CN108262047A - A kind of nickel-molybdenum series hydrocatalyst and preparation method thereof - Google Patents
A kind of nickel-molybdenum series hydrocatalyst and preparation method thereof Download PDFInfo
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- CN108262047A CN108262047A CN201611263029.4A CN201611263029A CN108262047A CN 108262047 A CN108262047 A CN 108262047A CN 201611263029 A CN201611263029 A CN 201611263029A CN 108262047 A CN108262047 A CN 108262047A
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The present invention relates to a kind of nickel molybdenum series catalysts and preparation method thereof, and in particular to a kind of using nickeliferous aluminium oxide as the preparation method of the nickel molybdenum system hydrogenation catalyst of carrier.Containing active component nickel and molybdenum, 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, active component nickel is made to be effectively dispersed 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.The nickel molybdenum hydrogenation catalyst hydrogenation activity and high selectivity, chemical stability and thermal stability of the present invention is good.
Description
Technical field
The present invention relates to a kind of nickel-molybdenum series catalysts and preparation method thereof, and in particular to a kind of using nickeliferous aluminium oxide as load
The preparation method of the nickel-molybdenum series hydrocatalyst of body.
Background technology
Many countries are using the yield of ethylene as the mark of state's petrochemical industry development level.It is quick with China's economy
Development, ethylene yield increase year by year.Important by-products of the drippolene as cracking of ethylene, account for about the 50% of ethylene production capacity
~80%.This part byproduct how is made good use of, will great influence be generated to the economic benefit for improving enterprise.Meanwhile it cracks
Also lead to vapour containing impurity such as various unsaturated hydrocarbons and sulphur, nitrogen, oxygen such as a large amount of diolefin, alkyl alkenyl arene, indenes in gasoline
Oil nature is unstable.It is industrially generally refined using two-stage hydrogenation, is first added hydrogen saturation chain conjugation through one section of Low Temperature Liquid
Alkene, cyclic conjugated alkene and styrene etc.；Again the organic impurities of sulfur-bearing, nitrogen, oxygen etc. is removed through two sections of high temperature gas phase hydrogenations simultaneously
Make to produce benzene, toluene and dimethylbenzene as aromatics extraction raw material after monoolefin hydrogenation saturation.Therefore, with pyrolysis gasoline hydrogenation catalyst
Hydrogen addition technology for core is an important branch in field of hydrogenation, have in the post processing of preparing ethylene by steam cracking act foot it is light
The status of weight.The one-stage hydrogenation catalyst used at present is roughly divided into two classes, and a kind of active component is nickel non-precious metal catalyst；
Another kind of active component is the catalyst used in noble metal, the use of raw material is narrow fraction.Non-precious metal catalyst is poor because of structure
The factors such as different and tenor height have certain anti-impurity and water-resistant capacity, and price advantage is also than more significant.Therefore your non-gold
Gradually substitution noble metal catalyst adds hydrogen catalyst series to metal catalyst industrialization product applied to pyrolysis product.
US3472763 reports a kind of diene selective hydrogenation catalyst, active component Ni contents 1~20%, auxiliary agent
MoO3Content 1~5%, auxiliary agent alkali metal and alkaline earth metal content 1~5%, catalyst pores, which are held, is more 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.
CN200710179630.X discloses a kind of molybdenum-nickel hydrogenation catalyst and preparation method thereof, provides a kind of molybdenum nickel and adds
Hydrogen catalyst, it is further provided a kind of to prepare active constituent loading height, the side of the high molybdenum-nickel hydrogenation catalyst of reactivity
Method.The catalyst by weight, including MoO320~40%, NiO 2.5~12%, TiO21-6%, P2O51.5-4.5%,
Surplus is γ-Al2O3.Ti, Mo, P are introduced between carrier molding, and the hydrogenation catalyst with high desulfurization removing nitric activity is made.
CN1218822A reports a kind of Ni/Al2O3Suitable for the selective hydrocatalyst of pyrolysis gasoline cut fraction, this is urged
Agent is in obtained on the alumina support containing lithium or alkaline-earth metal by nickel load, 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 the methods of pH value swing method, the organic expanding agent of addition, hydro-thermal process such as may be used in carrying alumina production procedure to 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 the 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, the carrier hole hold for 0.4cm3/ g~1.0cm3/ g, specific surface area 160m2/ g~
420m2/ g, average pore size are 8.0nm~15.0nm, and the ratio more than 6.0nm holes accounts for the 85% more of its total hole, Kong Rong, average
Aperture is larger, and macropore proportion is more, 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 add in and divide
Suspension is made in the mixed liquor of the nano aluminium oxide of powder, is added with stirring nickel salt solution, after stirring evenly, is dripped in mixed liquor
Enter ammonium hydroxide, add distilled water, obtain navy blue nickel amine complex ([Ni (NH3)6]2+)-aluminium oxide mixed solution C, using
Hydrothermal aging is filtered, washed, dries, and obtains cladding product among green；Roasting is restored again, obtains black nickel coated oxygen
Change 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
Be by the way that by nickel, zirconium, if necessary, the acidic aqueous solution of the also salt of aluminium is added to silicon, if necessary, the also compound of aluminium
Alkaline aqueous solution or suspension in, the pH of the mixture so obtained is made to be reduced at least 6.5, then by further adding
Alkaline solution adjusts pH value to 7-8, detach the solid so deposited, dry, be molded and be sintered.In addition it also discloses
Prepare catalyst method and its preparing 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 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 calcination temperature to NiCoMo/A12O3The influence of catalyst rhohene desulfiirization activity.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
When activating for 600 DEG C, with alumina support strong interaction generation spinel structure occurs for metal 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 generation spinel structure can occur during burning, 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.Different from other metals, rare nickeliferous plan is thin
Diaspore is reported, because generally requiring to carry out high-temperature roasting when preparing catalyst carrier with it.
Improve hydrogenation catalyst comprehensive performance focus on following three aspects (1) exploitation it is a kind of it is novel be suitable for plus
The carrier material of hydrogen catalyst；(2) activity of hydrocatalyst constituent content is improved；(3) auxiliary agent and active ingredient dispersion agents are added in
Improve active component utilization rate.
The catalyst with higher hydrogenation activity is prepared, corresponding active metal component content also will height.Simple should
Hydrotreating catalyst is prepared with infusion process, the solution for preparing high activity metal constituent content is needed to carry out dipping system to carrier
.Therefore there are the following problems in dipping process：(1) since the water absorption rate of carrier is certain, using incipient impregnation method
Maceration extract given volume, active metal component addition is excessively high to cause dissolving incomplete；(2) preparing in catalyst process needs
Repeatedly dipping active component, twice, three times even four times could be by the activity component impregnation to carrier of certain content, this just makes
Into the problems such as preparation section is cumbersome, long preparation period, loss of active component；(3) it is repeatedly generally required during dipping
Organic or inorganic dispersant is added in maceration extract to increase the dispersion degree of active metal component, but these meetings in last handling process
There are problems that removing.
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, the catalysis of high-content active metal component is reduced to reach
The problem of load difficulty encountered in agent preparation process.But by kneading method using the form of kneading by active metallic compound
With aluminum hydroxide solid elastomer powder or the direct mixed-forming of alumina powder, there are the uneven and catalyst strengths of crystal grain mixing for this method
The problems such as variation, while be not easy to combine between simple kneading each component and form specific skeleton structure.
Invention content
The purpose of the present invention is to provide a kind of New Nickel-molybdenum system hydrogenation catalysts and preparation method thereof, are suitable for higher
The preparation requirement of active metal component content catalyst.
The nickel-molybdenum series hydrocatalyst of the present invention, it is characterised in that：Containing active component nickel and molybdenum, using nickeliferous aluminium oxide as
Carrier is counted by 100wt% of total catalyst weight, containing 10~20wt% of nickel oxide (preferably 14.5~18.5wt%, including
Nickel oxide in alumina carrier containing Ni), 0.1~5wt% of molybdenum oxide (preferably 0.3~2wt%), cerium oxide and/or oxidation
0~5wt% of lanthanum (preferably 0.2~2wt%), 0~6wt% of alkali metal and/or alkaline earth oxide (preferably 0.5~
3wt%)；50~150m of specific surface area of catalyst2/ g, hole hold 0.30~0.55cm3/ g, 0.6~1.1g/cm of heap density3.It is nickeliferous
The presoma of alumina support is nickeliferous boehmite, have in the preparation process of the nickeliferous boehmite acid-base neutralization and into
Glue process.
Carrier in the nickel-molybdenum series hydrocatalyst of the present invention is nickeliferous aluminium oxide, needs to prepare the nickeliferous thin water of plan first
The presoma of aluminium stone, i.e. alumina carrier containing Ni is nickeliferous boehmite, be not boehmite with nickel compound containing or
The simple physical blending of nickel salt solution or cladding, but acid-base reaction occurs, there is plastic process, 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 the nickeliferous plan
Boehmite and carrier prepared therefrom also have suitable pore-size distribution.
Nickeliferous boehmite through be molded, dry, roast obtained from alumina carrier containing Ni.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 is preferably (to intend thin water with nickeliferous
Aluminium stone total weight is counted for 100wt%), 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 in preparation process
Journey.
Alumina carrier containing Ni in the present invention used in catalyst, preferably by nickeliferous boehmite through being molded, roasting
And obtain, contain δ-Al2O3、δ-NiAl26O40And NiAl2O4Crystal form, and 0.45≤B1/B2≤0.85 in XRD spectra, B1 refer to
2 θ are the integrated intensity at 34.2~39.8 ° of peak in XRD spectra, and B2 refers to the product at the peak that 2 θ are 43.3~48.5 ° in XRD spectra
Divide intensity.
In alumina carrier containing Ni in the present invention 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 less than 30wt%.
Final catalyst is regarded in the present invention using purpose difference, the preparation method of nickeliferous boehmite, nickel source, nickel contain
Amount, alumina carrier containing Ni calcination for activation temperature etc. can be different.Preferably nickel content is in the alumina carrier containing Ni of the present invention
0.1~10wt%, preferably 0.5~5wt%.25~250m of specific surface area20.15~0.85cm of/g, Kong Rongwei3/ g, aperture for 8~
40nm。
In the present invention active component nickel, molybdenum be in the form of soluble-salt add in, nickel source be selected from nickel nitrate, nickel acetate,
The one or more of nickel chloride or nickel sulfate, preferably nickel nitrate, nickel acetate.Molybdenum is preferably added in the form of ammonium molybdate.This hair
The bright preparation method to catalyst does not limit in detail, and equi-volume impregnating preparation such as can be used, by nickeliferous and molybdenum soluble-salt
Aqueous solution be impregnated on carrier, 3~8h is roasted at 300~500 DEG C after dry.It is counted by 100wt% of total catalyst weight,
Nickel Content In Catalyst is calculated as with oxide：10~20wt% of nickel oxide (preferably 14.5~18.5wt%), molybdenum oxide 0.1~
5wt% (preferably 0.3~2wt%).
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 0.2~2wt%.After adding in cerium and/or lanthanum, catalyst carrier crystal grain is long when can inhibit high-temperature roasting
Greatly, the dispersion degree of active component nickel is improved, 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
It measures as 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.It, can be to catalyst carrier table by adding alkali metal and/or alkaline-earth metal
The acid-base property in face plays adjustment effect, can improve hydrogenation activity and stabilized hydrogenation by adjusting catalyst surface acid-base property, have
Conducive to carbonaceous, the deposition of colloid in hydrogenation process is reduced, so as to extend the service life of catalyst.In the present invention alkali metal and/
Or alkaline-earth 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 add 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 adds in simultaneously.
The present invention also provides a kind of preparation method of more specific nickel-molybdenum series hydrocatalyst, with nickeliferous and molybdenum molten
Liquid impregnates alumina carrier containing Ni by one or multi-step, and catalyst is obtained by drying, roasting；Alumina carrier containing Ni is by containing
Nickel boehmite is through being molded, drying, roasting and obtain；Wherein nickeliferous boehmite is preferably obtained by following methods, specifically
Process includes the following steps：
(1) it neutralizes and bottom water is added in kettle, 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 it is 50~90 DEG C to adjust mixed solution temperature, 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 is added in (1), constant ventilation stirring；
(5) 50~90 DEG C of rate-determining steps (4) gelling temperature, plastic pH value 7~10；
(6) it after cemented into bundles, through aging, is filtered, washed, dries obtained nickeliferous boehmite.
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 in preparation method of the present invention described in step (1)；Step (2) described temperature preferably 60~
80 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
For subzero temperature difference preferably no more than 3 DEG C, three's temperature is preferably identical.
The raw material of industry can be used in aluminium salt and nickel salt described in the preparation method of nickeliferous boehmite.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 acid nickel salt aqueous solution can be that the mixing of 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 mix, and obtain the acidic aqueous solution of aluminium containing salt and nickel salt, PH
It is 2~5 to be worth, 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 plastic is made 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, adds water when filtering may be used
Washing, mashing washing the modes such as wash using lower alcohols, and 40~80 DEG C of temperature, pH value 4~8, wash time are controlled during washing
For 20~40min, washing times are 2~5 times.
Drying mode described in step (6) may be used 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 add in peptizing agent, extrusion aid and aluminium oxide as needed
One or more of dry glue powder, the substance specifically used and addition 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 and sulfuric acid, and addition is to 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；Institute
It states aluminum oxide dry glue powder to be made using conventional method, but addition is less than well the 10wt% of nickeliferous boehmite gross mass again.
The method of roasting and condition roast common method and condition for catalyst carrier, can be used vertical heater, converter and
Mesh-belt kiln is roasted, and the roasting condition of the carrier is preferably：800~1200 DEG C of 4~10h of roasting, calcination temperature preferably 850
~1100 DEG C.
The catalyst of the present 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 especially suitable for reaction of the diolefin hydrogenate for monoolefine.
It is nickel and boehmite can organically be combined using specific carrier, advantage in catalyst of the present invention
Come, active component nickel is made to be effectively dispersed in boehmite, and form the alumina carrier containing Ni of specific crystal formation, while to carrying
The pore structure and acidity of body have preferable adjustment effect, and final catalyst obtained has higher hydrogenation activity.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
Contain the compound of a certain amount of active metal component in carrier, greater activity metal component content catalyst can be substantially reduced
Prepare difficulty.On the basis of catalyst performance is ensured, achieve the purpose that simplified catalyst preparation process, optimization preparation process.
The nickel-molybdenum hydrogenation catalyst hydrogenation activity and high selectivity, chemical stability and thermal stability of the present invention is good.
Specific embodiment
Active metallic content is measured using atom absorption method in nickel-molybdenum series hydrocatalyst in the present invention；Using Germany
The D8Advance types x-ray powder diffraction instrument (XRD) of Bruker companies production measures the crystal form of carrier, actual conditions：CuK α spokes
It penetrates, 40 kilovolts, 40 milliamperes, 0.02 ° of sweep 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 the integrated intensity at the peak that 2 θ in XRD spectra are 43.3~48.5 °.
Analysis method：
Oil distillation：It is measured using oil product test method SYB-2110-60；
Bromine valency：Using SH/T 0236-92 standard tests；
Diene：Using SH/T 0714-2002 standard tests；
Specific surface：Using 19587 standard tests of GB/T；
Kong Rong, aperture and pore-size distribution：GB/T 21650.2-2008 standard tests；
Water content：Using GB/T 11133-89 standard tests；
Sulfur content：It is measured using WK-2B microcoulombs instrument；
Nitrogen content：It is measured using KY-3000N chemiluminescences azotometer；
Arsenic content：It is measured using DV-4300 Atomic Emission Spectrometer AESs.
It is further illustrated the present invention below by embodiment, but is not regarded as that present invention is limited only by this.
Embodiment 1
(1) nickeliferous boehmite
By a concentration of 45g Al of 1L2O3The nickel nitrate solution mixing of a concentration of 8g NiO/L of aluminum sulfate solution and 1L of/L is equal
Even to be packed into the container of high level, compound concentration is 145g Al2O3/ L sodium aluminate solutions 1L is packed into the container of high level, and two
Connect peristaltic pump under container and carry out the stainless steel appearance that flow control flows into the belt stirrer equipped with 5L bottoms water and tank bottom can be passed through gas
In device, 55 DEG C of reaction and gelling temperature, control flow-rate adjustment reaction system (including plastic) pH value are 9.2, after reaction, are led to
It crosses dropwise addition ammonium hydroxide and adjusts slurry pH value to 9.5, aging 30min, 55 DEG C of aging temperature is separated by filtration mother liquor, washing, and 120 DEG C dry
Nickeliferous boehmite is made in dry 2h.
(2) nickeliferous carrier
The nickeliferous boehmite of preparation is weighed, with nitric acid, citric acid, sesbania powder and water mixer kneader into plastic, is squeezed
Item is molded, and then obtains alumina carrier containing Ni in 120 DEG C of dry 4h, 600 DEG C of roasting 4h.Prepare lanthanum nitrate, lithium carbonate and lemon
Lemon aqueous acid is impregnated into using equi-volume impregnating on nickeliferous carrier, is contained in 120 DEG C of dry 4h, 1000 DEG C of roasting 4h
The carrier of nickel, lanthanum and lithium.
(3) catalyst
By nickel nitrate, ammonium molybdate is soluble in water that maceration extract is made, and is impregnated into what is prepared in (2) using equi-volume impregnating
On 100g carriers, 120 DEG C of drying, 380 DEG C of roasting 4h obtain catalyst C1.
Embodiment 2
(1) nickeliferous boehmite
By a concentration of 50gAl of 1L2O3The nickel nitrate solution mixing of a concentration of 3g NiO/L of aluminum sulfate solution and 0.5L of/L is equal
Even to be packed into the container of high level, compound concentration is 150g Al2O3//L sodium aluminate solutions 1L is packed into the container of high level,
Connect peristaltic pump under two containers and carry out the stainless steel that flow control flows into the belt stirrer equipped with 5L bottoms water and tank bottom can be passed through gas
In container, 60 DEG C of reaction and gelling temperature, control flow-rate adjustment reaction system (including plastic) pH value are 9.0, after reaction,
Slurry pH value is adjusted to 9.6 by the way that ammonium hydroxide is added dropwise, and aging 25min, 55 DEG C of aging temperature is separated by filtration mother liquor, washing.At 90 DEG C
Dry 3h, 120 DEG C of dry 2h, are made nickeliferous boehmite.
(2) nickeliferous carrier
The nickeliferous boehmite of preparation is weighed, with nitric acid, citric acid, sesbania powder and water mixer kneader into plastic, is squeezed
Item is molded, and then obtains nickeliferous carrier in 120 DEG C of dry 4h, 950 DEG C of roasting 4h.
(3) catalyst
By nickel acetate, ammonium molybdate is soluble in water that maceration extract is made, and is impregnated into what is prepared in (2) using equi-volume impregnating
On 100g carriers, 120 DEG C of drying, 380 DEG C of roasting 4h obtain catalyst C2.
Embodiment 3
(1) nickeliferous boehmite
By a concentration of 45g Al of 1L2O3The nickel nitrate solution mixing of a concentration of 25g NiO/L of aluminum sulfate solution and 1L of/L is equal
Even to be packed into the container of high level, compound concentration is 150g Al2O3/ L sodium aluminate solutions 1L is packed into the container of high level, and two
Connect peristaltic pump under container and carry out the stainless steel appearance that flow control flows into the belt stirrer equipped with 5L bottoms water and tank bottom can be passed through gas
In device, 65 DEG C of reaction and gelling temperature, control flow-rate adjustment reaction system (including plastic) pH value are 9.5, after reaction, are led to
It crosses dropwise addition ammonium hydroxide and adjusts slurry pH value to 9.5, aging 20min, 60 DEG C of aging temperature is separated by filtration mother liquor, washing.At 120 DEG C
Dry 4h, is made nickeliferous boehmite.
(2) nickeliferous carrier
The nickeliferous boehmite of preparation is weighed, with magnesium nitrate, nitric acid, citric acid, sesbania powder and water mixer kneader into can
Then plastomer, extruded moulding obtain nickeliferous carrier in 120 DEG C of dry 4h, 650 DEG C of roasting 4h.Prepare lanthanum nitrate, lithium carbonate and
Aqueous citric acid solution is impregnated into using equi-volume impregnating on nickeliferous carrier, is obtained in 120 DEG C of dry 4h, 900 DEG C of roasting 4h
The carrier of nickeliferous, magnesium, lanthanum and lithium.
(3) catalyst
By nickel acetate, ammonium molybdate is soluble in water that maceration extract is made, and is impregnated into what is prepared in (2) using equi-volume impregnating
On 100g carriers, 120 DEG C of drying, 350 DEG C of roasting 4h obtain catalyst C3.
Embodiment 4
(1) nickeliferous boehmite
By a concentration of 185g Al of 1L2O3The nickel nitrate solution of a concentration of 15g NiO/L of sodium aluminate solution and 1L of/L mixes
Conjunction is homogeneously disposed in belt stirrer and tank bottom can be passed through in the rustless steel container of gas, is passed through the gaseous mixture of carbon dioxide and air
Body, carbon dioxide in gas mixture a concentration of 70v%, flow 3Nm3/h.35 DEG C of reaction and gelling temperature, control flow-rate adjustment are anti-
It is 9.5 to answer system (including plastic) pH value, and stopping is passed through carbon dioxide, aging 45min, and 45 DEG C of aging temperature is separated by filtration mother
Liquid, washing.Nickeliferous boehmite is made in 110 DEG C of dry 3h.
(2) nickeliferous carrier
The nickeliferous boehmite of preparation is weighed, with nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader into plastic
Then body, extruded moulding obtain nickeliferous carrier in 120 DEG C of dry 4h, 620 DEG C of roasting 4h.It prepares lithium carbonate and citric acid is water-soluble
Liquid is impregnated into using equi-volume impregnating on nickeliferous carrier, is obtained nickeliferous and lithium in 120 DEG C of dry 4h, 1020 DEG C of roasting 4h
Carrier.
(3) catalyst
By nickel nitrate, ammonium molybdate is soluble in water that maceration extract is made, and is impregnated into what is prepared in (2) using equi-volume impregnating
On 100g carriers, 120 DEG C of drying, 400 DEG C of roasting 4h obtain catalyst C4.
Embodiment 5
(1) nickeliferous boehmite
By a concentration of 190gAl of 1L2O3The nickel nitrate solution mixing of a concentration of 8gNiO/L of sodium aluminate solution and 1L of/L is equal
It is even to be placed in belt stirrer and tank bottom is passed through in the rustless steel container of gas, the mixed gas of carbon dioxide and air is passed through, is mixed
Close carbon dioxide in gas a concentration of 60v%, flow 5Nm3/h.40 DEG C of reaction and gelling temperature control flow-rate adjustment reactant
(including plastic), pH value is 10.0 for system, and stopping is passed through carbon dioxide, aging 35min, and 40 DEG C of aging temperature is separated by filtration mother liquor,
Washing.In 110 DEG C of dry 3h, nickeliferous boehmite is made.
(2) nickeliferous carrier
The nickeliferous boehmite of preparation is weighed, with nitric acid, phosphoric acid, sesbania powder and water mixer kneader into plastic, extrusion
Then molding obtains nickeliferous carrier in 120 DEG C of dry 4h, 970 DEG C of roasting 4h.
(3) catalyst
Maceration extract in water is made in nickel acetate, ammonium molybdate, lanthanum nitrate co-dissolve, is impregnated into the 100g prepared in (2)
On carrier, 120 DEG C of drying, 480 DEG C of roasting 3h obtain catalyst C5.
Embodiment 6
(1) nickeliferous boehmite
By a concentration of 197g Al of 1L2O3The nickel nitrate solution of a concentration of 2.5gNiO/L of sodium aluminate solution and 1L of/L mixes
Conjunction is homogeneously disposed in belt stirrer and tank bottom can be passed through in the rustless steel container of gas, is passed through the gaseous mixture of carbon dioxide and air
Body, carbon dioxide in gas mixture a concentration of 70v%, flow 4Nm3/h.30 DEG C of reaction and gelling temperature, control flow-rate adjustment are anti-
It is 9.5 to answer system (including plastic) pH value, and stopping is passed through carbon dioxide, aging 30min, and 40 DEG C of aging temperature is separated by filtration mother
In 100 DEG C of dry 2h, 120 DEG C of dry 2h, nickeliferous boehmite is made in liquid, washing.
(2) nickeliferous carrier
The nickeliferous boehmite of preparation is weighed, mixes and pinches with magnesium nitrate, lithium carbonate, nitric acid, citric acid, sesbania powder and water
Plastic is synthesized, then extruded moulding obtains the carrier of nickeliferous, magnesium and lithium in 120 DEG C of dry 4h, 920 DEG C of roasting 4h.
(3) catalyst
By nickel nitrate, ammonium molybdate is soluble in water that maceration extract is made, and is impregnated into what is prepared in (2) using equi-volume impregnating
On 100g carriers, 120 DEG C of drying, 380 DEG C of roasting 4h obtain catalyst C6.
Embodiment 7
(1) nickeliferous boehmite
By a concentration of 195g Al of 1L2O3The nickel nitrate solution mixing of a concentration of 7gNiO/L of aluminum nitrate solution and 0.5L of/L
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 5L bottoms water and tank bottom can be passed through in the rustless steel container of gas, reacts
And 50 DEG C of gelling temperature, control flow-rate adjustment reaction system (including plastic) pH value are 7.5, after reaction, add in ammonium hydroxide tune
Plasm PH value 8.5, aging 60min are saved, 45 DEG C of aging temperature is separated by filtration mother liquor, washs.In 90 DEG C of dry 3h, 120 DEG C of dryings
Nickeliferous boehmite is made in 2h.
(2) nickeliferous carrier
The nickeliferous boehmite of preparation is weighed, with nitric acid, phosphoric acid, sesbania powder and water mixer kneader into plastic, extrusion
Then molding obtains nickeliferous carrier in 120 DEG C of dry 4h, 350 DEG C of roasting 4h.It is water-soluble to prepare lanthanum nitrate, lithium carbonate and citric acid
Liquid is impregnated into using equi-volume impregnating on nickeliferous carrier, and nickeliferous, lanthanum and lithium are obtained in 120 DEG C of dry 4h, 980 DEG C of roasting 4h
Carrier.
(3) catalyst
By nickel nitrate, ammonium molybdate is soluble in water that maceration extract is made, and is impregnated into what is prepared in (2) using equi-volume impregnating
On 100g carriers, 120 DEG C of drying, 380 DEG C of roasting 4h obtain catalyst C7.
Embodiment 8
(1) nickeliferous boehmite
By a concentration of 100gAl of 2L2O3The 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 a concentration of 60v%, flow 3Nm3/
h.35 DEG C of reaction and gelling temperature, control flow-rate adjustment reaction system (including plastic) pH value are 10.0, and stopping is passed through titanium dioxide
Carbon.Under blowing air stirring condition, the nickel nitrate solution of a concentration of 24gNiO/L of 0.5L is added in, after stablizing 30min, by the way that ammonia is added dropwise
It is 9.5 that water, which adjusts plasm PH value, and aging 30min, 40 DEG C of aging temperature are separated by filtration mother liquor after reaction, wash.At 90 DEG C
Dry 3h, 120 DEG C of dry 2h, are made nickeliferous boehmite.
(2) nickeliferous carrier
The nickeliferous boehmite of preparation is weighed, with nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader into plastic
Then body, extruded moulding obtain nickeliferous carrier in 120 DEG C of dry 4h, 990 DEG C of roasting 4h.
(3) catalyst
By nickel nitrate, ammonium molybdate is soluble in water that maceration extract is made, and is impregnated into (2) and prepared using two step equi-volume impregnatings
100g carriers on, a step using equi-volume impregnating dipping nickel nitrate total amount 65%, 120 DEG C drying, 350 DEG C roasting 4h,
Two steps are urged using 35% and ammonium molybdate of equi-volume impregnating dipping nickel nitrate total amount, 120 DEG C of drying, 380 DEG C of roasting 4h
Agent C8.
Embodiment 9
(1) nickeliferous boehmite
By a concentration of 92gAl of 2L2O3The sodium aluminate solution of/L is placed in belt stirrer and tank bottom can be passed through the stainless steel of gas
In container, it is passed through the mixed gas of carbon dioxide and air, carbon dioxide in gas mixture a concentration of 60v%, flow 3Nm3/h。
35 DEG C of reaction and gelling temperature, control flow-rate adjustment reaction system (including plastic) pH value are 10.0, and stopping is passed through carbon dioxide.
Under blowing air stirring condition, the nickel nitrate solution of a concentration of 7gNiO/L of 1L is added in, after stablizing 20min, is adjusted by the way that ammonium hydroxide is added dropwise
Plasm PH value is 9.5, after reaction aging 40min, and 45 DEG C of aging temperature is separated by filtration mother liquor, washing.In 120 DEG C of dryings
Nickeliferous boehmite is made in 4h.
(2) nickeliferous carrier
The nickeliferous boehmite of preparation is weighed, with nitric acid, citric acid, sesbania powder and water mixer kneader into plastic, is squeezed
Item is molded, and then obtains nickeliferous carrier in 120 DEG C of dry 4h, 1050 DEG C of roasting 4h.
(3) catalyst
By nickel nitrate, ammonium molybdate is soluble in water that maceration extract is made, and is impregnated into what is prepared in (2) using equi-volume impregnating
On 100g carriers, 120 DEG C of drying, 400 DEG C of roasting 4h obtain catalyst C9.
Comparative example 1
This comparative example prepares nickeliferous carrier according to the method that embodiment in CN1123392C describes, and is as follows：
It weighs 200g aluminum hydroxide solid elastomers powder and 10.0g sesbania powders after mixing, then weighs 40g carbon blacks and 18.5g alkali
Formula nickelous carbonate after mixing, adds in tetrabutylammonium hydroxide (the wherein C previously measured with graduated cylinder wherein16H37NO's
Content about 10w%) 76ml, is stirred with glass bar, tetrabutylammonium hydroxide solution is made to be come into full contact with mixture, place 20min
Afterwards, it adds it to and is mixed in the aluminum hydroxide solid elastomer powder of sesbania powder, again mixing；
By acetic acid and citric acid, the mixed solution of deionized water, it is added to and is mixed with basic nickel carbonate, carbon black and sesbania powder
In aluminum hydroxide solid elastomer powder, kneading is extruded into cloverleaf pattern item, at 120 DEG C into after uniform paste plastic on banded extruder
After dry 3.5h, 4h is roasted at 950 DEG C, alumina carrier containing Ni is made.
Maceration extract is made in nickel nitrate, ammonium molybdate, lithium carbonate co-dissolve in water, the 100g for being impregnated into above-mentioned preparation contains
On nickel carrier, 120 DEG C of drying, 420 DEG C of roasting 4h obtain catalyst D1.
Comparative example 2
This comparative example prepares nickeliferous carrier according to the method that embodiment in CN1123392C describes, and is as follows：
It weighs 200g aluminum hydroxide solid elastomers powder and 6.0g sesbania powders after mixing, then weighs 30g carbon blacks and 8.4g alkali formulas
Nickelous carbonate after mixing, adds in tetrabutylammonium hydroxide (the wherein C previously measured with graduated cylinder wherein16H37The content of NO
About 10w%) 40ml, it is stirred with glass bar, tetrabutylammonium hydroxide solution is made to be come into full contact with mixture, it, will after placing 30min
It is added in the aluminum hydroxide solid elastomer powder for being mixed with sesbania powder, again mixing；
By acetic acid and citric acid, the mixed solution of deionized water, it is added to and is mixed with basic nickel carbonate, carbon black and sesbania powder
In aluminum hydroxide solid elastomer powder, kneading is extruded into cloverleaf pattern item, at 110 DEG C into after uniform paste plastic on banded extruder
After dry 4h, alumina carrier containing Ni is made.Lithium carbonate aqueous solution is prepared, nickeliferous carrier is impregnated into using equi-volume impregnating
On, obtain nickeliferous, lanthanum carrier in 120 DEG C of dry 4h, 900 DEG C of roasting 4h.
Maceration extract in water is made in nickel nitrate, ammonium molybdate co-dissolve, is impregnated into the nickeliferous carriers of 100g of above-mentioned preparation
On, 120 DEG C of drying, 420 DEG C of roasting 4h obtain catalyst D2.
Comparative example 3
(1) boehmite
By a concentration of 50g Al of 1L2O3A concentration of 150g Al of aluminum sulfate solution and 1.5L of/L2O3/ L sodium aluminate solutions
Be respectively charged into the container of high level, connect under two containers peristaltic pump carry out flow control flow into equipped with 5L bottoms water belt stirrer and
Tank bottom can be passed through in the rustless steel container of gas, 50 DEG C of reaction and gelling temperature, control flow-rate adjustment reaction system (including into
Glue) pH value be 9.0, after reaction, by be added dropwise ammonium hydroxide adjust slurry pH value be 9.5, aging 30min, 50 DEG C of aging temperature,
Mother liquor is separated by filtration, is washed.Boehmite is obtained in 90 DEG C of dry 3h, 120 DEG C of dry 2h.
(2) carrier
The boehmite of preparation is weighed, with lithium carbonate, nitric acid, phosphoric acid, sesbania powder and water mixer kneader into plastic, is squeezed
Item is molded, and carrier then is made in 120 DEG C of dry 4h, 950 DEG C of roasting 4h.
(3) catalyst
Maceration extract in water is made in nickel nitrate, ammonium molybdate and lanthanum nitrate co-dissolve, is impregnated into the 100g prepared in (2)
On carrier, 120 DEG C of drying, 390 DEG C of roasting 3h obtain catalyst D3.
Comparative example 4
(1) boehmite
By a concentration of 150g Al of 2L2O3The 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 a concentration of 60v%, flow 4Nm3/
h.35 DEG C of reaction and gelling temperature, control flow-rate adjustment reaction system (including plastic) pH value are 10.0, and stopping is passed through titanium dioxide
Carbon, aging 30min, 45 DEG C of aging temperature are separated by filtration mother liquor, washing.120 DEG C of dry 4h, obtain boehmite.
(2) carrier
The boehmite of preparation is weighed, with nitric acid, phosphoric acid, sesbania powder and water mixer kneader into plastic, extruded moulding,
Then carrier is made in 120 DEG C of dry 4h, 1000 DEG C of roasting 4h.
(3) catalyst
Maceration extract in water is made in nickel nitrate, ammonium molybdate, cerous nitrate, lanthanum nitrate co-dissolve, is impregnated into (2) and prepares
100g carriers on, 120 DEG C drying, 410 DEG C roasting 3h, obtain catalyst D4.
Comparative example 5
(1) boehmite
By a concentration of 150gAl of 2L2O3The 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 a concentration of 70v%, flow 3Nm3/
h.35 DEG C of reaction and gelling temperature, control flow-rate adjustment reaction system (including plastic) pH value are 9.5, and stopping is passed through titanium dioxide
Carbon, aging 20min, 45 DEG C of aging temperature are separated by filtration mother liquor, washing.It must intend thin water in 90 DEG C of dry 3h, 120 DEG C of dry 2h
Aluminium stone.
(2) carrier
The boehmite of preparation is weighed, with nitric acid, phosphoric acid, citric acid, sesbania powder and water mixer kneader into plastic, is squeezed
Item is molded, and then obtains carrier in 120 DEG C of dry 4h, 600 DEG C of roasting 4h.Magnesium nitrate, lithium carbonate aqueous solution are prepared, using etc.
Volume impregnation method is impregnated on carrier, and the carrier containing magnesium and lithium is obtained in 120 DEG C of dry 4h, 980 DEG C of roasting 4h.
(3) catalyst
Nickel acetate, ammonium molybdate are dissolved in the water, maceration extract is made, be impregnated on the 100g carriers prepared in (2), 120 DEG C
Drying, 400 DEG C of roasting 3h, obtains catalyst D5.
Comparative example 6
(1) boehmite
Prepare a concentration of 100gAl of 2L2O3The ammonia spirit of the aluminum nitrate solution of/L and a concentration of 8wt% are respectively charged into a high position
In the container at place, peristaltic pump progress belt stirrer of the flow control inflow equipped with 3L bottoms 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 and gelling temperature, control flow-rate adjustment reaction system (including plastic) pH value are 8.0,
After reaction, it adds in ammonium hydroxide and adjusts plasm PH value 8.5, aging 30min, 50 DEG C of aging temperature is separated by filtration mother liquor, washes
It washs.In 120 DEG C of dry 2h, boehmite is obtained.
(2) carrier
Weigh the boehmite of preparation, with nitric acid, citric acid, sesbania powder and water mixer kneader into plastic, extrusion into
Type, then in 120 DEG C of dryings, 880 DEG C of roasting 4h obtain carrier.
(3) catalyst
By nickel nitrate, ammonium molybdate is soluble in water that maceration extract is made, and is impregnated into (2) and prepared using two step equi-volume impregnatings
100g carriers on, a step using equi-volume impregnating dipping nickel nitrate total amount 65%, 120 DEG C drying, 350 DEG C roasting 4h,
Two steps are urged using 35% and ammonium molybdate of equi-volume impregnating dipping nickel nitrate total amount, 120 DEG C of drying, 420 DEG C of roasting 4h
Agent D6.
Catalyst D1~D6 catalyst physical property and composition are shown in Table in catalyst C1~C9 and comparative example 1-6 in embodiment 1-9
1。
1 embodiment catalyst of table and comparative example catalyst physical property and composition
Evaluating catalyst：
Using drippolene, feedstock property is shown in Table 2 for raw material, and C1~C9 and D1~D6 catalyst are evaluated.Respectively
300h is evaluated, per 12h sampling analyses bromine valency and diene, average data see the table below 3.
Evaluating catalyst carries out on 100ml adiabatic reactor hydrogenation reaction devices, and catalyst is first at 380~450 DEG C
10h is restored under hydrogen, then cools to 70 DEG C, the laggard feedstock oils of 4h are passivated with the hexamethylene of the 1000ppm containing dimethyl disulfide.It comments
Valency process conditions：Reaction pressure 2.8MPa, 50 DEG C of inlet temperature, fresh feed oil air speed 3.0h-1, hydrogen is with oil volume than 200: 1
(volume ratio is in terms of green oil).
2 hydrogenating materials oil nature of table
3 evaluating catalyst average data of table
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| Hydrogenated products diene/(gI/100g) | 1.71 | 2.01 | 1.64 | 1.42 | 1.54 | 1.65 | 2.14 | 1.12 |
| Hydrogenated products bromine valency gBr/100g | 21.7 | 22.6 | 20.7 | 24.5 | 25.8 | 24.1 | 22.5 | 26.2 |
| Catalyst is numbered | C9 | D1 | D2 | D3 | D4 | D5 | D6 | |
| Hydrogenated products diene/(gI/100g) | 2.54 | 2.65 | 2.38 | 2.84 | 2.98 | 2.11 | 1.87 | |
| Hydrogenated products bromine valency gBr/100g | 19.8 | 25.5 | 28.4 | 23.4 | 23.5 | 25.6 | 27.0 |
As can be seen from the above Examples and Comparative Examples, the nickel-molybdenum system prepared using the nickeliferous aluminium oxide of the present invention adds hydrogen to urge
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 has higher hydrogenation activity and stability.
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 deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (16)
1. a kind of nickel-molybdenum series hydrocatalyst, containing active component nickel and molybdenum in catalyst, using nickeliferous aluminium oxide as carrier,
It is characterized in that：It is counted by 100wt% of catalyst weight, contains 10~20wt% of nickel oxide, preferably 14.5~18.5wt%, oxygen
Change 0.1~5wt% of molybdenum, preferably 0.3~2wt%, cerium oxide and/or lanthana 0~5wt%, preferably 0.2~2wt%, alkali
Metal and/or alkaline earth oxide 0~6wt%, preferably 0.5~3wt%；50~150m of specific surface area of catalyst2/ g, hole
Hold 0.30~0.55cm3/ g, 0.6~1.1g/cm of heap density3；The presoma of alumina carrier containing Ni is nickeliferous boehmite,
There are acid-base neutralization and plastic process in the preparation process of the nickeliferous boehmite；Nickeliferous aluminium oxide is impregnated containing active component solution
Through drying, roasting, nickel-molybdenum series hydrocatalyst is made in carrier.
2. nickel-molybdenum 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；Using nickeliferous boehmite total weight as
100wt% is counted, and nickel content is 0.1~10wt%, preferably 0.5~5wt%.
3. nickel-molybdenum 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-molybdenum series hydrocatalyst according to claim 1, it is characterised in that：Alumina carrier containing Ni is by nickeliferous plan
Boehmite is obtained through being molded, roasting, and contains δ-Al2O3、δ-NiAl26O40And NiAl2O4Crystal form, and 0.45 in XRD spectra≤
B1/B2≤0.85, B1 refer to the integrated intensity at the peak that 2 θ are 34.2~39.8 ° in XRD spectra, and B2 refers to that 2 θ are in XRD spectra
The integrated intensity at 43.3~48.5 ° of peak.
5. nickel-molybdenum 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-molybdenum 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 less than 30wt%.
7. nickel-molybdenum 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 calcination temperature.
8. a kind of preparation method of nickel-molybdenum series hydrocatalyst described in claim 1, it is characterised in that：With nickeliferous and molybdenum
Solution impregnates alumina carrier containing Ni by one or multi-step, and catalyst is obtained by drying, roasting；Alumina carrier containing Ni by
Nickeliferous boehmite is obtained through being molded, roasting；Wherein nickeliferous boehmite is obtained by following methods, and detailed process includes
Following steps：
(1) it neutralizes and bottom water is added in kettle, 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, it is 50~90 DEG C, wherein acidic aluminum brine to adjust its solution temperature
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) the alkali metal aluminate solution cocurrent that the acidic aqueous solution and step (3) obtained step (2) obtains adds in step
(1) in the neutralization kettle in, constant ventilation stirring, until plastic；
(5) 50~90 DEG C of rate-determining steps (4) gelling temperature, plastic pH value 7~10；
(6) it after cemented into bundles, through aging, is filtered, washed, dries obtained nickeliferous boehmite.
9. the preparation method of nickel-molybdenum 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-molybdenum 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-molybdenum series hydrocatalyst according to claim 8, it is characterised in that：In step (5), into
50~70 DEG C of glue temperature；Plastic pH value 7.5~9.5.
12. the preparation method of nickel-molybdenum series hydrocatalyst according to claim 8, it is characterised in that：It is step (3)
The pH value of middle alkali metal aluminate solution is 9~14, preferable ph 12~14.
13. the preparation method of nickel-molybdenum series hydrocatalyst according to claim 8, it is characterised in that：Acid aluminium salt is water-soluble
Mixed solution of the liquid for 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 refer to sodium metaaluminate or potassium metaaluminate solution.
14. the preparation method of nickel-molybdenum series hydrocatalyst according to claim 8, it is characterised in that：In step (2), acid
Property aluminium salt and acid nickel salt solution mix, 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-molybdenum series hydrocatalyst according to claim 8, it is characterised in that：In step (6), always
It is 50~80 DEG C to change temperature, and ageing time is 10~60min.
16. the preparation method of nickel-molybdenum series hydrocatalyst according to claim 8, it is characterised in that：With nickeliferous and molybdenum
Solution impregnates alumina carrier containing Ni by one or multi-step, and catalyst is made by drying, roasting；Its roasting condition is：300
3~8h is roasted at~500 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479333A (en) * | 2019-08-27 | 2019-11-22 | 韩宝亭 | A kind of preparation method of environment-friendly type hydrorefining catalyst for heavy oil |
| CN112547067A (en) * | 2019-09-10 | 2021-03-26 | 中石化南京化工研究院有限公司 | Preparation method of catalyst for slurry bed methane synthesis reaction |
| CN113559870A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139217A (en) * | 2010-02-03 | 2011-08-03 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN102268285A (en) * | 2011-07-08 | 2011-12-07 | 中国石油天然气股份有限公司 | Pre-hydrotreatment method of reforming feedstocks |
| CN103055876A (en) * | 2013-01-22 | 2013-04-24 | 新地能源工程技术有限公司 | Preparation method of wide-temperature methanation catalyst |
| 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 |
| EP3101000A1 (en) * | 2014-01-28 | 2016-12-07 | Nippon Shokubai Co., Ltd. | Hydrogenation reaction method |
-
2016
- 2016-12-30 CN CN201611263029.4A patent/CN108262047B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139217A (en) * | 2010-02-03 | 2011-08-03 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN102268285A (en) * | 2011-07-08 | 2011-12-07 | 中国石油天然气股份有限公司 | Pre-hydrotreatment method of reforming feedstocks |
| 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 |
| CN103055876A (en) * | 2013-01-22 | 2013-04-24 | 新地能源工程技术有限公司 | Preparation method of wide-temperature methanation catalyst |
| EP3101000A1 (en) * | 2014-01-28 | 2016-12-07 | Nippon Shokubai Co., Ltd. | Hydrogenation reaction method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479333A (en) * | 2019-08-27 | 2019-11-22 | 韩宝亭 | A kind of preparation method of environment-friendly type hydrorefining catalyst for heavy oil |
| CN112547067A (en) * | 2019-09-10 | 2021-03-26 | 中石化南京化工研究院有限公司 | Preparation method of catalyst for slurry bed methane synthesis reaction |
| CN112547067B (en) * | 2019-09-10 | 2023-06-20 | 中国石油化工股份有限公司 | Preparation method of catalyst for slurry bed methane synthesis reaction |
| CN113559870A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method and application thereof |
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