CN108855129A - A kind of nickel-silver series hydrocatalyst and preparation method thereof - Google Patents

A kind of nickel-silver series hydrocatalyst and preparation method thereof Download PDF

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CN108855129A
CN108855129A CN201710339787.8A CN201710339787A CN108855129A CN 108855129 A CN108855129 A CN 108855129A CN 201710339787 A CN201710339787 A CN 201710339787A CN 108855129 A CN108855129 A CN 108855129A
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nickel
nickeliferous
preparation
catalyst
silver
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CN108855129B (en
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胡晓丽
孙利民
钱颖
马好文
郑云弟
展学成
梁顺琴
王斌
梁玉龙
谢培思
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China Petroleum and Natural Gas Co Ltd
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    • 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
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    • 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
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    • B01J35/635—0.5-1.0 ml/g
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
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Abstract

The present invention relates to a kind of nickel-silver series catalysts and preparation method thereof, and in particular to a kind of using nickeliferous aluminium oxide as the preparation method of the nickel-silver series hydrocatalyst of carrier.Containing active component nickel and silver, using nickeliferous aluminium oxide as carrier, the presoma of alumina carrier containing Ni is nickeliferous boehmite, there is acid-base neutralization and plastic process in the preparation process of the nickeliferous boehmite.Specific carrier is used in catalyst of the present invention, advantage is organically combine nickel and boehmite, it is effectively dispersed in active component nickel in boehmite, and form the alumina carrier containing Ni of specific crystal formation, there is preferable adjustment effect to the pore structure and acidity of carrier simultaneously, with merely using preparation catalyst compared with, have many advantages, such as that process is simple, while the easy modulation of carrier material performance.Nickel-silver hydrogenation catalyst hydrogenation activity and selectivity of the invention is high, and chemical stability and thermal stability are good.

Description

A kind of nickel-silver series hydrocatalyst and preparation method thereof
Technical field
The present invention relates to a kind of nickel-silver catalyst and preparation method thereof, and in particular to one kind is using nickeliferous aluminium oxide as carrier Nickel-silver hydrogenation catalyst preparation method.
Background technique
2017, Chinese ethylene production capacity will continue in rising trend.Important by-products of the drippolene as cracking of ethylene, Account for about the 50%~80% of ethylene production capacity.This part byproduct how is made good use of, the economic benefit for improving enterprise will be produced Raw great influence.Meanwhile in drippolene also containing the various unsaturated hydrocarbons such as a large amount of diolefin, alkyl alkenyl arene, indenes with And the impurity such as sulphur, nitrogen, oxygen, cause gasoline property unstable.It is industrial generally to be refined using two-stage hydrogenation, it is first low through one section Warm liquid-phase hydrogenatin saturation chain conjugated alkene, cyclic conjugated alkene and styrene etc.；Contain again through two sections of high temperature gas phase hydrogenation removals The organic impurities of sulphur, nitrogen, oxygen etc. simultaneously as aromatics extraction raw material produces benzene, toluene and dimethylbenzene after being saturated monoolefin hydrogenation.Cause This, is an important branch in field of hydrogenation by the hydrogen addition technology of core of pyrolysis gasoline hydrogenation catalyst, in steam cracking system There is very important status in the post-processing of ethylene.Currently used one-stage hydrogenation catalyst is roughly divided into two classes, and one kind is living Property component is nickel non-precious metal catalyst；Another kind of active component is catalyst used in noble metal.Non-precious metal catalyst Because the factors such as architectural difference and tenor height have certain anti-impurity and water-resistant capacity, price advantage is also than more significant.Cause This non-precious metal catalyst industrialization product is gradually replacing noble metal catalyst to be applied to pyrolysis product and is adding hydrogen series catalyst Agent.
CN101254465B has studied a kind of catalyst for cracking carbon five selective hydrogenation, includes following mass percent Component：Nickel 10%~35%, lanthanum 0.5%~3%, silver-colored 0.3%~3%, alumina support 59%~89.2%, with catalyst Gross mass meter.Potassium and/or strontium and lead can also be included.The catalyst can be used for cracking carbon five selective hydrogenation, it may also be used for Cracking c_5 adds hydrogen entirely, it has excellent conversion ratio, selective and good stability.
US3472763 reports a kind of diene selective hydrogenation catalyst, active component Ni content 1~20%, auxiliary agent MoO3Content 1~5%, auxiliary agent alkali metal and alkaline earth metal content 1~5%, catalyst pores, which are held, is greater than 0.4ml/g, and specific surface is big In 30m2/ g, this catalyst are to impregnate Al by the aqueous solution of active component and auxiliary agent2O3Carrier is made.
CN1218822A reports a kind of Ni/Al2O3Suitable for the selective hydrocatalyst of pyrolysis gasoline cut fraction, this is urged Agent is by nickel load in obtained on the alumina support containing lithium or alkaline-earth metal, this catalyst is bearing plus hydrogen load and adding It is not good enough in terms of stabilized hydrogen.
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 the aluminium oxide of catalyst carrier for hydrgenating material is improved by these methods Performance is limited.The property for preparing aqua oxidation aluminum feedstock used in alumina support is to produce excellent properties carrying alumina One of body 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, account for the 85% more of its total hole greater than the ratio in the hole 6.0nm, Kong Rong, average Aperture is larger, and macropore proportion is more, 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 the salt of aluminium to be added to silicon, if necessary, there are also the compounds of aluminium Alkaline aqueous solution or suspension in, so that the pH of the mixture so obtained is reduced at least 6.5, then by further adding Alkaline solution adjusts pH value to 7-8, separates the solid so deposited, dries, forms and is 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, still The catalyst activity 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 Phys Chem B, 2002,106:5897-5906 " equally obtains similar conclusion.Since nickel and alumina support are roasted in high temperature Strong interaction can occur during burning and generate spinel structure, be remarkably decreased so as to cause catalyst activity, therefore in high temperature It is all as prudent using the two as possible before roasting, avoid the generation of spinel structure.It is different from other metals, it is rare it is nickeliferous intend it is thin Diaspore report generally requires to carry out high-temperature roasting when because preparing catalyst carrier with it.
In the preparation process of catalyst carrier, the compound containing active metal component is introduced in the form of kneading, Make the compound for containing a certain amount of active metal component in shaping carrier, reduces the catalysis of high-content active metal component to reach The problem of load difficulty encountered in agent preparation process.But by active metallic compound by way of kneading method is using kneading With aluminum hydroxide solid elastomer powder or the direct mixed-forming of alumina powder, there are crystal grain to mix uneven and catalyst strength for this method The problems such as variation, while being also not easy to combine between simple kneading each component and forming specific skeleton structure.
Summary of the invention
The present invention provides a kind of nickel-silver series hydrocatalyst and preparation method thereof.
Nickel-silver series hydrocatalyst of the invention contains active component nickel and silver, using nickeliferous aluminium oxide as carrier, with catalysis Agent total weight is 100% meter, containing 10~20wt% of nickel oxide (preferably 14.5~18.2wt%), silver oxide 0.01~ 3wt% (preferably 0.05~1.5wt%), 0~5wt% of cerium oxide and/or lanthana (preferably 0.2~1.2wt%), alkali gold Category and/or 0~6wt% of alkaline earth oxide (preferably 0.5~3wt%)；50~150m of specific surface area of catalyst2/ g, hole Hold 0.25~0.55ml/g, 0.5~1.1g/cm of heap density3.The presoma of alumina carrier containing Ni is nickeliferous boehmite, Nickel and boehmite can organically be combined, while the nickeliferous boehmite and carrier prepared therefrom are with suitable Suitable pore-size distribution.
Carrier in nickel-silver series hydrocatalyst of the invention is nickeliferous aluminium oxide, needs to prepare first and nickeliferous intends thin water Aluminium stone, the i.e. presoma of alumina carrier containing Ni are nickeliferous boehmites, be not boehmite and nickel compound containing or The simple physical of nickel salt solution blends or cladding, but acid-base reaction occurs, and has plastic process, and final be made has specific nickel With the carrier of aluminium mixing crystalline form.Only in this way nickel and boehmite can organically be combined, preferably this is nickeliferous quasi- Boehmite and carrier prepared therefrom also have suitable pore-size distribution.
Nickeliferous boehmite is through alumina carrier containing Ni obtained from molding, drying, roasting.Depending on finally containing in the present invention Nickel alumina support is different using purpose, the preparation method of nickeliferous boehmite, nickel source, nickel content, alumina carrier containing Ni Preparation method, calcination for activation temperature etc. can be different.
The presoma of alumina carrier containing Ni of the present invention, that is, nickeliferous boehmite preferably (intends thin water with nickeliferous Aluminium stone total weight is 100wt% meter), 0.1~10wt% of nickel content, preferably 0.5~5wt%；300~420m of specific surface area2/ g, Hole holds 0.7~1.2cm3/ g, 5~10nm of aperture；The nickeliferous boehmite has acid-base neutralization and plastic mistake during the preparation process Journey.
Alumina carrier containing Ni used in catalyst in the present invention, is preferably formed by nickeliferous boehmite, is roasted And obtain, contain δ-Al2O3、δ-NiAl26O40And NiAl2O4Crystal form, and 0.45≤B1/B2≤0.85 in XRD spectra, B1 refer 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.
In the present invention in alumina carrier containing Ni used in catalyst, contain δ-Al2O3、δ-NiAl26O40And NiAl2O4It is brilliant The mixed crystal of type, best δ-Al2O3、δ-NiAl26O40And NiAl2O4Account for 30~100wt% of alumina carrier containing Ni total weight.It removes Contain δ-Al2O3、δ-NiAl26O40And NiAl2O4Outside the mixed crystal of crystal form, θ-Al can be also contained in carrier2O3、α-Al2O3And/or γ-Al2O3, best α-Al2O3Content is lower than 30wt%.
It is different using purpose that final catalyst is regarded in the present invention, the preparation method of nickeliferous boehmite, nickel source, nickel contain Amount, alumina carrier containing Ni calcination for activation temperature etc. can be different.Best nickel content is in alumina carrier containing Ni of the invention 0.1~10wt%, preferably 0.5~5wt%.25~250m of specific surface area20.15~0.85cm of/g, Kong Rongwei3/ g, aperture be 8~ 40nm。
In the present invention active component nickel, silver be in the form of soluble-salt be added, nickel source be selected from nickel nitrate, nickel acetate, The one or more of nickel chloride or nickel sulfate, preferably nickel nitrate, nickel acetate.Silver is preferably added in the form of silver nitrate.This hair The bright preparation method to catalyst does not limit in detail, equi-volume impregnating preparation such as can be used, by nickeliferous and silver-colored soluble-salt Aqueous solution be impregnated on carrier, 3~8h is roasted at 300~500 DEG C after dry.By total catalyst weight for 100wt% in terms of, Nickel Content In Catalyst is calculated as with oxide：10~20wt% of nickel oxide (preferably 14.5~18.2wt%), silver oxide 0.01 ~3wt% (preferably 0.05~1.5wt%).
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 0.2~1.2wt%.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 nickel improves the hydrogenation selectivity and stability of catalyst.Cerium and/or lanthanum be most in the present invention It is to be added in the form of soluble nitrate well.
Alkali metal and/or alkaline-earth metal (existing in the form of an oxide) can also be contained in catalyst of the present invention, contained Amount is 0~6wt%, preferably 0.5~3wt%.Alkali metal and/or alkaline-earth metal are one in Li, Na, K, Ca, Mg, Sr, Be In or a variety of, preferably one or both of Li, Mg.When catalyst is used for selective hydrogenation of cracked gasoline, alkene in oil product, two Alkene is easy polymerization and forms colloid and inactivate, can be to the acid of catalyst support surface by addition alkali metal and/or alkaline-earth metal Alkalinity plays adjustment effect, can improve hydrogenation activity and stabilized hydrogenation by adjusting catalyst surface acid-base property, be conducive to drop Carbonaceous, the deposition of colloid in low hydrogenation process, to extend the service life of catalyst.Alkali metal and/or alkaline earth in the present invention Metal is preferably to be added in the form of soluble nitrate, acetate or citrate.
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.
The present invention also provides a kind of preparation method of more specific nickel-silver series hydrocatalyst, with nickeliferous and silver-colored molten Liquid impregnates alumina carrier containing Ni by one or more steps, obtains catalyst by drying, roasting；Alumina carrier containing Ni is by containing Nickel boehmite through molding, drying, roasting and obtain；Wherein nickeliferous boehmite is preferably obtained by following methods, specifically 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 aqueous solution of aluminium containing salt and nickel salt, and adjusting mixed solution temperature is 50~90 DEG C, wherein acid Aluminum saline solution concentration is preferably 10~80g Al2O3/ 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；
(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)；Step (5) plastic pH value preferably 7~9.
Preferably 60~80 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.
The pH value of alkali metal aluminate solution is 9~14 in step (3) in preparation method of the present invention, preferable ph 12~ 14。
In preparation method of the present invention in step (5), preferably 50~70 DEG C of gelling temperature；Plastic pH value preferably 7.5~9.5.
The raw material of industry can be used in aluminium salt described in the preparation method of nickeliferous boehmite and nickel salt.The acidity Aluminum saline solution can be the mixed solution of one or more of aluminium chloride, aluminum sulfate and aluminum nitrate, preferably sulfuric acid aluminum solutions. The mixing that the acid nickel salt aqueous solution can be one or more of nickel chloride, nickel sulfate, nickelous bromide and nickel nitrate is molten Liquid, preferably nickel nitrate solution.Acid aluminium salt and acid nickel salt solution mixing, obtain the acidic aqueous solution of aluminium containing salt and nickel salt, PH Value is 2~5, preferable ph 2~4.The alkali metal aluminate solution refers to sodium metaaluminate or potassium metaaluminate solution.
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 aluminum oxide dry glue powder is added One or more of, the substance and additional amount specifically used can have knowledge by this field and be determined.For example, the glue Solvent can one or more of for nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid, additional amount be need molded samples total weight 3~ 10wt%；The extrusion aid can be sesbania powder etc., and dosage is generally the 2~6wt% for needing molded samples total weight；The oxygen Change aluminium dry glue powder to be made using conventional method, but additional amount is preferably lower than the 10wt% of nickeliferous boehmite gross mass.
The method of roasting and condition are that catalyst carrier roasts common method and condition, can be used vertical heater, converter and Mesh-belt kiln is roasted, and the roasting condition of the carrier is：800~1200 DEG C of 4~10h of roasting, maturing temperature preferably 850~ 1100℃.The maturing temperature of the carrier is the maturing temperature of carrier before impregnating active component Ni, Ag, to guarantee needed for catalyst Specific surface, Kong Rong, and make finally be made with specific nickel and aluminium mixing crystalline form carrier.Before this temperature calcination, Ke Nengjing It crosses low-temperature bake and prepares carrier, but be middle transition calcination steps.
Preparation method of the present invention is to impregnate alumina carrier containing Ni by one or more steps with nickeliferous and silver-colored solution, by Catalyst is made in dry, roasting；Its roasting condition is：3~8h is roasted at 300~500 DEG C.
Catalyst of the invention before the use, preferably at 380~450 DEG C with 6~16h of hydrogen reducing, it is of the invention plus Hydrogen catalyst is the reaction of monoolefine especially suitable for diolefin hydrogenate.
Specific carrier is used in catalyst of the present invention, advantage is organically combine nickel and boehmite Come, is effectively dispersed in active component nickel in boehmite, and form the alumina carrier containing Ni of specific crystal formation, while to load The pore structure and acidity of body have preferable adjustment effect, and final catalyst obtained hydrogenation activity with higher.With It is compared using preparation catalyst merely, has many advantages, such as that process is simple, while the easy modulation of carrier material performance.
In the preparation process of catalyst used carrier precursor, the compound containing active component is first introduced, is made obtained The compound for containing a certain amount of active metal component in carrier, will be greatly reduced greater activity metal component content catalyst Prepare difficulty.On the basis of guaranteeing catalyst performance, achieve the purpose that simplified catalyst preparation process, optimization preparation process. Nickel-silver hydrogenation catalyst hydrogenation activity and selectivity of the invention is high, and chemical stability and thermal stability are good.
Specific embodiment
Active metallic content is measured using atom absorption method in nickel-silver series hydrocatalyst in the present invention；Using Germany The crystal form of D8Advance type x-ray powder diffraction instrument (XRD) the measurement carrier of Bruker company production, actual conditions：CuK α spoke It penetrates, 40 kilovolts, 40 milliamperes, 0.02 ° of scanning speed/step, 0.5 second/step, B1 refers to the peak that 2 θ are 34.2~39.8 ° in XRD spectra Integrated intensity, B2 refers to that 2 θ in XRD spectra are the integrated intensity at 43.3~48.5 ° of peak.
Analysis method：
Oil distillation：It is measured using oil product test method SYB-2110-60；
Bromine valency：Using SH/T 0236-92 standard test；
Diene：Using SH/T 0714-2002 standard test；
Specific surface：Using 19587 standard test of GB/T；
Kong Rong, aperture and pore-size distribution：GB/T 21650.2-2008 standard test；
Water content：Using GB/T 11133-89 standard test；
Sulfur content：It is measured using WK-2B microcoulomb instrument；
Nitrogen content：It is measured using KY-3000N chemiluminescence azotometer；
Arsenic content：It is measured using DV-4300 Atomic Emission Spectrometer AES.
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) nickeliferous boehmite
It is 65g Al by 3L concentration2O3The nickel nitrate solution that the aluminum nitrate solution and 1L concentration of/L is 11.8g NiO/L mixes It is uniformly packed into the container of high level, the ammonia spirit that compound concentration is 8wt% is packed into the container of high level, is connected under two containers Peristaltic pump carries out belt stirrer of the flow control inflow equipped with 3L bottom water and tank bottom can be passed through in the rustless steel container of gas, reacts Temperature 50 C, it is 7.5 that control flow, which adjusts reacting system PH value, after reaction, ammonium hydroxide is added and adjusts plasm PH value 8.5, aging 60 minutes, it is separated by filtration mother liquor, is washed.Nickeliferous boehmite is made in 90 DEG C of dry 3h, 120 DEG C of dry 2h.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with nitric acid, phosphoric acid, sesbania powder and water mixer kneader at plastic, extrusion Molding, then obtains nickeliferous precursor carrier in 120 DEG C of dry 4h, 620 DEG C of roasting 4h.Prepare lanthanum nitrate aqueous solution, using etc. bodies On product impregnation to nickeliferous carrier, nickeliferous, lanthanum carrier is obtained in 120 DEG C of dry 4h, 880 DEG C of roasting 4h.
(3) catalyst
By nickel nitrate, silver nitrate is soluble in water that maceration extract is made, and is impregnated into using equi-volume impregnating and to be prepared in (2) On 80g carrier, 120 DEG C of drying, 380 DEG C of roasting 4h obtain catalyst C1.
Embodiment 2
(1) nickeliferous boehmite
It is 50g Al by 4L concentration2O3The nickel nitrate solution that the aluminum nitrate solution and 0.5L concentration of/L is 14.5g NiO/L is mixed It closes and is uniformly packed into the container of high level, the ammonia spirit that compound concentration is 8wt% is packed into the container of high level, under two containers Even peristaltic 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, instead 55 DEG C of temperature are answered, it is 7.7 that control flow, which adjusts reacting system PH value, after reaction, ammonium hydroxide is added and adjusts plasm PH value 8.6, aging 30 minutes, it is separated by filtration mother liquor, is washed.120 DEG C of dry 5h, are made nickeliferous boehmite.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with lithium carbonate, nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader At plastic, extruded moulding obtains nickeliferous and lithium carrier then in 120 DEG C of dry 4h, 940 DEG C of roasting 4h.
(3) catalyst
By nickel acetate, silver nitrate is soluble in water that maceration extract is made, and is impregnated into using equi-volume impregnating and to be prepared in (2) On 80g carrier, 120 DEG C of drying, 420 DEG C of roasting 4h obtain catalyst C2.
Comparative example 1
(1) boehmite
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 8.0 that control flow, which adjusts reacting system PH value, after reaction, ammonia is added Water adjusts plasm PH value 8.5, aging 40 minutes, is separated by filtration mother liquor, washs.In 120 DEG C of dry 2h, thin water aluminium must be intended Stone.
(2) carrier
The boehmite for weighing preparation, with nitric acid, citric acid, phosphoric acid, sesbania powder, lithium carbonate and water mixer kneader at can Then plastomer, extruded moulding obtain the carrier containing lithium in 120 DEG C of dry 6h, 920 DEG C of roasting 4h.
(3) catalyst
Nickel nitrate and silver nitrate are dissolved in the water, maceration extract is made, is impregnated on the 80g carrier prepared in (2), 120 DEG C Drying, 450 DEG C of roasting 3h obtain catalyst D1.
Embodiment 3
(1) nickeliferous boehmite
It is 50g Al by 1L concentration2O3The nickel nitrate solution that the aluminum sulfate solution and 0.5L concentration of/L is 6g NiO/L mixes It is uniformly packed into the container of high level, compound concentration is 50g Al2O3//L sodium aluminate solution 3L 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 that control flow, which adjusts reacting system PH value, is by the way that ammonium hydroxide adjusting plasm PH value is added dropwise 9.6, 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.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with nitric acid, phosphoric acid, sesbania powder and water mixer kneader at plastic, extrusion Molding, then obtains nickeliferous precursor carrier in 120 DEG C of dry 4h, 600 DEG C of roasting 4h.Prepare magnesium nitrate, lithium carbonate and citric acid Aqueous solution is impregnated into nickeliferous precursor carrier using equi-volume impregnating, is contained in 120 DEG C of dry 4h, 960 DEG C of roasting 4h The carrier of nickel, magnesium and lithium.
(3) catalyst
By nickel acetate, silver nitrate is soluble in water that maceration extract is made, and is impregnated into using equi-volume impregnating and to be prepared in (2) On 80g carrier, 120 DEG C of drying, 360 DEG C of roasting 4h obtain catalyst C3.
Comparative example 2
(1) boehmite
It is 50g Al by 1L concentration2O3The aluminum sulfate solution and 3L concentration of/L is 50g Al2O3/ L sodium aluminate solution difference It is packed into the container of high level, peristaltic pump is connected under two containers and carries out belt stirrer and tank bottom that flow control inflow is equipped with 2L bottom water It can be passed through in the rustless steel container of gas, 50 DEG C of reaction temperature, it is 9 that control flow, which adjusts pH value of reaction system, by the way that ammonia is added dropwise It is 9.5 that water, which adjusts slurry pH value, and aging 30 minutes, are separated by filtration mother liquor after reaction, washing.In 90 DEG C of dry 3h, 120 DEG C Dry 2h, obtains boehmite.
(2) carrier
Weigh preparation intends thin water aluminium, with lithium carbonate, nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader at plastic Carrier is made then in 120 DEG C of dry 4h, 940 DEG C of roasting 4h in body, extruded moulding.
(3) catalyst
Using two step preparation catalysts.The first step, nickel nitrate and magnesium nitrate are dissolved in water and are configured to maceration extract, use Equi-volume impregnating is impregnated on the 80g carrier prepared in (2), and the 60% of dipping nickel nitrate total amount.120 DEG C of drying, 350 DEG C of roastings 4h is burnt, second step is using equi-volume impregnating dipping silver nitrate and the 40% of remaining nickel nitrate total amount, 120 DEG C of drying, 380 DEG C of roastings 4h is burnt, catalyst D2 is obtained.
Embodiment 4
(1) nickeliferous boehmite
It is 22.5g Al by 2L concentration2O3The nickel nitrate solution that the aluminum sulfate solution and 1L concentration of/L is 15.8g NiO/L is mixed It closes and is uniformly packed into the container of high level, compound concentration is 50g Al2O3The container of/L sodium aluminate solution 3L loading high level It is interior, 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 the stainless of gas In steel container, 65 DEG C of reaction temperature, it is 9.0 that control flow, which adjusts reacting system PH value, adjusts slurry pH value by the way that ammonium hydroxide is added dropwise It is 9.5, aging 40 minutes, are separated by filtration mother liquor after reaction, washing.In 120 DEG C of dry 4h, it is made nickeliferous and intends thin water aluminium Stone.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with cerous nitrate, nitric acid, phosphoric acid, sesbania powder and water mixer kneader at plastic Body, extruded moulding obtain nickeliferous and cerium carrier then in 120 DEG C of dry 4h, 1050 DEG C of roasting 4h.
(3) catalyst
By nickel acetate, silver nitrate is soluble in water that maceration extract is made, and is impregnated into using equi-volume impregnating and to be prepared in (2) On 80g carrier, 120 DEG C of drying, 400 DEG C of roasting 4h obtain catalyst C4.
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 8.5g sesbania powder after mixing, then weighs 38g carbon black and 11.65g 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%) 67ml, is stirred with glass bar, comes into full contact with tetrabutylammonium hydroxide solution with mixture, placed 35 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 3.5 hours dry, nickeliferous precursor carrier is made in 550 DEG C of roasting 4h.Cerous nitrate aqueous solution is prepared, is soaked using equi-volume impregnating In stain to nickeliferous precursor carrier, 110 DEG C of dry 6h, 1020 DEG C of roasting 4h obtain nickeliferous and cerium carrier.
Maceration extract is made in nickel nitrate and silver nitrate co-dissolve in water, is impregnated into the nickeliferous carrier of 80g of above-mentioned preparation On, 120 DEG C of drying, 460 DEG C of roasting 4h obtain catalyst D4.
Catalyst D1~D4 catalyst physical property and composition are shown in Table in catalyst C1~C8 and comparative example 1-4 in embodiment 1-8 1。
Embodiment 5
(1) nickeliferous boehmite
It is 50g Al by 4L 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 8.95g NiO/L is packed into the container of high level, and lower even peristaltic pump carries out flow velocity Control.It is passed through the mixed gas of carbon dioxide and air, while prepared nickel nitrate solution is added dropwise, titanium dioxide in mixed gas Concentration of carbon is 60v%, flow 4Nm3/h.35 DEG C of reaction temperature, reaction end pH value 9.7, stopping is passed through carbon dioxide, aging 35 Minute, it is separated by filtration mother liquor, is washed.In 110 DEG C of dry 6h, nickeliferous boehmite is made.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with nitric acid, phosphoric acid, sesbania powder, lanthanum nitrate and water mixer kneader at plastic Body, extruded moulding obtain nickeliferous and lanthanum precursor carrier then in 120 DEG C of dry 4h, 580 DEG C of roasting 4h.Prepare lithium carbonate and Aqueous citric acid solution is impregnated into nickeliferous and lanthanum precursor carrier using equi-volume impregnating, in 120 DEG C of dry 4h, 1020 DEG C of roastings 4h is burnt, the carrier of nickeliferous, lanthanum and lithium is obtained.
(3) catalyst
Maceration extract is made in nickel acetate, silver nitrate co-dissolve in water, is impregnated on the 80g carrier prepared in (2), 120 DEG C of drying, 450 DEG C of roasting 3h obtain catalyst C5.
Comparative example 4
(1) boehmite
It is 50g Al by 4L 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 70v%, flow 3Nm3/ h.35 DEG C of reaction temperature, reaction end pH value 9.5, stopping is passed through carbon dioxide, aging 30 minutes, is separated by filtration mother liquor, washs. Boehmite is obtained in 90 DEG C of dry 3h, 120 DEG C of dry 2h.
(2) carrier
The boehmite for weighing preparation is squeezed with nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader at plastic Item molding, then obtains precursor carrier in 120 DEG C of dry 4h, 650 DEG C of roasting 4h.Prepare lanthanum nitrate, lithium carbonate and citric acid water Solution is impregnated on carrier using equi-volume impregnating, obtains the load containing lanthanum and lithium in 110 DEG C of dry 6h, 990 DEG C of roasting 4h Body.
(3) catalyst
Nickel acetate, silver nitrate are dissolved in the water, maceration extract is made, is impregnated on the 80g carrier prepared in (2), 120 DEG C Drying, 410 DEG C of roasting 5h obtain catalyst D3.
Embodiment 6
(1) nickeliferous boehmite
It is 46.25g Al by 4L 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, the nickel nitrate solution that 1L concentration is 12.45g NiO/L is packed into the container of high level, and lower even peristaltic pump carries out Flow control.It is passed through the mixed gas of carbon dioxide and air, while prepared nickel nitrate solution is added dropwise, two in mixed gas Oxidation concentration of carbon is 70v%, flow 3Nm3/h.35 DEG C of reaction temperature, reaction end pH value 9.5, stopping is passed through carbon dioxide, always Change 45 minutes, be separated by filtration mother liquor, washs.120 DEG C of dry 4h, are made nickeliferous boehmite.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with lithium carbonate, nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader At plastic, then extruded moulding obtains nickeliferous carrier in 120 DEG C of dry 4h, 1000 DEG C of roasting 4h.
(3) catalyst
By nickel nitrate, silver nitrate and lanthanum nitrate is soluble in water that maceration extract is made, and is impregnated into (2) using equi-volume impregnating On the 80g carrier of preparation, 120 DEG C of drying, 350 DEG C of roasting 4h obtain catalyst C6.
Embodiment 7
(1) nickeliferous boehmite
It is 50g Al by 4L 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 3Nm3/ h.35 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide.Under blowing air stirring condition, 1L concentration, which is added, is The nickel nitrate solution of 5.13g NiO/L is 9.5 by the way that ammonium hydroxide is added dropwise to adjust plasm PH value, after reaction after stablizing 25 minutes Aging 30 minutes, it is separated by filtration mother liquor, is washed.Nickeliferous boehmite is made in 90 DEG C of dry 3h, 120 DEG C of dry 2h.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader at plastic Then body, extruded moulding obtain nickeliferous carrier in 120 DEG C of dry 4h, 1100 DEG C of roasting 4h.
(3) catalyst
By nickel acetate, silver nitrate is soluble in water that maceration extract is made, and is impregnated into using equi-volume impregnating and to be prepared in (2) On 80g carrier, 120 DEG C of drying, 370 DEG C of roasting 4h obtain catalyst C7.
Embodiment 8
(1) nickeliferous boehmite
It is 50g Al by 4L 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.35 DEG C of reaction temperature, reaction end pH value 10, stopping is passed through carbon dioxide.Under blowing air stirring condition, 1L concentration, which is added, is The nickel nitrate solution of 18.6g NiO/L is 9.5 by the way that ammonium hydroxide is added dropwise to adjust plasm PH value, after reaction after stablizing 25 minutes Aging 40 minutes, it is separated by filtration mother liquor, is washed.In 120 DEG C of dry 4h, nickeliferous boehmite is made.
(2) nickeliferous carrier
The nickeliferous boehmite for weighing preparation, with lanthanum nitrate, nitric acid, citric acid, phosphoric acid, sesbania powder and water mixer kneader At plastic, then extruded moulding obtains nickeliferous carrier in 120 DEG C of dry 4h, 980 DEG C of roasting 4h.
(3) catalyst
It is impregnated on the 80g carrier prepared in (2) using two step equi-volume impregnatings, the first step is made into total nickel content 40% Nickel acetate solution impregnated carrier, 120 DEG C of drying, 350 DEG C of roasting 4h, second step is made nickel nitrate and silver nitrate are soluble in water Maceration extract, is added the nickel content of residue 60%, 120 DEG C of drying, and 380 DEG C of roasting 4h obtain catalyst C8.
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~C8 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 at 380~450 DEG C It is restored 10 hours under hydrogen, then cools to 35 DEG C, be passivated the laggard raw material of 4h with the hexamethylene of the 1000ppm containing dimethyl disulfide Oil.Evaluate process conditions：Reaction pressure：2.8MPa, inlet temperature：50 DEG C, fresh feed oil air speed：3.0h-1, hydrogen and oil volume Than：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-silver 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 (16)

1. a kind of nickel-silver series hydrocatalyst, active component nickel and silver are contained in catalyst, using nickeliferous aluminium oxide as carrier, It is characterized in that：By catalyst weight for 100wt% in terms of, contain 10~20wt% of nickel oxide, preferably 14.5~18.2wt%, oxygen Change silver 0.01~3wt%, preferably 0.05~1.5wt%, cerium oxide and/or lanthana 0~5wt%, preferably 0.2~ 1.2wt%, alkali metal and/or alkaline earth oxide 0~6wt%, preferably 0.5~3wt%；Specific surface area of catalyst 50~ 150m2/ g, hole hold 0.25~0.55cm3/ g, 0.5~1.1g/cm of heap density3；The presoma of alumina carrier containing Ni is nickeliferous quasi- Boehmite has acid-base neutralization and plastic process in the preparation process of the nickeliferous boehmite；It is impregnated containing active component solution Nickel-silver series hydrocatalyst is made through drying, roasting in alumina carrier containing Ni.
2. nickel-silver series hydrocatalyst according to claim 1, it is characterised in that：The specific surface of nickeliferous boehmite 300~420m of product20.7~1.2cm of/g, Kong Rongwei3/ g, aperture are 5~10nm；It is with nickeliferous boehmite total weight 100wt% meter, nickel content are 0.1~10wt%, preferably 0.5~5wt%.
3. nickel-silver series hydrocatalyst according to claim 1, it is characterised in that：With alumina carrier containing Ni total weight For 100% meter, the nickel content of alumina carrier containing Ni is 0.1~10wt%, preferably 0.5~5wt%, specific surface area 25~ 250m20.15~0.85cm of/g, Kong Rongwei3/ g, aperture are 8~40nm.
4. nickel-silver series hydrocatalyst according to claim 1, it is characterised in that：Alumina carrier containing Ni is by nickeliferous quasi- Boehmite is obtained through molding, roasting, contains δ-Al2O3、δ-NiAl26O40And NiAl2O4Crystal form, and 0.45 in XRD spectra≤ B1/B2≤0.85, B1 refer to that the integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, B2 refer to that 2 θ are in XRD spectra The integrated intensity at 43.3~48.5 ° of peak.
5. nickel-silver series hydrocatalyst 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.
6. nickel-silver series hydrocatalyst according to claim 1, it is characterised in that：Also contain in alumina carrier containing Ni θ-Al2O3、α-Al2O3And/or γ-Al2O3；Best α-Al2O3Content is lower than 30wt%.
7. nickel-silver series hydrocatalyst according to claim 4, it is characterised in that：Alumina carrier containing Ni roasting condition For：800~1200 DEG C of 4~10h of roasting, preferably 850~1100 DEG C of maturing temperature.
8. a kind of preparation method of nickel-silver series hydrocatalyst described in claim 1, it is characterised in that：With nickeliferous and silver-colored Solution impregnates alumina carrier containing Ni by one or more steps, obtains catalyst by drying, roasting；Alumina carrier containing Ni by Nickeliferous boehmite is obtained through molding, roasting；Wherein nickeliferous boehmite is obtained by following methods, and detailed process includes 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 It is uniformly mixed, obtains the acidic aqueous solution of aluminium containing salt and nickel salt, adjusting its solution temperature is 50~90 DEG C, wherein acidic aluminum salt water Solution concentration 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；
(6) it after cemented into bundles, through aging, is filtered, washed, dries nickeliferous boehmite is made.
9. the preparation method of nickel-silver series hydrocatalyst according to claim 8, it is characterised in that：In in step (1) Air is passed through with the bottom of kettle.
10. the preparation method of nickel-silver series hydrocatalyst according to claim 8, it is characterised in that：It is adjusted in step (2) The temperature for saving the acidic aqueous solution is 50~70 DEG C.
11. the preparation method of nickel-silver series hydrocatalyst according to claim 8, it is characterised in that：In step (5), at 50~70 DEG C of glue temperature；Plastic pH value 7.5~9.5.
12. the preparation method of nickel-silver series hydrocatalyst according to claim 8, it is characterised in that：Alkali in step (3) The pH value of metal aluminate solution is 9~14, preferable ph 12~14.
13. the preparation method of nickel-silver series hydrocatalyst according to claim 8, it is characterised in that：Acid aluminium salt is water-soluble Liquid is the mixed solution of one or more of aluminium chloride, aluminum sulfate and aluminum nitrate, preferably sulfuric acid aluminum solutions；Acid nickel salt is water-soluble Liquid is the mixed solution of one or more of nickel chloride, nickel sulfate, nickelous bromide and nickel nitrate, preferably nickel nitrate solution；Alkali gold Belong to aluminate solution and refers to sodium metaaluminate or potassium metaaluminate solution.
14. the preparation method of nickel-silver series hydrocatalyst according to claim 8, it is characterised in that：In step (2), acid Property aluminium salt and acid nickel salt aqueous solution mixing, obtain the acidic aqueous solution of aluminium containing salt and nickel salt, pH value is 2~5, preferable ph 2 ~4.
15. the preparation method of nickel-silver series hydrocatalyst according to claim 8, it is characterised in that：In step (6), always Changing temperature is 50~80 DEG C, and ageing time is 10~60min.
16. the preparation method of nickel-silver series hydrocatalyst according to claim 8, it is characterised in that：With nickeliferous and silver-colored Solution impregnates alumina carrier containing Ni by one or more steps, by drying, roasts obtained catalyst；Its roasting condition is：300 3~8h is roasted at~500 DEG C.
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CN103769104A (en) * 2012-10-20 2014-05-07 中国石油化工股份有限公司 Nickel base selective hydrogenation catalyst, preparation method and application thereof
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