogen catalyst, the content of the molybdenum is generally not more than 15 weight %, and the content of the tungsten is not generally high In 35 weight %, the content of the nickel is generally not more than 10 weight %；Preferably, in terms of oxide and with the hydrogenation catalyst Butt weight on the basis of, the content of the molybdenum is 0~15 weight %, and the content of the tungsten is 4~35 weight %, the nickel Content is 1~10 weight %；It is further preferred that being counted by oxide and on the basis of the butt weight of the hydrogenation catalyst, The content of the molybdenum is 3~10 weight %, and the content of the tungsten is 5~32 weight %, and the content of the nickel is 2~8 weight %.
The specific surface area of hydrogenation catalyst uses National Standard of the People's Republic of China GB/T19587-2004 in the disclosure It is measured, the pore volume and pore-size distribution of the hydrogenation catalyst use Petrochemical Engineering Analysis method (RIPP test methods) RIPP 151-90 are measured, and the RIPP standard methods for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui is fixed etc. Compile, nineteen ninety version.It is described can a few hole apertures be the pore-size distribution in the corresponding aperture of peak highest point, specifically, BET method survey The pore structure of sample is measured, while specific pore volume product can be obtained to the differential (dV/dr) in aperture with the distribution curve in aperture, some hole Specific pore volume product corresponding to footpath represents the differential (dV/dr) in aperture the pore volume corresponding to the hole near this aperture, its Hole aperture corresponding to middle maximum dV/dr is known as can a few hole apertures.If there is it is multiple can a few hole apertures, take and therein compare hole Corresponding to volume maximum can a few hole apertures.
The hydrogenation catalyst that the disclosure provides is suitable for carrying out hydrodemetallization to hydrocarbon raw material, and it is easy to be particularly suitable for those The metal types of superficial deposit, such as iron, calcium, to reduce the content of metal in hydrocarbon raw material.The hydrocarbon raw material can be each Kind heavy mineral oil or artificial oil or their mixed fraction oil, such as vacuum gas oil (VGO), metal removal oil, reduced crude, depitching Decompression residuum, decompression residuum, coker distillate, shale oil, asphalt sand oil, liquefied coal coil.
According to the conventional method in this area, the hydrogenation catalyst that the disclosure provides before the use, can be deposited in hydrogen Under, presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140-370 DEG C, this presulfurization can be in reactor Outer progress also can be In-situ sulphiding in reactor, is translated into sulfide type.
Hydrogenation catalyst is hydrogenated with for hydrocarbon raw material made from the preparation method of the hydrogenation catalyst provided using the disclosure During demetalization, it can be used under conventional hydrodemetallization process conditions, such as 200-650 DEG C of reaction temperature, preferably 300-510 DEG C, reaction pressure 3-24 megapascal, preferably 4-15 megapascal, when liquid hourly space velocity (LHSV) 0.1-30 is small-1, hydrogen/oil mol ratio 15-35.
The disclosure will be further illustrated by embodiment below, but the disclosure is not therefore any way limited.
The water absorbent rate assay method of high water absorption compound is as follows in the embodiment of the present disclosure：Weigh a certain amount of at 120 DEG C High water absorption compound after when drying 2 is small is placed in beaker, adds deionized water, and keep deionized water not have high water absorption chemical combination Thing, after high water absorption compound absorbs saturation, is filtered with funnel, weighed, and water absorbent rate Q is calculated using following formula：
Q=(W1-W0)/W0, in formula,
W1 is the weight of high water absorption compound after water suction, and W0 is the weight of high water absorption compound before water suction.
Comparative example 1
Thin boehmite powder (be derived from Shandong Aluminum Plant, 69.5 heavy % of solid content (600 DEG C/3h), similarly hereinafter) 150g is taken, is added Concentration is the salpeter solution 128mL of 3.5 weight %, and kneading is extruded into the cylindrical bar of diameter 1.8mm, 8 are dried at 120 DEG C after twenty minutes After hour, 3h is roasted at 600 DEG C, is denoted as shaping carrier DA, the physico-chemical property of shaping carrier DA is as shown in table 1.
According to tungsten oxide content in the catalyst using dry basis as 17.0 weight %, nickel oxide content be 3.8 weight % match somebody with somebody Put nickel nitrate (analysis is pure, the sharp chemical reagent factory of Beijing benefit) and ammonium metatungstate (industrial goods, from Chang Ling catalyst plant) mixing leaching Stain solution, after the saturation impregnated shaped support DA of hole, when then drying 4 is small at 120 DEG C, then roasts 3 at 410 DEG C Hour, keep during roasting air mass flow not less than 130 cubic metres/(kilogram hour), obtain hydrogenation catalyst, be denoted as hydrogenation and urge Agent DA.The physico-chemical property of hydrogenation catalyst DA is as shown in table 1.
Comparative example 2
SB powder (SASOL German companies produce, 73.5 heavy % of solid content (600 DEG C/3h)) 140g is taken, it is 2 heavy % to add concentration Salpeter solution 123mL, kneading is extruded into the cylindrical bar of diameter 1.8mm after twenty minutes, when drying 8 is small at 120 DEG C after, in 600 3h is roasted at DEG C, is denoted as shaping carrier DB, the physico-chemical property of shaping carrier DB is as shown in table 1.
According to tungsten oxide content in the catalyst using dry basis as 15.0 weight %, nickel oxide content be 1.5 weight % match somebody with somebody Put nickel nitrate (analysis is pure, the sharp chemical reagent factory of Beijing benefit) and ammonium metatungstate (industrial goods, from Chang Ling catalyst plant) mixing leaching Stain solution, after the saturation impregnated shaped support DB of hole, when then drying 3 is small at 120 DEG C, then roasts 3 at 400 DEG C Hour, keep during roasting air mass flow not less than 150 cubic metres/(kilogram hour), obtain hydrogenation catalyst, be denoted as hydrogenation and urge Agent DB.The physico-chemical property of hydrogenation catalyst DB is as shown in table 1.
Comparative example 3
Take CL powder (boehmite powder, catalyst Chang Ling branch company production, 72.0 heavy % of solid content (600 DEG C/3h), under 140g together), adds salpeter solution 135mLs of the concentration for 3 weight %, and kneading is extruded into the cylindrical bar of diameter 1.8mm after twenty minutes, and 120 After when drying 8 is small at DEG C, 3h is roasted at 600 DEG C, is denoted as shaping carrier DC, the physico-chemical property of shaping carrier DC is as shown in table 1.
According to tungsten oxide content in the catalyst using dry basis as 14.0 weight %, nickel oxide content be 4.7 weight % match somebody with somebody Put nickel nitrate (analysis is pure, the sharp chemical reagent factory of Beijing benefit) and ammonium metatungstate (industrial goods, from Chang Ling catalyst plant) mixing leaching Stain solution, after the saturation impregnated shaped support DC of hole, when then drying 5 is small at 120 DEG C, then roasts 3 at 390 DEG C Hour, keep during roasting air mass flow not less than 170 cubic metres/(kilogram hour), obtain hydrogenation catalyst, be denoted as hydrogenation and urge Agent DC.The physico-chemical property of hydrogenation catalyst DC is as shown in table 1.
Comparative example 4
Taking thin boehmite powder 50.0g, Siral40 powder, (SASOL German companies produce, solid content (600 DEG C/3h) 77.5 heavy %, silica content 41.2%) 84.0g, salpeter solution 122mL of the concentration for 3.5 weight % is added, kneading is after twenty minutes Be extruded into the cylindrical bar of diameter 1.8mm, when drying 8 is small at 120 DEG C after, roast 3h at 600 DEG C, be denoted as shaping carrier DD, into The physico-chemical property of type carrier DD is as shown in table 1.
According to tungsten oxide content in the catalyst using dry basis as 16.0 weight %, nickel oxide content be 2.5 weight % match somebody with somebody Put nickel nitrate (analysis is pure, the sharp chemical reagent factory of Beijing benefit) and ammonium metatungstate (industrial goods, from Chang Ling catalyst plant) mixing leaching Stain solution, after the saturation impregnated shaped support DD of hole, when drying 5 is small at 120 DEG C, then roasting 3 is small at 400 DEG C When, keep during roasting air mass flow not less than 110 cubic metres/(kilogram hour), obtain catalyst, be denoted as hydrogenation catalyst DD.The physico-chemical property of hydrogenation catalyst DD is as shown in table 1.
Embodiment 1
5g xanthan rubber powders are added in 250ml three-necked flasks, 50ml water is measured and adds in the lump, regulation system pH value to 11- 12,70 DEG C of waters bath with thermostatic control heating, after activating 1h, cool to 45 DEG C or so it is spare.With the NaOH solution of concentration 30% in ice-water bath In, neutralization 25g acrylic acid to pH is 7.The acrylic acid become reconciled by is in N2It is added drop-wise in xanthan gum solution under protection, adds at the same time 0.35g initiator potassium persulfates, then add 0.1g crosslinking agents N, N '-methylene-bisacrylamide, and temperature is increased to 55 DEG C, instead Answer 2h.Product shreds into little particle under the immersion of alcohol, with scissors, is subsequently placed into constant temperature oven, the dry 2h at 80 DEG C Ground 200 mesh sieve obtains super absorbent resin afterwards, and the water absorbent rate Q for measuring super absorbent resin is 300.
Take super absorbent resin 0.5g, stirring is lower plus deionized water 400mL, after the paste that solution becomes similar jelly with After CL powder 140g mixing, add salpeter solution 115mL of the concentration for 1.5 weight %, kneading is extruded into the cylinder of diameter 1.8mm after twenty minutes Shape bar, when drying 8 is small at 120 DEG C after, roast 3h at 600 DEG C, be denoted as shaping carrier A, the physico-chemical property such as table of shaping carrier A Shown in 1.
According to tungsten oxide content in the catalyst using dry basis as 13.5 weight %, nickel oxide content be 2.6 weight % match somebody with somebody Put nickel nitrate (analysis is pure, the sharp chemical reagent factory of Beijing benefit) and ammonium metatungstate (industrial goods, from Chang Ling catalyst plant) mixing leaching Stain solution, after the saturation impregnated shaped support A of hole, when then drying 5 is small at 120 DEG C, then roasts 3 at 400 DEG C Hour, keep during roasting air mass flow not less than 140 cubic metres/(kilogram hour), obtain catalyst, be denoted as hydrogenation catalyst A.The physico-chemical property of hydrogenation catalyst A is as shown in table 1.
Embodiment 2
5g xanthan rubber powders are added in 250ml three-necked flasks, 50ml water is measured and adds in the lump, regulation system pH value to 11- 12,70 DEG C of waters bath with thermostatic control heating, after activating 1h, cool to 45 DEG C or so it is spare.With the NaOH solution of concentration 30% in ice-water bath In, neutralization 25g acrylic acid to pH is 7.The acrylic acid become reconciled by is in N2It is added drop-wise in xanthan gum solution under protection, adds at the same time 0.35g initiator potassium persulfates, then add 0.15g crosslinking agents N, N '-methylene-bisacrylamide, and temperature is increased to 55 DEG C, React 2h.Product shreds into little particle under the immersion of alcohol, with scissors, is subsequently placed into constant temperature oven, dry at 80 DEG C Ground 200 mesh sieve obtains super absorbent resin after 2h, and the water absorbent rate Q for measuring super absorbent resin is 800.
Take super absorbent resin 0.5g, stirring is lower plus deionized water 600mL, after the paste that solution becomes similar jelly with After CL powder 140g mixing, add salpeter solution 115mL of the concentration for 1.5 weight %, kneading is extruded into the cylinder of diameter 1.8mm after twenty minutes Shape bar, when drying 8 is small at 120 DEG C after, roast 3h at 600 DEG C, be denoted as shaping carrier B, the physico-chemical property such as table of shaping carrier B Shown in 1.
According to tungsten oxide content in the catalyst using dry basis as 13.5 weight %, nickel oxide content be 2.6 weight % match somebody with somebody Put nickel nitrate (analysis is pure, the sharp chemical reagent factory of Beijing benefit) and ammonium metatungstate (industrial goods, from Chang Ling catalyst plant) mixing leaching Stain solution, after the saturation impregnated shaped support B of hole, when then drying 5 is small at 120 DEG C, then roasts 3 at 400 DEG C Hour, keep during roasting air mass flow not less than 140 cubic metres/(kilogram hour), obtain catalyst, be denoted as hydrogenation catalyst B.The physico-chemical property of hydrogenation catalyst B is as shown in table 1.
Embodiment 3
5g xanthan rubber powders are added in 250ml three-necked flasks, 50ml water is measured and adds in the lump, regulation system pH value to 11- 12,70 DEG C of waters bath with thermostatic control heating, after activating 1h, cool to 45 DEG C or so it is spare.With the NaOH solution of concentration 30% in ice-water bath In, neutralization 25g acrylic acid to pH is 7.The acrylic acid become reconciled by is in N2It is added drop-wise in xanthan gum solution under protection, adds at the same time 0.35g initiator potassium persulfates, then add 0.2g crosslinking agents N, N '-methylene-bisacrylamide, and temperature is increased to 55 DEG C, instead Answer 2h.Product shreds into little particle under the immersion of alcohol, with scissors, is subsequently placed into constant temperature oven, the dry 2h at 80 DEG C Ground 200 mesh sieve obtains super absorbent resin afterwards, and the water absorbent rate Q for measuring super absorbent resin is 1200.
Take super absorbent resin 0.5g, stirring is lower plus deionized water 800mL, after the paste that solution becomes similar jelly with After CL powder 140g mixing, add salpeter solution 115mL of the concentration for 1.5 weight %, kneading is extruded into the cylinder of diameter 1.8mm after twenty minutes Shape bar, when drying 8 is small at 120 DEG C after, roast 3h at 600 DEG C, be denoted as shaping carrier C, the physico-chemical property such as table of shaping carrier C Shown in 1.
According to tungsten oxide content in the catalyst using dry basis as 13.5 weight %, nickel oxide content be 2.6 weight % match somebody with somebody Put nickel nitrate (analysis is pure, the sharp chemical reagent factory of Beijing benefit) and ammonium metatungstate (industrial goods, from Chang Ling catalyst plant) mixing leaching Stain solution, after the saturation impregnated shaped support C of hole, when then drying 5 is small at 120 DEG C, then roasts 3 at 400 DEG C Hour, keep during roasting air mass flow not less than 140 cubic metres/(kilogram hour), obtain catalyst, be denoted as hydrogenation catalyst C.The physico-chemical property of hydrogenation catalyst C is as shown in table 1.
Comparative example 5
Konjaku flour (Xi'an good harvest bio tech ltd produces, water absorbent rate 120) 5.0g is taken, adds room temperature deionization Water 20mL is mixed well, and stirs the lower deionized water 350mL for adding 60 DEG C, SB powder 140g are added after obtaining paste, it is 1.8 to add concentration The salpeter solution 125mL of weight %, kneading are extruded into the cylindrical bar of diameter 1.8mm after twenty minutes, when drying 8 is small at 120 DEG C after, in 3h is roasted at 600 DEG C, is denoted as shaping carrier DE, the physico-chemical property of shaping carrier DE is as shown in table 1.
According to tungsten oxide content in the catalyst using dry basis as 13.5 weight %, nickel oxide content be 2.6 weight % match somebody with somebody Put nickel nitrate (analysis is pure, the sharp chemical reagent factory of Beijing benefit) and ammonium metatungstate (industrial goods, from Chang Ling catalyst plant) mixing leaching Stain solution, after the saturation impregnated shaped support DE of hole, when then drying 5 is small at 120 DEG C, then roasts 3 at 400 DEG C Hour, keep during roasting air mass flow not less than 140 cubic metres/(kilogram hour), obtain catalyst, be denoted as hydrogenation catalyst DE.The physico-chemical property of hydrogenation catalyst DE is as shown in table 1.
Hydrogenation catalyst is evaluated
To use feedstock oil be the normal two wires in the Yanshan Mountain for evaluation, is 10 to weigh % and call in iron naphthenate and be according to content according to content 3 weight % call in CS2。
The normal two wires feedstock oil specific nature in the Yanshan Mountain is：Density (20 DEG C) is 0.8256g/cm3, sulfur nutrient is 0.32%, nitrogen content is 29 μ g/g；Boiling range (D-86), 177 DEG C of IBP, 10%218 DEG C, 30%247 DEG C, 50%261 DEG C, 70%273 DEG C, 90%294 DEG C, 322 DEG C of FBP.
Evaluation uses autoclave, takes the feedstock oil 400mL of reconciliation to add in autoclave, by CATALYST EXAMPLE and comparative example (being 3.5g) is placed in basketry after sealing pressure testing, by H2Pressure brings up to 6.0MPa, and temperature is brought up to 360 DEG C, continues React 6 it is small when after remove, extracted by toluene, the iron and the deposit depth of iron deposited in analysis of catalyst, concrete outcome is shown in Table 2.Iron is measured using Rigaku ZSX Primus II type Xray fluorescence spectrometers, and deposition of iron depth uses FEI Company's Quanta 200F Flied emission environmental scanning electronic microscope scanning electron microscope (SEM) is tested.
By table 1-2 as it can be seen that compared with comparative example, the hydrogenation catalyst provided using the disclosure can improve hydrogenation catalyst Metal deposition capability and deposit depth.
Table 1
Table 2
Embodiment Catalyst Iron deposition/weight % Deposition of iron depth/μm
Comparative example 1 DA 2.53 80
Comparative example 2 DB 1.86 72
Comparative example 3 DC 2.98 120
Comparative example 4 DD 2.16 74
Embodiment 1 A 6.82 270
Embodiment 2 B 6.41 257
Embodiment 3 C 7.38 285
Comparative example 5 DE 2.33 72

Claims (13)

1. a kind of preparation method of hydrogenation catalyst, this method include：
Extrusion molding is carried out after carrier precursor is mixed with high water absorption compound and water, obtains carrier precursor wet bar；Wherein, The water absorbent rate of the high water absorption compound is 250-1500, and the particle diameter of the high water absorption compound is less than 100 microns；
Resulting vehicle precursor wet bar is dried and roasted successively, obtains shaping carrier；
By gained shaping carrier supported active metals element.
2. according to the method described in claim 1, wherein, the high water absorption compound is selected from carbohydrate, starch, cellulose and height At least one of Molecularly Imprinted Polymer.
3. according to the method described in claim 1, wherein, the high water absorption compound is resin；The resin is selected from starch At least one in resinoid, cellulosic resin, polyacrylate resinoid, polyvinyl alcohol resin and polyoxyethylene resinoid Kind.
4. according to the method described in claim 1, wherein, with the carrier precursor, high water absorption compound and water of dry basis Weight ratio be 100：(0.1-5)：(25-1600).
5. according to the method described in claim 1, wherein, with the carrier precursor, high water absorption compound and water of dry basis Weight ratio be 100：(0.2-2)：(50-1000).
6. according to the method described in claim 1, wherein, the preparation method of the hydrogenation catalyst further includes：By carrier predecessor Thing, high water absorption compound and water carry out the extrusion molding again after being mixed with peptizing agent；Wherein, the peptizing agent is water-soluble for hydrochloric acid Liquid and/or aqueous solution of nitric acid, the concentration of the peptizing agent is 0.5-5 weights %.
7. according to the method described in claim 1, wherein, the carrier precursor is boehmite.
8. according to the method described in claim 1, wherein, the condition of the drying includes：Temperature is 80-200 DEG C, time 1- 12 it is small when；The condition of the roasting includes：Temperature is 350-800 DEG C, and when the time is 1-10 small, calcination atmosphere is oxygen-containing atmosphere.
9. according to the method described in claim 1, wherein, the step of load, includes：Shaping carrier is used containing at least A kind of soluble metal compound of group VIII metal and the soluble metal compound of at least one vib metals it is molten Liquid is impregnated, and is then dried and is roasted.
10. according to the method described in claim 9, wherein, the soluble metal compound of the group VIII metal be selected from At least one of nitrate, acetate, soluble carbonate salt, chloride and soluble complexes of nickel, the group VIB gold The soluble metal compound of category be selected from molybdic acid, para-molybdic acid, molybdate, paramolybdate, wolframic acid, metatungstic acid, ethyl metatungstic acid, At least one of tungstates, metatungstate and ethyl metatungstate.
11. according to the method described in claim 1, wherein, the duct performance index of the hydrogenation catalyst is 12-20；Wherein, The duct performance index is calculated using Formulas I, and the Formulas I is：
TI=0.1S/ [1+5ABS (1-V)]+logR；
Wherein, TI is the duct performance index, and TI is dimensionless number；S be the hydrogenation catalyst specific surface area, unit For rice2/ gram；V is the pore volume of the hydrogenation catalyst, and unit is ml/g；R can a few hole holes for the hydrogenation catalyst Footpath, unit are angstrom；The ABS is ABS function.
12. according to the method for claim 11, wherein, the duct performance index is 13-16.
13. the method according to claim 1 or 11, wherein, the specific surface area of the hydrogenation catalyst is 120-350 meters2/ Gram, pore volume be 0.4-1.25 mls/g, can a few hole apertures be 10-1000 angstroms.
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