CN109794255A - The method that a kind of alloy phase catalyst and preparation method thereof and small molecular alcohol prepare higher alcohol - Google Patents
The method that a kind of alloy phase catalyst and preparation method thereof and small molecular alcohol prepare higher alcohol Download PDFInfo
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- CN109794255A CN109794255A CN201910105480.0A CN201910105480A CN109794255A CN 109794255 A CN109794255 A CN 109794255A CN 201910105480 A CN201910105480 A CN 201910105480A CN 109794255 A CN109794255 A CN 109794255A
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Abstract
The present invention relates to a kind of methods that catalyst technical field more particularly to alloy phase catalyst and preparation method thereof and small molecular alcohol prepare higher alcohol.The invention discloses a kind of alloy phase catalysts, comprising: metal M and W metal, the metal M and the W metal form MNixAlloy phase；The metal M is Sn, Cu or Mg, then x is respectively 3,1,1.5.The catalyst is heterogeneous catalysis, in aqueous catalysis small molecular alcohol synthesis higher alcohol, it is easily isolated and recycles, it can also be recycled after recycling, in addition, the catalyst is without precious metal, cost is saved, it solves the existing catalyst presence for preparing higher alcohol and is not readily separated and corrodes equipment, and the problem lower to the selectivity of the more advanced alcohol of C5+.
Description
Technical field
The present invention relates to catalyst technical field more particularly to a kind of alloy phase catalyst and preparation method thereof and small molecules
The method that alcohol prepares higher alcohol.
Background technique
Ethyl alcohol is as the alcohol-based fuel developed first, and hygroscopicity is high, energy density is low, cannot use pipeline.And amylalcohol,
The C5+ long-chain higher alcohol such as hexanol has many advantages, such as that energy density is high, hydrophobicity is easily isolated well, is easily passivated, in addition to can be fine
It is used in chemical industry as extractant, is also considered as a kind of liquid combination of high added value, be used as fuel combination
Component facilitate fuel burning when it is more complete, improve efficiency of combustion, reduce soot emissions, and application when can be with existing mine
Object energy infrastructure is compatible, is a kind of alcohol-based fuel of great potential.Currently, higher alcohol is based primarily upon the life of petrochemistry approach
It produces.Petrochemistry rule is small molecular alcohol can be converted to high molecular weight under the catalysis of metal sodium alkoxide by Guerbet reaction
Branch or straight chain alcohol, but homogeneous catalyst used in the process there are problems that being not readily separated and corroding equipment, and its
Middle primary product is all C4 butanol, and the selectivity of the more advanced alcohol of C5+ is lower.
Summary of the invention
The present invention provides the method that a kind of alloy phase catalyst and preparation method thereof and small molecular alcohol prepare higher alcohol, solutions
The existing catalyst for preparing higher alcohol of having determined, which exists, is not readily separated and corrodes equipment, and to the selectivity of the more advanced alcohol of C5+ compared with
Low problem.
Its specific technical solution is as follows:
The present invention provides a kind of alloy phase catalysts, comprising: metal M and W metal, the metal M and the W metal
Form MNixAlloy phase；
The metal M is Sn, Cu or Mg, then x is respectively 3,1 and 1.5, i.e. SnNi3, CuNi and MgNi1.5, preferably Sn,
X is 3.
Preferably, the specific surface area of the alloy phase catalyst is 40m2/g-60m2/ g, more preferably 47m2/ g, aperture are
30nm-80nm, more preferably 50nm, partial size 50nm-100nm, more preferably 80nm.
In the present invention, W metal is the active constituent of the catalyst in alloy phase catalyst, and metal M is electronic auxiliary, warp
The MNi formed after reduction activation processingxThe catalytic dehydrogenation ability of Ni active sites mutually can be effectively controlled in alloy.Alloy phase catalyst is
Therefore solid catalyst after the solid catalyst carries out catalysis reaction in water phase, carries out simple centrifugal filtration and drying
Afterwards, that is, it may be recovered.In addition, alloy phase catalyst provided by the invention is non-precious metal catalyst, reaction cost is saved.
The present invention also provides the preparation methods of above-mentioned alloy phase catalyst, comprising the following steps:
Moisture will be removed after the salt solution impregnation Raney Ni powder of M, then carry out in-situ reducing reaction, obtains the alloy
Phase catalyst；
M in the salting liquid of the M is selected from Sn, Cu or Mg, preferably Sn.
In the present invention, Raney's nickel (Raney Ni) powder uses commercially available industry Raney Ni powder；Salting liquid is preferably
Cl-, SO4 2-Or NO3-, preferably SnCl4；The time of the reduction reaction is 3-6h, and preferably 4h, temperature is 300-500 DEG C,
Preferably 500 DEG C.
In the present invention, after obtaining the alloy phase catalyst, protect the catalyst not oxidized using water seal method.
Preferably, the mass ratio of the Ni in the alloy phase catalyst in the M and Raney Ni is 1/20-1/2, preferably
It is 1/10.
Preferably, the time of the dipping is 6-12h, and preferably 8h, the temperature of the dipping is 20-60 DEG C, preferably
20℃。
Preferably, the removing moisture specifically: 100-120 DEG C of removing moisture in a hydrogen atmosphere, preferably 100 DEG C are removed
Remove moisture.
Preferably, the in-situ reducing reaction carries out in hydrogen gas stream；
The air speed of the reduction reaction is 2000h-1-5000h-1, preferably 3000h-1。
It is modified using the salt solution impregnation of M using industrial Raney Ni powder as carrier in the present invention, after reduction activation
Form MNixThe catalytic dehydrogenation ability of Ni active sites can be effectively controlled in alloy phase, easy to operate.
The present invention also provides a kind of methods that small molecular alcohol prepares higher alcohol, comprising the following steps:
The aqueous solution of small molecular alcohol is reacted under alkaline condition with above-mentioned alloy phase catalyst, obtains higher alcohol；
The carbon atom number of the small molecular alcohol is a for 2-4, preferably one of ethyl alcohol, propyl alcohol and butanol or a variety of, more
The preferably mixture of the mixture of ethyl alcohol, n-butanol, normal propyl alcohol, ethyl alcohol and normal propyl alcohol, ethyl alcohol and n-butanol, normal propyl alcohol and just
Mixture, ethyl alcohol and the normal propyl alcohol of butanol and the mixture of n-butanol, the carbon atom number of the higher alcohol are at least 5, preferably
It is 5-16.
In the present invention, higher alcohol is preferably the isomery alcohol that carbon atom number is 5-16, and isomery alcohol has higher compared with straight chain alcohol
Octane number, it is preferably to be used as high-quality fuel combination.
In the present invention, the chain growth of small molecular alcohol is the multistep reaction being catalyzed by two different catalytic active sites, packet
Include alcohol dehydrogenase, aldehyde adds hydrogen and aldol reaction.Small molecular alcohol first occurs under the catalysis of the metal active position of alloy phase catalyst
Dehydrogenation generates aldehydes intermediate, and aldol condensation and spontaneous de- occurs for the aldehydes and alcohols in system and then be catalyzed under alkaline condition
Chain growth is realized in water reaction, and is finally hydrogenated to long-chain alcohol, which cooperates in the presence of alloy phase catalyst and alkali and urge
Change lower complete.
In the present invention, small molecular alcohol can be obtained by cellulose hydrogenolysis, avoid the fringe cost of alcohols separating-purifying.
In the present invention, the device of the reaction is slurry bed system steel reactor；
Before carrying out the reaction, further includes: the slurry bed system steel reactor is sealed and the 6MPa leak detection that builds the pressure, really
Gas reactor is replaced repeatedly with high-purity hydrogen after recognizing sealing normally until air excludes completely in kettle；
It is described after reaction, further includes: the slurry bed system steel reactor is cooled to room temperature and is centrifuged and is filtered
Afterwards, liquid phase and solid phase are obtained, as shown in Figure 1, wherein liquid phase stratification after being centrifuged obtains organic phase and water phase, organic phase
Middle primary product is higher alcohol, and water phase is water and unreacted small molecular alcohol, can continue cycling through use, after the cleaned drying of solid phase
To used alloy phase catalyst.Reaction also generates gaseous hydrogen, methane and carbon dioxide etc. simultaneously.The alloy phase catalyst
Only need to simply be separated by filtration can be recycled, i.e. reusable after dry, and the alloy phase catalyst is non-corrosive.
Preferably, the reaction temperature is 150-280 DEG C, and preferably 250 DEG C, the reaction time is 12-72h, preferably
For for 24 hours, the initial pressure of the reaction is 0.1-2MPa, preferably 0.1MPa.
Preferably, the alkaline source for providing the alkaline condition is NaOH or KOH；
The molar ratio of the alkali compounds and the small molecular alcohol is 1/25-1/8, more preferably 1/25.
As can be seen from the above technical solutions, the invention has the following advantages that
The present invention provides a kind of alloy phase catalysts, which is heterogeneous catalysis, in aqueous catalysis small molecule
Alcohol synthesizes in higher alcohol, is easily isolated and recycles, can also recycle after recycling, in addition, the catalyst is without precious metal, section
Cost is saved.
The present invention also provides a kind of preparation method of alloy phase catalyst, which can be obtained using infusion process
Alloy phase catalyst, it is easy to operate simple, it is suitble to industrial production.
The present invention also provides a kind of methods that small molecular alcohol prepares higher alcohol, are mutually catalyzed using alloy provided by the invention
Agent can one-step method aqueous catalysis small molecular alcohol synthesize higher alcohol, small molecular alcohol raw material can directly adopt alcohol solution, compared to biography
The alcohols of system converts, and avoids the process of the alcohol separating-purifying of high energy consumption.By experimental data it is found that being obtained using the catalyst
To reaction product organic phase in primary product be C5-C16 higher alcohol, and be branched degree 90% or more.Therefore, should
Advanced isomery alcohol has higher value relative to small molecular alcohol and non-isomery higher alcohol, can be widely used for plasticizer, surface is lived
Property agent and solvent etc..Advanced isomery alcohol is obtained in the present invention compared to ethyl alcohol more preferably engine fuel, can be blended with diesel oil,
It is good with calorific value height, hydrophobicity, it can effectively reduce the combustion tail gas pollutant emission of conventional fuel oil, be a kind of very promising hair
Motivation alternative fuel.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings.
Fig. 1 is the process flow chart for the method that a kind of small molecular alcohol provided by the invention prepares higher alcohol.
Fig. 2 is the SnNi that the embodiment of the present invention 1 provides3The XRD diffraction of alloy phase catalyst (Sn/Ni mass ratio is 1/10)
Map；
Fig. 3 is the SnNi that the embodiment of the present invention 1 provides3The SEM Electronic Speculum of alloy phase catalyst (Sn/Ni mass ratio is 1/10)
Figure.
Specific embodiment
The embodiment of the invention provides a kind of alloy phase catalysts and preparation method thereof and small molecular alcohol to prepare higher alcohol
Method is not readily separated and corrodes equipment for solving the problems, such as that the existing catalyst for preparing higher alcohol exists.
It in order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below will be to of the invention real
The technical solution applied in example is clearly and completely described, it is clear that the embodiments described below are only present invention a part
Embodiment, and not all embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of all other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
(1)SnNi3The preparation of alloy phase alloy phase catalyst.
Wherein Sn/Ni mass ratio is 1/10.Preparation process uses SnCl4(20 DEG C) dipping RaneyNi8h of room temperature, have impregnated
In 100 DEG C of removing moisture under hydrogen atmosphere protection after, then in 3000h-1Hydrogen stream in 500 DEG C of reduction 4h, obtain
SnNi3Alloy phase catalyst.
As shown in Fig. 2, can determine that SnNi is prepared in the embodiment of the present invention by XRD diffracting spectrum3Alloy is mutually catalyzed
Agent.
As shown in figure 3, passing through SnNi3Alloy phase electron microscope can see, SnNi3Alloy catalyst is by metallic particles heap
Product forms, and there are pore structure abundant, and cellular structure is made of the macropore that intergranular is mesoporous and particle packing is formed, particle
Partial size average out to 80nm, specific surface area are average out to 47m2/ g, aperture averaging 50nm.
(2) preparation of higher alcohol.
Reaction raw materials are the mixed solution of second alcohol and water, wherein ethanol/water mass ratio=1, respectively take 15g in experiment；NaOH
For alkali source, alkali/alcohol molar ratio is 1/25, takes 0.5g in experiment；SnNi3Alloy phase catalyst and raw alcohol mass ratio are 1/30,
0.5g is taken in experiment；
Reaction carries out in the steel reactor of 60ml, aqueous solution, alkali source and the SnNi of ethyl alcohol3Alloy phase catalyst is added
After slurry reactor kettle, seals autoclave body and the 6MPa that builds the pressure hunts leak, replace gas in kettle repeatedly with high-purity hydrogen after confirmation sealing is normal
Body is until air excludes completely in kettle.Reaction initial pressure is 0.1MPa, and reaction temperature is 250 DEG C, speed of agitator 600rpm, instead
Answer duration for 24 hours.It is cooled to room temperature reaction kettle after reaction, after being centrifuged and being filtered, liquid phase and solid phase is obtained, collects gas
Phase and liquid product, stratification obtains organic phase and water phase after liquid product centrifugation, and organic phase primary product is higher alcohol.
Embodiment 2
(1)SnNi3The preparation of alloy phase catalyst is the same as embodiment 1.
(2) preparation of higher alcohol.
Reaction raw materials are the mixed solution of normal propyl alcohol and water, wherein n-propanol/water mass ratio=1, respectively take 15g in experiment；
NaOH is alkali source, and alkali/alcohol molar ratio is 1/25, takes 0.4g in experiment；Sn-Ni catalyst and raw alcohol mass ratio are 1/30, real
0.5g is taken in testing；
Reaction carries out in the steel reactor of 60ml, and it is anti-that slurry bed system is added in aqueous solution, alkali source and the catalyst of normal propyl alcohol
After answering kettle, seals autoclave body and the 6MPa that builds the pressure hunts leak, replace gas reactor repeatedly with high-purity hydrogen until kettle after confirmation sealing is normal
Interior air excludes completely.Reaction initial pressure is 0.1MPa, and reaction temperature is 250 DEG C, speed of agitator 600rpm, reacts duration
24h.It is cooled to room temperature reaction kettle after reaction, after being centrifuged and being filtered, liquid phase and solid phase is obtained, collects gas phase and liquid
Phase product, stratification obtains organic phase and water phase after liquid product centrifugation, and organic phase primary product is higher alcohol.
Embodiment 3
(1) preparation of Sn-Ni alloy phase catalyst is the same as embodiment 1.
(2) preparation of higher alcohol.
Reaction raw materials are the mixed solution of n-butanol and water, wherein n-butanol/water mass ratio=1, respectively take 15g in experiment；
NaOH is alkali source, and alkali/alcohol molar ratio is 1/25, takes 0.33g in experiment；Sn-Ni catalyst and raw alcohol mass ratio are 1/30, real
0.5g is taken in testing；
Reaction carries out in the steel reactor of 60ml, and it is anti-that slurry bed system is added in aqueous solution, alkali source and the catalyst of n-butanol
After answering kettle, seals autoclave body and the 6MPa that builds the pressure hunts leak, replace gas reactor repeatedly with high-purity hydrogen until kettle after confirmation sealing is normal
Interior air excludes completely.Reaction initial pressure is 0.1MPa, and reaction temperature is 250 DEG C, speed of agitator 600rpm, reacts duration
24h.It is cooled to room temperature reaction kettle after reaction, after being centrifuged and being filtered, liquid phase and solid phase is obtained, collects gas phase and liquid
Phase product, stratification obtains organic phase and water phase after liquid product centrifugation, and organic phase primary product is higher alcohol.
Embodiment 4
(1) preparation of Sn-Ni alloy phase catalyst is the same as embodiment 1.
(2) preparation of higher alcohol.
Reaction raw materials are the mixed solution of ethyl alcohol, normal propyl alcohol and water, and wherein ethyl alcohol, normal propyl alcohol and water quality ratio are 1:1:1,
Ethyl alcohol, normal propyl alcohol and water respectively take 10g in experiment；NaOH is alkali source, and alkali/alcohol molar ratio is 1/25, takes 0.61g in experiment；Sn-Ni
Catalyst and raw alcohol mass ratio are 1/30, take 0.67g in experiment；
Reaction carries out in the steel reactor of 60ml, and slurry is added in aqueous solution, alkali source and the catalyst of ethyl alcohol and normal propyl alcohol
After state bed reaction kettle, seals autoclave body and the 6MPa that builds the pressure hunts leak, replace gas reactor repeatedly with high-purity hydrogen after confirmation sealing is normal
Until air excludes completely in kettle.Reaction initial pressure is 0.1MPa, and reaction temperature is 250 DEG C, speed of agitator 600rpm, reaction
Duration is for 24 hours.It is cooled to room temperature reaction kettle after reaction, after being centrifuged and being filtered, liquid phase and solid phase is obtained, collects gas phase
And liquid product, stratification obtains organic phase and water phase after liquid product centrifugation, and organic phase primary product is higher alcohol.
Embodiment 5
(1) preparation of Sn-Ni alloy phase catalyst is the same as embodiment 1.
(2) preparation of higher alcohol.
Reaction raw materials are the mixed solution of ethyl alcohol, n-butanol and water, and wherein the mass ratio of ethyl alcohol, n-butanol and water is 1:1:
1, ethyl alcohol, n-butanol and water respectively take 10g in experiment；NaOH is alkali source, and alkali/alcohol molar ratio is 1/25, takes 0.56g in experiment；Sn-
Ni catalyst and raw alcohol mass ratio are 1/30, take 0.67g in experiment；
Reaction carries out in the steel reactor of 60ml, and slurry is added in aqueous solution, alkali source and the catalyst of ethyl alcohol and n-butanol
After state bed reaction kettle, seals autoclave body and the 6MPa that builds the pressure hunts leak, replace gas reactor repeatedly with high-purity hydrogen after confirmation sealing is normal
Until air excludes completely in kettle.Reaction initial pressure is 0.1MPa, and reaction temperature is 250 DEG C, speed of agitator 600rpm, reaction
Duration is for 24 hours.It is cooled to room temperature reaction kettle after reaction, after being centrifuged and being filtered, liquid phase and solid phase is obtained, collects gas phase
And liquid product, stratification obtains organic phase and water phase after liquid product centrifugation, and organic phase primary product is higher alcohol.
Embodiment 6
(1) preparation of Sn-Ni alloy phase catalyst is the same as embodiment 1.
(2) preparation of higher alcohol.
Reaction raw materials are the mixed solution of normal propyl alcohol, n-butanol and water, and wherein the mass ratio of normal propyl alcohol, n-butanol and water is
1:1:1, normal propyl alcohol, n-butanol and water respectively take 10g in experiment；NaOH is alkali source, and alkali/alcohol molar ratio is 1/25, is taken in experiment
0.48g；Sn-Ni catalyst and raw alcohol mass ratio are 1/30, take 0.67g in experiment；
Reaction carries out in the steel reactor of 60ml, and aqueous solution, alkali source and the catalyst of normal propyl alcohol and n-butanol are added
After slurry reactor kettle, seals autoclave body and the 6MPa that builds the pressure hunts leak, replace gas in kettle repeatedly with high-purity hydrogen after confirmation sealing is normal
Body is until air excludes completely in kettle.Reaction initial pressure is 0.1MPa, and reaction temperature is 250 DEG C, speed of agitator 600rpm, instead
Answer duration for 24 hours.It is cooled to room temperature reaction kettle after reaction, after being centrifuged and being filtered, liquid phase and solid phase is obtained, collects gas
Phase and liquid product, stratification obtains organic phase and water phase after liquid product centrifugation, and organic phase primary product is higher alcohol.
Embodiment 7
(1) preparation of Sn-Ni alloy phase catalyst is the same as embodiment 1.
(2) preparation of higher alcohol.
Reaction raw materials are the mixed solution of ethyl alcohol, normal propyl alcohol, n-butanol and water, wherein ethyl alcohol, normal propyl alcohol, n-butanol and water
Mass ratio be 1:1:1:1, ethyl alcohol, normal propyl alcohol, n-butanol and water respectively take 7.5g in experiment；NaOH is alkali source, alkali/alcohol molar ratio
It is 1/25, takes 0.62g in experiment；Sn-Ni catalyst and raw alcohol mass ratio are 1/30, take 0.75g in experiment；
Reaction carries out in the steel reactor of 60ml, ethyl alcohol, the aqueous solution of normal propyl alcohol and n-butanol, alkali source and catalyst
After slurry reactor kettle is added, seals autoclave body and the 6MPa that builds the pressure hunts leak, replace kettle repeatedly with high-purity hydrogen after confirmation sealing is normal
Interior gas is until air excludes completely in kettle.Reaction initial pressure is 0.1MPa, and reaction temperature is 250 DEG C, speed of agitator
600rpm, reaction duration is for 24 hours.It is cooled to room temperature reaction kettle after reaction, after being centrifuged and being filtered, liquid phase is obtained and consolidates
Phase collects gas phase and liquid product, and stratification obtains organic phase and water phase after liquid product centrifugation, and organic phase primary product is
Higher alcohol.
Embodiment 8
The difference of the present embodiment and embodiment 1 is only that Sn/Ni mass ratio is 1/20, remaining step is all the same.
Comparative example 1
(1) preparation of AlNi alloy phase alloy phase catalyst.
Wherein Al/Ni mass ratio is 1/10.Preparation process uses Al (NO3)3·9H2(20 DEG C) dipping RaneyNi of O room temperature
8h, in 100 DEG C of removing moisture under hydrogen atmosphere protection after the completion of dipping, then in 3000h-1Hydrogen stream in 500 DEG C also
Former 4h obtains AlNi alloy phase catalyst.
(2) preparation of higher alcohol.
Reaction raw materials are the mixed solution of second alcohol and water, wherein ethanol/water mass ratio=1:1, respectively take 15g in experiment；
NaOH is alkali source, and alkali/alcohol molar ratio is 1/25, takes 0.5g in experiment；AlNi alloy phase catalyst and raw alcohol mass ratio are 1/
30,0.5g is taken in experiment；
Reaction carries out in the steel reactor of 60ml, and aqueous solution, alkali source and the AlNi alloy phase catalyst of ethyl alcohol are added
After slurry reactor kettle, seals autoclave body and the 6MPa that builds the pressure hunts leak, replace gas in kettle repeatedly with high-purity hydrogen after confirmation sealing is normal
Body is until air excludes completely in kettle.Reaction initial pressure is 0.1MPa, and reaction temperature is 250 DEG C, speed of agitator 600rpm, instead
Answer duration for 24 hours.It is cooled to room temperature reaction kettle after reaction, after being centrifuged and being filtered, liquid phase and solid phase is obtained, collects gas
It is mutually stood after being centrifuged with liquid product, liquid product without layering, only water phase, oil-free phase higher alcohol generates.
Embodiment 9
Gas-chromatography GC and gas chromatography mass spectrometry GCMS detection raw alcohol is passed through respectively to the organic phase of embodiment 1 to embodiment 7
Conversion ratio, the yield of organic phase, carbon atom number be 5 or more higher alcohol content and carbon atom number be 5 or more isomery alcohol
Content.The results are shown in Table 1.
Table 1 is the Measurement results of embodiment 9
As can be known from the results of Table 1, in embodiment 1 to 8, ethyl alcohol, propyl alcohol and the aqueous solution of butanol all can be mutually catalyzed in alloy
Agent catalysis generate C5+ higher alcohol, C3, C4 alcohol compared to C2 ethyl alcohol be easier occur C-C key be condensed, reaction conversion ratio it is higher and
C5-C16 alcohol selectivity is higher.GCMS analysis is the result shows that its product is mainly carbochain dimerization, trimerization, four poly- and heteromeric growths
Product is branched the statistics of degree calculation shows that wherein the minimum isomery rate of C5+ alcohols is reached as high as up to 89.8% to it respectively
97.8%, that is, the higher alcohol product for reacting generation is mainly the isomery alcohol being branched.In comparative example 1, AlNi alloy is harmonious metallographic
Catalyst only has water phase, and oil-free phase higher alcohol generates.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding
Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of alloy phase catalyst characterized by comprising metal M and W metal, the metal M and the W metal shape
At MNixAlloy phase；
The metal M is Sn, Cu or Mg, then x is respectively 3,1,1.5.
2. alloy phase catalyst according to claim 1, which is characterized in that the specific surface area of the alloy phase catalyst is
40m2/g-60m2/ g, aperture 30nm-80nm, partial size 50nm-100nm.
3. alloy phase catalyst according to claim 1, which is characterized in that the quality of the metal M and the W metal
Than for 1/20-1/2.
4. the preparation method of alloy phase catalyst described in claims 1 to 3 any one, which comprises the following steps:
Moisture will be removed after the salt solution impregnation Raney's nickel powder of M, then carry out in-situ reducing reaction, obtained the alloy and be mutually catalyzed
Agent；
M in the salting liquid of the M is Sn, Cu or Mg.
5. the preparation method according to claim 4, which is characterized in that the time of the dipping is 6h-12h, the dipping
Temperature be 20 DEG C -60 DEG C.
6. the preparation method according to claim 4, which is characterized in that the removing moisture specifically: in a hydrogen atmosphere
100-120 DEG C of removing moisture.
7. the preparation method according to claim 4, which is characterized in that in-situ reducing reaction in hydrogen gas stream into
Row；
The air speed of the reduction reaction is 2000h-1-5000h-1。
8. a kind of method that small molecular alcohol prepares higher alcohol, which comprises the following steps:
By alloy phase catalyst described in the aqueous solution of small molecular alcohol and claims 1 to 3 any one under alkaline condition into
Row reaction, obtains higher alcohol；
The carbon atom number of the small molecular alcohol is 2-4, and the carbon atom number of the higher alcohol is at least 5.
9. according to the method described in claim 8, it is characterized in that, the reaction temperature is 150 DEG C -280 DEG C, when the reaction
Between be 12h-72h, the initial pressure of the reaction is 0.1MPa-2MPa.
10. according to the method described in claim 8, being NaOH or KOH it is characterized in that it provides the alkali source of the alkaline condition；
The molar ratio of the alkali compounds and the small molecular alcohol is 1/25-1/8.
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