CN108855128A - Selective hydrogenation catalyst and preparation method thereof - Google Patents

Selective hydrogenation catalyst and preparation method thereof Download PDF

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Publication number
CN108855128A
CN108855128A CN201710339315.2A CN201710339315A CN108855128A CN 108855128 A CN108855128 A CN 108855128A CN 201710339315 A CN201710339315 A CN 201710339315A CN 108855128 A CN108855128 A CN 108855128A
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nickel
solution
preparation
hydrogenation catalyst
selective hydrogenation
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CN108855128B (en
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胡晓丽
梁顺琴
王斌
展学成
郑云弟
孙利民
钱颖
马好文
刘肖飞
孙雪芹
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J35/613—10-100 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
    • B01J35/61—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
    • B01J35/633—Pore volume less than 0.5 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
    • B01J35/635—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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a selective hydrogenation catalyst and a preparation method thereof, in particular to a preparation method of a palladium-silver hydrogenation catalyst taking nickel-containing alumina as a carrier. Contains active components of palladium and silver, nickel-containing alumina is used as a carrier, the precursor of the nickel-containing alumina carrier is nickel-containing pseudo-boehmite, and the preparation process of the nickel-containing pseudo-boehmite comprises the acid-base neutralization and gelling process. The catalyst uses a specific carrier, has the advantages that nickel and pseudo-boehmite can be organically combined to form a nickel-containing alumina carrier with a specific crystal form, and simultaneously has a better regulation effect on the pore structure and acidity of the carrier, and the active components of the prepared catalyst are highly dispersed.

Description

A kind of selective hydrogenation catalyst and preparation method thereof
Technical field
The present invention relates to a kind of selective hydrogenation catalysts and preparation method thereof, and in particular to one kind is to carry with nickeliferous aluminium oxide Palladium-silver catalyst of body and preparation method thereof.
Background technique
Head product in catalytic cracking and steam cracking process contains more alkadienes and alkynes, in certain reaction Temperature, alkadienes and alkynes are in addition to itself is easy polymerization, it is also possible to it reacts with the gaseous olefin in gasoline, production colloid etc. Coking presoma, usually uses plus the method choice of hydrogen is removed.
Selective hydrogenation catalyst used in industry is mainly the metallic catalyst loaded at present, and active component is mainly palladium Or two kinds of nickel.Two kinds of catalyst have the advantage of its own to answer due to its own intrinsic feature, for different raw material oil natures Use range.Pd/Al2O3The catalyst pretreatment that has many advantages, such as to drive is simple, start-up temperature is low, it is active it is high, treating capacity is big；Ni/ Al2O3There is some superiority, therefore in the higher situation of impurity content in terms of the impurity such as the anti-arsenic of catalyst, resistance to colloid and water resistant, Nickel-base catalyst has metastable performance.To improve activity or the selectivity of catalyst, people's also often addition A certain amount of metal promoter.
US4484015A provides a kind of composition and method, and composition contains palladium and silver, and palladium and the respective dosage of silver are enough to make The abundant selective hydrogenation of certain unsaturated hydrocarbons.It is lower insatiable hunger for high unsaturated hydrocarbons (such as alkynes or alkadienes) selective hydrogenation With hydrocarbon (such as olefine or monoolefine).Composition includes the compound of certain alkali metal containing, such as potassium fluoride in turn.But the catalyst Activity need to be further increased.
CN1181283B provides a kind of catalyst and preparation method thereof, for high unsaturated hydrocarbons (such as alkynes or diene) selectivity It is hydrogenated to lower unsaturated hydrocarbons.Catalyst contains palladium, silver and spinelle.Wherein, palladium and the respective dosage of silver are enough to make certain not The abundant selective hydrogenation of saturated hydrocarbons.As a kind of selection, palladium is present in the surface layer on spinelle surface.Catalyst includes certain The compound of kind alkali metal containing.
CN102728351B is related to one kind for drippolene or its fraction selective hydrocatalyst, the catalyst As the aluminium oxide-titanium oxide compound of carrier, and the active component Pd and Ag being carried on the carrier, it is total with catalyst Weight is 100% meter, Pd content 0.15-0.5wt%, Ag content 0.8-4.5wt%.Catalyst can be used for drippolene or it is evaporated Divide plus hydrogen has anti-As impurity ability strong, the big feature of charging capacity.
CN102430406B discloses a kind of hydrogenation catalyst, it is characterised in that active constituent is metallic state palladium and rare earth oxygen Compound, the content of Metal Palladium is 0.2~5wt% in catalyst, and the content of rare earth oxide is 0.1~2.5wt%.The catalyst It is to be configured to palladium-rare earth aqueous solution with water-soluble containing palladium compound, water-soluble compounds containing rare earth and water, with palladium-rare earth water Solution impregnating carrier.Prepared catalyst, 50~200 DEG C of progress reduction treatments in a hydrogen atmosphere before use, makes palladium chemical combination Oxidation state divalent palladium in object is reduced to metallic state palladium, is used for hexanolactam hydrogenation after-refining technique.
Following three aspects (1) that focus on for improving palladium series hydrocatalyst comprehensive performance develop a kind of novel be applicable in In the carrier material of palladium series hydrocatalyst；(2) modulation palladium series hydrocatalyst active component content；(3) auxiliary agent and work is added Property ingredient dispersion agents improve active component comprehensive utilization ratio.
Hydrated alumina such as boehmite and boehmite etc. are widely used as the raw material for preparing alumina support, Although in carrying alumina production procedure can using as the methods of pH value swing method, the organic expanding agent of addition, hydro-thermal process come Improve the property of the aluminium oxide as carrier, but improves the property of catalyst carrier for hydrgenating material oxidation aluminium by these methods It can be limited.The property for preparing aqua oxidation aluminum feedstock used in alumina support is to produce excellent properties alumina support One of most critical factor.
CN1123392C describes a kind of alumina carrier containing Ni and preparation method thereof, by alkali-treated nickeliferous chemical combination The mixture of object and carbon black and aluminum hydroxide solid elastomer powder kneading, being made a kind of through extruded moulding and drying, roasting nickeliferous is 2.0%~14.0% alumina support, it is 0.4cm which, which holds,3/ g~1.0cm3/ g, specific surface area 160m2/ g~ 420m2/ g, average pore size are 8.0nm~15.0nm, greater than 85% or more, the Kong Rong, average that the ratio in the hole 6.0nm accounts for its total hole Aperture is larger, is particularly suitable for the carrier as hydrorefining catalyst for heavy oil.
CN200710179630.X discloses a kind of preparation method of nickel-coated alumina powder, it is characterised in that will be added and divide Suspension is made in the mixed liquor of the nano aluminium oxide of powder, is added with stirring nickel salt solution, after mixing evenly, drips in mixed liquor Enter ammonium hydroxide, add distilled water, obtains navy blue nickel amine complex ([Ni (NH3)6]2+)-Aluminium oxide mixed solution C, using water Heat ageing is filtered, washed, dries, and obtains coating product among green；Roasting is restored again, the oxidation of black nickel coated is obtained Aluminium powder body.
CN1102862C discloses a kind of nickel-containing hydrogenationcatalysts, contains：In terms of nickel oxide, the nickel of 65-80%, with dioxy SiClx meter, the silicon of 10-25%, in terms of zirconium oxide, the zirconium of 2-10%, in terms of aluminium oxide, the aluminium of 0-10%, precondition is two The sum of content of silica and aluminium oxide is at least 15% (weight %, based on the total weight of catalyst), this catalyst It is by the way that by nickel, zirconium, if necessary, there are also the acidic aqueous solutions of aluminium salt to be added to silicon, if necessary, there are also the compounds of aluminium In alkaline aqueous solution or suspension, the pH of the mixture so obtained is made to be reduced at least 6.5, then by further adding alkali Property solution pH value is adjusted to 7~8, separate the solid so deposited, it is dry, form and be sintered.Furthermore it also discloses Prepare catalyst method and its in preparation medicinal white oils, high-purity medical paraffin and low boiling point low arene content or be free of The method of the hydrocarbon mixture of aromatic hydrocarbons.The preparation method of the catalyst is commonly used to prepare high-activity component content catalyst.But The catalyst strength prepared using this method is poor.
Article " the changes induced by calcination temperature in of Agudo A L etc. hydrodesulfurization activity of NiCo-Mo/Al2O3Catalysis, Applied Catalysis, 1987,30:185-188 " has investigated maturing temperature to NiCoMo/A12O3The active influence of catalyst rhohene desulfiirization.As a result table Bright, the desulphurizing activated of the catalyst activated at 500 DEG C is significantly higher than the catalyst activated under the conditions of 600 DEG C, this is because In 600 DEG C of activation, strong interaction generation spinel structure occurs for metal and alumina support so as to cause catalysis in catalyst Agent activity is remarkably decreased.Activation temperature is higher, and the nickel aluminate phase content of generation is higher, and the activity decline of catalyst is brighter It is aobvious."Influence of support-interaction on the sulfidation behavior and hydrodesulfurization activity of Al2O3Support W, CoW and NiW model catalysts, J PhysChem B, 2002,106:5897-5906 " equally obtains similar conclusion.Since nickel and alumina support are in high-temperature roasting Strong interaction can occur in the process and generate spinel structure, be remarkably decreased so as to cause catalyst activity, therefore roasted in high temperature It is all as prudent using the two as possible before burning, avoid the generation of spinel structure.It is different from other metals, it is rare nickeliferous to intend thin water Aluminium stone report generally requires to carry out high-temperature roasting when because preparing catalyst carrier with it.
The active component of Typical precious metal catalyst is easy to reunite and be poisoned and inactivate during the reaction, point of palladium metal Divergence is even more that numerous researchers attempt to solve the problems, such as.
Summary of the invention
The present invention provides a kind of palladium-silver system selective hydrogenation catalyst and preparation method thereof.
By catalyst weight be 100% in terms of, palladium content (in terms of simple substance) 0.05~0.8wt%, preferably 0.15~ 0.5wt%, 0.05~5wt% of silver oxide, preferably 0.2~3wt%, nickel (in terms of simple substance) 0.1~10wt%, preferably 0.5~ 5wt%；20~150m2/g of specific surface area of catalyst, preferably 60~120m2/g, hole 0.12~0.6ml/g of appearance, preferably 0.3~ 0.5ml/g；Alkali metal and/or alkaline earth oxide 0.1~10wt%, preferably 0.5~3wt%；Cerium oxide and/or lanthana 0~5wt%, preferably 0.5~1.2wt%.
A kind of palladium-silver selective hydrogenation catalyst contains active component palladium and silver in catalyst, is to carry with nickeliferous aluminium oxide Body is to contain palladium (in terms of simple substance) 0.05~0.8wt%, 0.05~5wt% of silver oxide in terms of 100% by total catalyst weight；It urges 20~150m of agent specific surface area2/ g, hole hold 0.12~0.6cm3/g.Alkali metal and/or alkaline earth oxide 0.1~ 10wt%；0~5wt% of cerium oxide and/or lanthana；The presoma of alumina carrier containing Ni is nickeliferous boehmite, nickeliferous There are acid-base neutralization and plastic process in the preparation process of boehmite；It is nickeliferous by the way that active component palladium-silver solution dipping will be contained Hydrogenation catalyst is made through drying, roasting in alumina support.
Palladium of the present invention-silver series hydrocatalyst, by catalyst weight be 100% in terms of, nickel content be 0.1~ 10wt%, preferably 0.5~5wt%, palladium content are 0.05~0.8wt%, preferably 0.15~0.5wt%；Aoxidize silver content 0.05 ~5wt%, preferably 0.2~3wt%；20~150m of specific surface area2/ g, preferably 60~120m2/g；Hole holds 0.12~0.6ml/g, It is preferred that 0.3~0.5ml/g.
It is containing alkali metal and/or alkaline-earth metal (existing in the form of an oxide), content in catalyst of the present invention 0.1~10wt%, preferably 0.5~3wt%.Alkali metal and/or alkaline-earth metal are in one in Li, Na, K, Ca, Mg, Sr, Be Or a variety of, preferably one or more of Li, K, Ca, Mg.When catalyst is for adding hydrogen, alkynes, alkadienes in oil product are easy Polymerization forms colloid and inactivates, and by addition alkali metal and/or alkaline-earth metal, can play to the acid-base property of catalyst support surface Adjustment effect can improve hydrogenation activity and stabilized hydrogenation by adjusting catalyst surface acid-base property, advantageously reduce and add hydrogen mistake Carbonaceous, the deposition of colloid in journey, to extend the service life of catalyst.
Rare-earth element cerium and/or lanthanum (existing in the form of an oxide), content 0 can be contained in catalyst of the present invention ~5wt%, preferably 0.5~1.2wt%.After cerium and/or lanthanum is added, catalyst carrier crystal grain is long when being able to suppress high-temperature roasting Greatly, the dispersion degree for improving active component improves the hydrogenation selectivity and stability of catalyst.
The present invention also provides a kind of palladium-silver series hydrocatalyst preparation methods, are prepared using conventional dipping method, The dip loading of Metal Palladium is identical as common lamella catalyst dipping technique.Invention also provides a kind of the specific of catalyst Preparation method：By alkali metal and/or the soluble-salt of alkaline-earth metal, lanthanum and/or cerium and active component, after water dissolution is added, leaching Stain obtains nickeliferous carrier through drying, roasting on alumina carrier containing Ni precursor；It is molten with the salt containing active component palladium and silver again Liquid impregnates nickeliferous carrier, and palladium and silver can use step impregnation, can also be used while impregnating, by washing, drying, roasting, i.e., Obtain catalyst.
Palladium of the present invention-silver series hydrocatalyst preparation method, active component solution can be palladium and silver-colored can Dissolubility salting liquid.Palladium salt can be palladium nitrate, palladium chloride, palladium acetate, preferably palladium chloride.The preferred silver nitrate of silver salt.In the present invention Alkali metal and/or alkaline-earth metal are preferably to be added in the form of soluble nitrate, acetate or citrate.In the present invention Cerium and/or lanthanum are preferably to be added in the form of soluble nitrate.
Rare-earth element cerium and/or lanthanum and alkali metal and/or alkaline-earth metal can be added in carrier forming process；? It can be added in advance into carrier before dipping active constituent after carrier molding；It can also be when impregnating active constituent, with Active constituent dipping solution is added simultaneously.
Palladium of the present invention-silver series hydrocatalyst, with the prior art it is maximum difference be with nickeliferous aluminium oxide Carrier, the presoma of alumina carrier containing Ni are nickeliferous boehmites.
The present invention also provides a kind of nickeliferous boehmite and carriers prepared therefrom, by the nickeliferous quasi- of this method preparation Boehmite organically combines nickel and boehmite, while having to the pore structure and acidity of nickeliferous boehmite Preferable adjustment effect.
The presoma of alumina carrier containing Ni of the present invention, that is, nickeliferous boehmite, specific surface area 300~ 420m20.7~1.2cm of/g, Kong Rongwei3/ g, aperture are 5~10nm；It is in terms of 100% by nickeliferous boehmite total weight, nickel contains Amount is 0.1~10wt%, preferably 0.5~5wt%.
Nickeliferous boehmite is prepared first, there is acid-base neutralization and plastic mistake in the preparation process of the nickeliferous boehmite Journey.Nickeliferous boehmite at least through molding, drying, roasting process and obtain alumina carrier containing Ni.
Alumina carrier containing Ni of the present invention, depending on finally different, the preparation side of nickeliferous boehmite using purpose Method, nickel source, nickel content, alumina carrier containing Ni preparation method, calcination for activation temperature etc. can be different.
Alumina carrier containing Ni of the present invention preferably contains δ-Al2O3、δ-NiAl26O40、NiAl2O4Crystal form, and XRD 0.45≤B1/B2≤0.85 in spectrogram, B1 refer to that the integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, B2 refer to The integrated intensity at the peak that 2 θ are 43.3~48.5 ° in XRD spectra.
In alumina carrier containing Ni of the present invention, preferably contain δ-Al2O3、δ-NiAl26O40、NiAl2O4Crystal form mixes Crystalline substance, best δ-Al2O3、δ-NiAl26O40And NiAl2O4Account for the 30%~100% of alumina carrier containing Ni total weight.In carrier also θ-Al can be contained2O3、α-Al2O3And/or γ-Al2O3, best α-Al2O3Lower than 30wt%.
Alumina carrier containing Ni of the invention, by alumina carrier containing Ni total weight be 100% in terms of, nickel content be 0.1~ 10wt%, preferably 0.75~7.5wt%.20~180m of specific surface area2/ g, hole hold 0.12cm3/ g~0.65cm3/g。
Nickeliferous boehmite of the invention is not the simple object for being boehmite and nickel compound containing or nickel salt solution Reason blending or cladding, but generation acid-base reaction, have plastic process, and final be made mixes containing for crystalline form with specific nickel and aluminium Nickel alumina support.
The present invention also provides a kind of preparation methods of more specific palladium-silver series hydrocatalyst, with containing active component palladium With the salt solution impregnation alumina carrier containing Ni of silver, palladium and silver are impregnated using step impregnation or simultaneously, by washing, drying, roasting It burns and obtains catalyst；Alumina carrier containing Ni by nickeliferous boehmite at least through molding, drying, roasting process and obtain；Its In nickeliferous boehmite preferably obtained by following methods, detailed process includes the following steps：
(1) it neutralizes in kettle and bottom water is added, bottom water is deionized water, is heated to 50~90 DEG C；
(2) acid aluminum saline solution, acid nickel salt aqueous solution are prepared respectively, by acid aluminium salt aqueous solution and acid nickel salt water Solution is uniformly mixed, and obtains the acidic mixed solution of aluminium containing salt and nickel salt, and adjusting the acidic mixed solution temperature is 50~90 DEG C, Preferable temperature is 50~70 DEG C, and wherein acid aluminium salt concentration of aqueous solution is 10~80g Al2O3/ L, acid nickel salt aqueous solution concentration For 3~50gNiO/L；
(3) alkali metal aluminate solution is prepared, alkali metal aluminate solution concentration is 50~300g Al2O3/L；
(4) (2) and (3) cocurrent are added in (1), constant ventilation stirring；
(5) 50~90 DEG C of gelling temperature of rate-determining steps (4), plastic pH value 7~10；
(6) it after cemented into bundles, through aging, is filtered, washed, dries nickeliferous boehmite is made.
Tank bottom can be passed through air in the preparation method step (1)；Preferably 50~70 DEG C of step (5) gelling temperature, pH value It is preferred that 7.5~9.5.
Preferably 50~70 DEG C of temperature described in step (1) in preparation method of the present invention；Step (2) described temperature preferably 50~ 70 DEG C, stablize 3~5min.Solution temperature is being just in acid aluminium salt and nickel salt mixed solution, alkali metal aluminate solution and plastic cans Subzero temperature difference is no more than 3 DEG C, and three's temperature is preferably identical.It is heavy that alkalinity can also be added in step (3) in alkali metal aluminate solution Shallow lake agent aqueous solution.Alkali metal aluminate solution (or mixed solution of itself and the formation of alkaline precipitating agent aqueous solution) pH value is 9~14, Preferable ph 12~14.
Aluminium salt, nickel salt and alkaline precipitating agent described in the preparation method of nickeliferous boehmite provided by the invention Using the raw material of industry.The acid aluminium salt aqueous solution can be one or more of aluminium chloride, aluminum sulfate and aluminum nitrate Mixed solution, preferably sulfuric acid aluminum solutions.The acid nickel salt aqueous solution can be nickel chloride, nickel sulfate, nickelous bromide and nitric acid The mixed solution of one or more of nickel, preferably nickel nitrate solution.Acid aluminium salt and acid nickel salt mixed solution pH value be 2~ 5, preferable ph 2~4.The alkali metal aluminate solution refers to sodium metaaluminate or potassium metaaluminate solution；The alkalinity is heavy Shallow lake agent refers to ammonium bicarbonate soln, sodium bicarbonate solution, ammonia spirit, sodium hydroxide solution or calcium hydroxide solution, preferably Ammonia spirit, NH3Content is 50~120g/L.
The aging of step (6) described material refers to the solution after making plastic under continuing ventilation stirring or stationary state one Kept for certain time at fixed temperature and pH value.Wherein aging temperature is 50~80 DEG C, and ageing time is 10~60min.
The mode of washing of step (6) described material is common sense well known to those skilled in the art, can add water using when filtering Washing, mashing washing the modes such as wash using lower alcohols, control 40~80 DEG C of temperature when washing, pH value 4~8, wash time For 20~40min, washing times are 2~5 times.
Drying mode described in step (6) can using oven drying, spray drying, mesh-belt kiln drying, fluidized bed drying, Natural drying, microwave drying etc., drying temperature are 70~150 DEG C, drying time 2~for 24 hours, and it is segmented preferably with different temperatures dry It is dry.
The nickeliferous boehmite of the present invention before shaping, can according to need and peptizing agent, extrusion aid and aluminium oxide is added One or more of dry glue powder, the substance specifically used and additional amount can have knowledge by this field and be determined.For example, The peptizing agent can be one or more of nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid, and additional amount is need molded samples total weight 3 ~10%；The extrusion aid can be sesbania powder, and dosage is need molded samples total weight 2~6%；The alumina dry glue Powder is made using conventional method, but additional amount is preferably lower than the 10% of nickeliferous boehmite gross mass.
The carrier calcination method and condition of catalyst is that catalyst carrier roasts common method and condition in the present invention, can be adopted It is roasted with vertical heater, converter and mesh-belt kiln, the roasting condition of the carrier is：800~1200 DEG C of 3~8h of roasting, roasting Preferably 900~1100 DEG C of temperature.The maturing temperature of the carrier is the maturing temperature of carrier before impregnating active component palladium, silver, with Specific surface, Kong Rong needed for guaranteeing catalyst, and make finally to be made the carrier with specific nickel and aluminium mixing crystalline form.In this temperature Before roasting, carrier may be prepared by low-temperature bake, but be middle transition calcination steps, maturing temperature is preferably 500~700 DEG C roasting 3~8h.300~550 DEG C of catalyst maturing temperature, roast 3~8h.
In the method for the invention, rare-earth element cerium and/or lanthanum and alkali metal and/or alkaline-earth metal are formed in carrier It is added in the process；Or after carrier molding, it is added in advance into carrier before dipping active component；Either in dipping activity Group timesharing, is added simultaneously with active constituent dipping solution.
Catalyst of the invention is before the use, of the invention preferably at 20~120 DEG C with hydrogen reducing 4~24 hours Hydrogenation catalyst is suitable for alkadienes and selective acetylene hydrocarbon hydrogenation.
Nickeliferous boehmite provided by the invention and carrier prepared therefrom, advantage are that nickel and thin water aluminium can will be intended Stone organically combines, and forms the alumina carrier containing Ni of specific crystal formation, while having to the pore structure and acidity of carrier Preferable adjustment effect.Had using the catalyst of alumina carrier containing Ni preparation to the noble metal active component of load preferable Peptizaiton, catalyst have preferable selectivity and stability.
Specific embodiment
Analysis method：
Catalyst forms content assaying method：Using national standard《Atomic absorption spectroscopy general rule》GB/T15337 With《Chemical reagent flame atom absorption spectrophotography method general rule》GB19723 analysis；
Specific surface area：Using 19587 standard test of GB/T；
Kong Rong：GB/T 21650.2-2008 standard test；
Crystalline form analysis：Using D8Advance type x-ray powder diffraction instrument (XRD) measurement of German Bruker company production The crystal form of carrier, actual conditions：CuK α radiation, 40 kilovolts, 40 milliamperes, 0.02 ° of scanning speed/step, 0.5 second/step, B1 referred to The integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, B2 refer to the product at the peak that 2 θ are 43.3~48.5 ° in XRD spectra Divide intensity；
Diene value：It is measured using UOP 326-2008 method；
Bromine valency：Using SH/T 0236-92 standard test.
Water content：Using GB/T 11133-89 standard test；
Sulfur content：It is measured using WK-2B microcoulomb instrument；
The present invention is further illustrated below by embodiment, but is not regarded as that present invention is limited only by this.
Embodiment 1
(1) preparation of nickeliferous carrier
It is 25g Al by 2L concentration2O3The nickel nitrate solution mixing that the aluminum sulfate solution and 1L concentration of/L is 3.2gNiO/L is equal In the even container for being packed into high level, compound concentration is 50g Al2O3/ L sodium aluminate solution 3L is packed into the container of high level, and two Connect the stainless steel that peristaltic pump progress flow control inflow is equipped with the belt stirrer of 2L bottom water and tank bottom can be passed through gas under container to hold In device, 65 DEG C of reaction temperature, it is 9.0 that control flow, which adjusts pH value of reaction system, is by the way that ammonium hydroxide adjusting slurry pH value is added dropwise 9.2, aging 35 minutes, are separated by filtration mother liquor after reaction, and nickeliferous boehmite is made in washing, drying.Weigh preparation Nickeliferous boehmite, is kneaded into plastic, extruded moulding, and nickeliferous carrier is made in drying, 600 DEG C of roastings.Preparation cerous nitrate, Magnesium nitrate solution impregnates nickeliferous carrier using equi-volume impregnating, in 120 DEG C of dry 4h, 980 DEG C of roasting 4h, obtains containing cerium, magnesium With nickel carrier.
(2) preparation of catalyst
Palladium nitrate, silver nitrate are configured to activity component impregnation liquid, solution ph=2.4 are adjusted, by prepared maceration extract It is impregnated on 100g carrier, removes extraction raffinate after twenty minutes, be washed with distilled water, aged, drying, 420 DEG C of roasting 4h are urged Agent C1.
Embodiment 2
(1) preparation of nickeliferous carrier
It is 25g Al by 2L concentration2O3The nickel nitrate solution that the aluminum sulfate solution and 1L concentration of/L is 10.5g NiO/L mixes It is uniformly packed into the container of high level, compound concentration is 75g Al2O3//L sodium aluminate solution 2L is packed into the container of high level, Connect peristaltic pump under two containers and carries out that flow control flows into the belt stirrer equipped with 2L bottom water and tank bottom can be passed through the stainless steel of gas In container, 60 DEG C of reaction temperature, it is 9.2 that control flow, which adjusts pH value of reaction system, is by the way that ammonium hydroxide adjusting slurry pH value is added dropwise 9.4, aging 30 minutes, are separated by filtration mother liquor after reaction, washing.It is made nickeliferous in 90 DEG C of dry 3h, 120 DEG C of dry 2h Boehmite.The nickeliferous boehmite for weighing preparation, is kneaded into plastic, extruded moulding, then in 120 DEG C of dry 4h, 620 DEG C of roasting 4h, obtain nickeliferous carrier.Calcium nitrate solution is prepared, nickeliferous carrier is impregnated using equi-volume impregnating, at 120 DEG C Dry 4h, 1000 DEG C of roasting 4h obtain calcic and nickel carrier.
(2) preparation of catalyst
Palladium chloride is configured to activity component impregnation liquid, adjusts solution ph=2.5, prepared maceration extract is impregnated into On 100g carrier, extraction raffinate is removed after 15 minutes, is washed with distilled water, after aged, dried, 420 DEG C of roasting 4h are made to be urged containing palladium Agent；Silver nitrate is configured to activity component impregnation liquid, and prepared maceration extract is impregnated on palladium-containing catalyst, aged, baking Dry, 450 DEG C of roasting 4h obtain catalyst C2.
Embodiment 3
(1) preparation of nickeliferous carrier
It is 40g Al by 5L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas In steel container, the nickel nitrate solution that 1L concentration is 4.5gNiO/L is packed into the container of high level, and lower even peristaltic pump carries out flow velocity control System.It is passed through the mixed gas of carbon dioxide and air, while prepared nickel nitrate solution, carbon dioxide in gas mixture is added dropwise Concentration is 60v%, flow 4Nm3/h.30 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide, and aging 35 divides Clock, is separated by filtration mother liquor, and nickeliferous boehmite is made in washing, drying.The nickeliferous boehmite for weighing preparation, is kneaded into Plastic, extruded moulding, drying obtain nickeliferous carrier in 110 DEG C of dry 6h, 580 DEG C of roasting 4h.Lanthanum nitrate hexahydrate is prepared, is adopted Nickeliferous carrier is impregnated with equi-volume impregnating, in 120 DEG C of dry 4h, 1020 DEG C of roasting 4h, is obtained containing lanthanum and nickel carrier.
(2) preparation of catalyst
Palladium nitrate and silver nitrate are configured to activity component impregnation liquid, solution ph=2.3 are adjusted, by prepared maceration extract It is impregnated on the nickeliferous carrier of 100g, removes extraction raffinate after twenty minutes, be washed with distilled water, after aged, dry, 450 DEG C of roasting 4h, Obtain catalyst C3.
Embodiment 4
(1) preparation of nickeliferous carrier
It is 40g Al by 5L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas In steel container, the nickel nitrate solution that 2L concentration is 7.9gNiO/L is packed into the container of high level, and lower even peristaltic pump carries out flow velocity control System.It is passed through the mixed gas of carbon dioxide and air, while prepared nickel nitrate solution, carbon dioxide in gas mixture is added dropwise Concentration is 70v%, flow 3Nm3/h.35 DEG C of reaction temperature, reaction end pH value 9.8, stopping is passed through carbon dioxide, and aging 30 divides Clock, is separated by filtration mother liquor, and nickeliferous boehmite is made in washing, drying.The nickeliferous boehmite for weighing preparation, with carbonic acid Lithium, nitric acid, citric acid, sesbania powder and water mixer kneader are at plastic, extruded moulding, in 110 DEG C of dry 6h, 960 DEG C of roasting 4h, It obtains containing lithium and nickel carrier.
(2) preparation of catalyst
Palladium nitrate, silver nitrate are configured to activity component impregnation liquid, solution ph=2.6 are adjusted, by prepared maceration extract It is impregnated on the nickeliferous carrier of 100g, removes extraction raffinate after 25 minutes, be washed with distilled water, aged, drying, 480 DEG C of roasting 4h are obtained To catalyst C4.
Embodiment 5
(1) preparation of nickeliferous carrier
It is 80g Al by 2.5L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through gas not It becomes rusty in steel container, is passed through the mixed gas of carbon dioxide and air, carbon dioxide in gas mixture concentration is 60v%, flow 3Nm3/h.35 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide.Under blowing air stirring condition, 0.5L is added Concentration is the nickel nitrate solution of 14.5g NiO/L, is 9.5 by the way that ammonium hydroxide is added dropwise to adjust slurry pH value after stablizing 30 minutes, reaction After aging 30 minutes, be separated by filtration mother liquor, it is washing, dry, nickeliferous boehmite is made.Weigh preparation it is nickeliferous intend it is thin Diaspore, is kneaded into plastic, and nickeliferous carrier is made in 110 DEG C of dry 6h, 650 DEG C of roasting 4h in extruded moulding.Prepare nitric acid Cerium solution impregnates nickeliferous carrier using equi-volume impregnating, in 120 DEG C of dry 5h, 920 DEG C of roasting 4h, obtains carrying containing cerium and nickel Body.
(2) preparation of catalyst
Palladium nitrate and silver nitrate are configured to activity component impregnation liquid, solution ph=2.7 are adjusted, by prepared maceration extract It is impregnated on the nickeliferous carrier of 100g, removes extraction raffinate after twenty minutes, be washed with distilled water, aged, drying, 460 DEG C of roasting 4h are obtained To catalyst C5.
Comparative example 1
(1) preparation of carrier
It is 50g Al by 1L concentration2O3The aluminum sulfate solution and 1.5L concentration of/L is 150g Al2O3/ L sodium aluminate solution Be respectively charged into the container of high level, connect under two containers peristaltic pump carry out flow control flow into equipped with 5L bottom water belt stirrer and Tank bottom can be passed through in the rustless steel container of gas, and 65 DEG C of reaction temperature, it is 9.0 that control flow, which adjusts pH value of reaction system, be passed through It is 9.2 that ammonium hydroxide, which is added dropwise, and adjusts slurry pH value, after reaction aging 35 minutes, is separated by filtration mother liquor, and washing, drying are made quasi- Boehmite.The boehmite for weighing preparation, is kneaded into plastic, extruded moulding, and nickeliferous load is made in drying, 600 DEG C of roastings Body.Cerous nitrate, magnesium nitrate solution are prepared, nickeliferous carrier is impregnated using equi-volume impregnating, in 120 DEG C of dry 4h, 970 DEG C of roastings 4h is obtained containing cerium and magnesium carrier.
(2) preparation of catalyst
Palladium nitrate, silver nitrate are configured to activity component impregnation liquid, solution ph=2.4 are adjusted, by prepared maceration extract It is impregnated on 100g carrier, removes extraction raffinate after twenty minutes, be washed with distilled water, aged, drying, 420 DEG C of roasting 4h are urged Agent D1.
Comparative example 2
(1) preparation of carrier
It is 110g Al by 2L concentration2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless of gas In steel container, it is passed through the mixed gas of carbon dioxide and air, carbon dioxide in gas mixture concentration is 60v%, flow 4Nm3/ h.30 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide, aging 35 minutes, is separated by filtration mother liquor, wash, It is dry, obtain boehmite.The boehmite for weighing preparation is kneaded into plastic, extruded moulding, drying, in 110 DEG C of dryings 6h, 580 DEG C of roasting 4h, obtains carrier.Lanthanum nitrate hexahydrate is prepared, using equi-volume impregnating impregnated carrier, in 120 DEG C of dryings 4h, 1000 DEG C of roasting 4h, obtains carrier containing lanthanum.
(2) preparation of catalyst
Palladium nitrate and silver nitrate are configured to activity component impregnation liquid, solution ph=2.3 are adjusted, by prepared maceration extract It is impregnated on 100g carrier, removes extraction raffinate after twenty minutes, be washed with distilled water, after aged, dry, 450 DEG C of roasting 4h are obtained Catalyst D2.
Comparative example 3
This comparative example prepares nickeliferous carrier according to the method that embodiment in CN1123392C describes, and specific step is as follows：
It weighs 200g aluminum hydroxide solid elastomer powder and 4.0g sesbania powder after mixing, then weighs 15g carbon black and 17.62g alkali After mixing, tetrabutylammonium hydroxide (the wherein C previously measured with graduated cylinder is wherein being added in formula nickelous carbonate16H37NO's Content about 10w%) 55ml, is stirred with glass bar, comes into full contact with tetrabutylammonium hydroxide solution with mixture, placed 20 minutes Afterwards, it adds it to and is mixed in the aluminum hydroxide solid elastomer powder of sesbania powder, mix again；
By the mixed solution of acetic acid and citric acid, deionized water, it is added to and is mixed with basic nickel carbonate, carbon black and sesbania powder In aluminum hydroxide solid elastomer powder, after kneading is at uniform paste plastic, cloverleaf pattern item is extruded on banded extruder, at 120 DEG C Dry, roasting, is made nickeliferous aluminium oxide.Magnesium nitrate aqueous solution is prepared, nickeliferous carrier is impregnated using equi-volume impregnating, 110 DEG C dry 6h, 1000 DEG C of roasting 4h obtain nickeliferous carrier.
Palladium nitrate and silver nitrate are configured to activity component impregnation liquid, solution ph=2.7 are adjusted, by prepared maceration extract It is impregnated on the nickeliferous carrier of 100g, removes extraction raffinate after twenty minutes, be washed with distilled water, aged, drying, 460 DEG C of roasting 4h are obtained To catalyst D3.
Embodiment 6
(1) preparation of nickeliferous carrier
It is 50g Al by 4L concentration2O3The nickel nitrate solution that the aluminum nitrate solution and 1L concentration of/L is 2gNiO/L is uniformly mixed It is packed into the container of high level, the ammonia spirit that compound concentration is 8wt% is packed into the container of high level, and wriggling is connected under two containers Pump carries out belt stirrer of the flow control inflow equipped with 2L bottom water and tank bottom can be passed through in the rustless steel container of gas, reaction temperature 45 DEG C, it is 7.8 that control flow, which adjusts pH value of reaction system, after reaction, ammonium hydroxide is added and adjusts slurry pH value 8.2, always Change 35 minutes, be separated by filtration mother liquor, nickeliferous boehmite is made in washing, drying.The nickeliferous boehmite of preparation is weighed, It is kneaded into plastic, then extruded moulding obtains nickeliferous carrier in 120 DEG C of dry 4h, 1060 DEG C of roasting 4h.
(2) preparation of catalyst
Palladium chloride is configured to activity component impregnation liquid, adjusts solution ph=2.2, prepared maceration extract is impregnated into On 100g carrier, extraction raffinate is removed after 35 minutes, is washed with distilled water, after aged, dried, 430 DEG C of roasting 4h are made to be urged containing palladium Agent；Silver nitrate is configured to activity component impregnation liquid, and prepared maceration extract is impregnated on palladium-containing catalyst, aged, baking Dry, 450 DEG C of roasting 4h obtain catalyst C6.
Comparative example 4
(1) preparation of carrier
Preparation 4L concentration is 50g Al2O3The aluminum nitrate solution and concentration of/L is that the ammonia spirit of 8wt% is respectively charged into a high position In the container at place, peristaltic pump progress belt stirrer of the flow control inflow equipped with 2L bottom water is connected under two containers and tank bottom can be passed through gas In the rustless steel container of body, 45 DEG C of reaction temperature, it is 7.8 that control flow, which adjusts pH value of reaction system, after reaction, ammonia is added Water adjusts slurry pH value 8.25, aging 35 minutes, is separated by filtration mother liquor, washing, dry, obtained boehmite.It weighs The boehmite of preparation, conjunction are kneaded into plastic, and extruded moulding obtains carrier in 120 DEG C of dry 4h, 1030 DEG C of roasting 4h.
(2) preparation of catalyst
Palladium chloride is configured to activity component impregnation liquid, adjusts solution ph=2.2, prepared maceration extract is impregnated into On 100g carrier, extraction raffinate is removed after 35 minutes, is washed with distilled water, after aged, dried, 430 DEG C of roasting 4h are made to be urged containing palladium Agent；Silver nitrate is configured to activity component impregnation liquid, and prepared maceration extract is impregnated on palladium-containing catalyst, aged, baking Dry, 450 DEG C of roasting 4h obtain catalyst D4.
Catalyst D1~D4 catalyst physical property and composition are shown in Table in catalyst C1~C6 and comparative example 1-4 in embodiment 1-6 1。
1 embodiment catalyst of table and comparative example catalyst physical property and composition
Evaluating catalyst：
Use drippolene for raw material, feedstock property is shown in Table 2, evaluates C1~C6 and D1~D4 catalyst.Respectively 300h is evaluated, every 12h sampling analysis bromine valency and diene, average data see the table below 3.
Evaluating catalyst is carried out on 100ml adiabatic reactor hydrogenation reaction device, and catalyst is first under 90 DEG C of hydrogen Reduction 8 hours, then cools to 45 DEG C.Evaluate process conditions：Reaction pressure：2.8MPa, inlet temperature：45 DEG C, fresh feed Oily air speed：3.5h-1, hydrogen and oil volume ratio：200: 1 (volume ratio is in terms of green oils).
2 hydrogenating materials oil nature of table
3 evaluating catalyst average data of table
As can be seen from the above Examples and Comparative Examples, hydrogen is added to urge using the nickel-molybdenum system of the nickeliferous aluminium oxide preparation of the present invention Agent, under identical evaluation process conditions, the diene of hydrogenated products, bromine valency are relatively low, this has been absolutely proved in embodiment The catalyst of preparation hydrogenation activity with higher and selectivity.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art It all should belong to the protection scope of the claims in the present invention.

Claims (14)

1. a kind of selective hydrogenation catalyst, it is characterised in that：Contain active component palladium and silver in catalyst, is with nickeliferous aluminium oxide Carrier is palladium content 0.05~0.8wt% in terms of simple substance, preferably 0.15~0.5wt% in terms of 100%, oxygen by total catalyst weight Change silver 0.05~5wt%, preferably 0.2~3wt%, nickel 0.1~10wt% in terms of simple substance, preferably 0.5~5wt%；Catalyst ratio 20~150m of surface area2/ g, preferably 60~120m2/ g, hole hold 0.12~0.6ml/g, preferably 0.3~0.5ml/g；Alkali metal and/ Or 0.1~10wt% of alkaline earth oxide, preferably 0.5~3wt%；Cerium oxide and/or lanthana 0~5wt%, preferably 0.5 ~1.2wt%；The presoma of alumina carrier containing Ni is nickeliferous boehmite, is had in the preparation process of nickeliferous boehmite Acid-base neutralization and plastic process；Alumina carrier containing Ni is impregnated by the way that active component palladium-silver solution will be contained, through drying, roasting, system Obtain hydrogenation catalyst.
2. selective hydrogenation catalyst according to claim 1, it is characterised in that：The specific surface area of nickeliferous boehmite 300~420m20.7~1.2cm of/g, Kong Rongwei3/ g, aperture are 5~10nm；With nickeliferous boehmite total weight for 100% Meter, nickel content are 0.1~10wt%, preferably 0.5wt~5wt%.
3. selective hydrogenation catalyst according to claim 1, it is characterised in that：Alumina carrier containing Ni intends thin water by nickeliferous Aluminium stone at least through molding, drying, roasting process and obtain, contain δ-Al2O3、δ-NiAl26O40And NiAl2O4Crystal form, and XRD is composed 0.45≤B1/B2≤0.85 in figure, B1 refer to that the integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, B2 refer to XRD The integrated intensity at the peak that 2 θ are 43.3~48.5 ° in spectrogram.
4. selective hydrogenation catalyst according to claim 1, it is characterised in that：δ-Al in alumina carrier containing Ni2O3、δ- NiAl26O40And NiAl2O4Account for 30~100wt% of alumina carrier containing Ni total weight.
5. selective hydrogenation catalyst according to claim 1, it is characterised in that：Contain θ-in alumina carrier containing Ni Al2O3、α-Al2O3And/or γ-Al2O3；Best α-Al2O3Content is lower than 30wt%.
6. selective hydrogenation catalyst according to claim 3, it is characterised in that：Alumina carrier containing Ni roasting condition is： 800~1200 DEG C of 4~10h of roasting, preferably 900~1100 DEG C of maturing temperature.
7. selective hydrogenation catalyst according to claim 1, it is characterised in that：Catalyst maturing temperature is 300~550 DEG C, calcining time is 3~8h.
8. a kind of preparation method of selective hydrogenation catalyst described in claim 1, it is characterised in that：With containing active component palladium With the salt solution impregnation alumina carrier containing Ni of silver, palladium and silver are impregnated using step impregnation or simultaneously, by washing, drying, roasting It burns and obtains catalyst；Alumina carrier containing Ni by nickeliferous boehmite at least through molding, drying, roasting process and obtain；Its In nickeliferous boehmite obtained by following methods, detailed process includes the following steps：
(1) it neutralizes in kettle and bottom water is added, bottom water is deionized water, is heated to 50~90 DEG C；
(2) acid aluminum saline solution, acid nickel salt aqueous solution are prepared respectively, by acid aluminium salt aqueous solution and acid nickel salt aqueous solution Be uniformly mixed, obtain the acidic aqueous solution of aluminium containing salt and nickel salt, adjust its solution temperature be 50~90 DEG C, preferable temperature be 50~ 70 DEG C, wherein acid aluminium salt concentration of aqueous solution is preferably 10~80gAl2O3/ L, acid nickel salt aqueous solution concentration is preferably 3~ 50gNiO/L；
(3) alkali metal aluminate solution is prepared, alkali metal aluminate solution concentration is preferably 50~300gAl2O3/L；
(4) (2) and (3) cocurrent are added in (1), constant ventilation stirring；
(5) 50~90 DEG C of gelling temperature of rate-determining steps (4), plastic pH value 7~10, optimum condition are 50~70 DEG C of gelling temperature； Plastic pH value 7.5~9.5；
(6) it after cemented into bundles, through aging, is filtered, washed, dries nickeliferous boehmite is made.
9. the preparation method of selective hydrogenation catalyst according to claim 8, it is characterised in that：Neutralization in step (1) The bottom of kettle is passed through air.
10. the preparation method of selective hydrogenation catalyst according to claim 8, it is characterised in that：It is alkali in step (3) The pH value of metal aluminate solution is 9~14, preferable ph 12~14.
11. the preparation method of selective hydrogenation catalyst according to claim 8, it is characterised in that：Acid aluminium salt aqueous solution For the mixed solution of one or more of aluminium chloride, aluminum sulfate and aluminum nitrate, preferably sulfuric acid aluminum solutions；Acid nickel salt aqueous solution It is the mixed solution of one or more of nickel chloride, nickel sulfate, nickelous bromide and nickel nitrate, preferably nickel nitrate solution；Alkali metal Aluminate solution refers to sodium metaaluminate or potassium metaaluminate solution.
12. the preparation method of selective hydrogenation catalyst according to claim 8, it is characterised in that：It is acid in step (2) Aluminium salt and acid nickel salt aqueous solution mixing, obtain the acidic aqueous solution of aluminium containing salt and nickel salt, and pH value is 2~5, and preferable ph 2~ 4。
13. the preparation method of selective hydrogenation catalyst according to claim 8, it is characterised in that：In step (6), aging Temperature is 50~80 DEG C, and ageing time is 10~60min.
14. the preparation method of selective hydrogenation catalyst according to claim 8, it is characterised in that：Rare-earth element cerium and/or Lanthanum and alkali metal and/or alkaline-earth metal are added in carrier forming process；Or after carrier molding, impregnate active component It is added in advance into carrier before；Either when impregnating active component, it is added simultaneously with active constituent dipping solution.
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