CN109794255B - Alloy phase catalyst and preparation method thereof, and method for preparing higher alcohol from micromolecular alcohol - Google Patents
Alloy phase catalyst and preparation method thereof, and method for preparing higher alcohol from micromolecular alcohol Download PDFInfo
- Publication number
- CN109794255B CN109794255B CN201910105480.0A CN201910105480A CN109794255B CN 109794255 B CN109794255 B CN 109794255B CN 201910105480 A CN201910105480 A CN 201910105480A CN 109794255 B CN109794255 B CN 109794255B
- Authority
- CN
- China
- Prior art keywords
- alcohol
- reaction
- alloy phase
- catalyst
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention relates to the technical field of catalysts, in particular to an alloy phase catalyst and a preparation method thereof, and a method for preparing higher alcohol from micromolecular alcohol. The invention discloses an alloy phase catalyst, which comprises: a metal M and a metal Ni, the metal M and the metal Ni forming MNixAn alloy phase; and the metal M is Sn, Cu or Mg, and x is 3, 1 and 1.5 respectively. The catalyst is a heterogeneous catalyst, is easy to separate and recover in the synthesis of higher alcohol by aqueous phase catalysis of small molecular alcohol, and can be recycled after recovery, in addition, the catalyst does not contain noble metals, so that the cost is saved, and the problems that the existing catalyst for preparing higher alcohol is not easy to separate and corrode equipment, and the selectivity to C5+ higher alcohol is low are solved.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an alloy phase catalyst and a preparation method thereof, and a method for preparing higher alcohol from micromolecular alcohol.
Background
Ethanol, as the first developed alcohol-based fuel, has high hygroscopicity, low energy density, and is not transportable by pipelines. And C5+ long-chain higher alcohols such as pentanol and hexanol have the advantages of high energy density, good hydrophobicity, easy separation, easy passivation and the like, can be used as an extracting agent in the fine chemical industry, is also considered as a liquid mixed fuel with high added value, is used as a mixed fuel component to help the fuel to be more complete in combustion, improves the combustion efficiency and reduces the soot emission, can be compatible with the existing mineral energy infrastructure in application, and is an alcohol-based fuel with great potential. At present, higher alcohols are produced mainly based on petrochemical routes. The petrochemical law is that small molecule alcohols can be converted into high molecular weight branched or straight chain alcohols catalyzed by sodium metal alkoxide through Guerbet reaction, but the homogeneous catalyst used in the process has the problems of difficult separation and corrosion of equipment, and the main products are C4 butanol, and the selectivity of C5+ higher alcohol is low.
Disclosure of Invention
The invention provides an alloy phase catalyst, a preparation method thereof and a method for preparing higher alcohol from micromolecular alcohol, and solves the problems that the existing catalyst for preparing higher alcohol is not easy to separate and corrode equipment, and the selectivity to higher alcohol of C5+ is low.
The specific technical scheme is as follows:
the invention provides an alloy phase catalyst, comprising: a metal M and a metal Ni, the metal M and the metal Ni forming MNixAn alloy phase;
the metal M is Sn, Cu or Mg, x is 3, 1 and 1.5 respectively, namely SnNi3CuNi and MgNi1.5Preferably Sn, x is 3.
Preferably, the alloy phase catalyst has a specific surface area of 40 m2/g -60 m2(iv)/g, more preferably 47 m2(ii) a pore diameter of 30 nm to 80 nm, more preferably 50 nm, and a particle diameter of 50 nm to 100 nm, more preferably 80 nm.
In the invention, metal Ni in the alloy phase catalyst is an active component of the catalyst, metal M is an electron assistant, and MNi is formed after reduction activation treatmentxThe alloy phase can effectively control the catalytic dehydrogenation capacity of the Ni active site. The alloy phase catalyst is a solid catalyst, so the solid catalyst can be recovered after being subjected to a catalytic reaction in a water phase, and then being subjected to simple centrifugal filtration and drying. In addition, the alloy phase catalyst provided by the invention is a non-noble metal catalyst, so that the reaction cost is saved.
The invention also provides a preparation method of the alloy phase catalyst, which comprises the following steps:
soaking Raney Ni powder in the salt solution of M, removing water, and carrying out in-situ reduction reaction to obtain the alloy phase catalyst;
m in the salt solution of M is selected from Sn, Cu or Mg, and is preferably Sn.
In the invention, the Raney nickel (Raney Ni) powder is commercially available industrial Raney Ni powder; the salt solution is preferably Cl-，SO4 2-Or NO3-Preferably SnCl4(ii) a The time of the reduction reaction is 3-6h, preferably 4h, and the temperature is 300-500 ℃, preferably 500 ℃.
In the invention, after the alloy phase catalyst is obtained, the water seal method is adopted to protect the catalyst from being oxidized.
Preferably, the mass ratio of M in the alloy phase catalyst to Ni in the Raney Ni is 1/20-1/2, preferably 1/10.
Preferably, the time of the impregnation is 6-12h, preferably 8h, and the temperature of the impregnation is 20-60 ℃, preferably 20 ℃.
Preferably, the water removal is specifically: the water is removed at 100-120 ℃ under a hydrogen atmosphere, preferably at 100 ℃.
Preferably, the in situ reduction reaction is carried out in a hydrogen gas stream;
the space velocity of the reduction reaction is 2000h-1-5000h-1Preferably 3000h-1. In the invention, industrial Raney Ni powder is used as a carrier, the carrier is impregnated and modified by a salt solution of M, and MNi is formed after reduction and activationxThe alloy phase can effectively control the catalytic dehydrogenation capacity of the Ni active site, and the operation is simple.
The invention also provides a method for preparing higher alcohol from small molecular alcohol, which comprises the following steps:
reacting aqueous solution of small molecular alcohol with the alloy phase catalyst under alkaline condition to obtain higher alcohol;
the carbon number of the small molecular alcohol is 2-4, preferably one or more of ethanol, propanol and butanol, more preferably ethanol, n-butanol, n-propanol, a mixture of ethanol and n-butanol, a mixture of n-propanol and n-butanol, and a mixture of ethanol and n-propanol and n-butanol, and the carbon number of the higher alcohol is at least 5, preferably 5-16.
In the present invention, the higher alcohol is preferably an isomeric alcohol having 5 to 16 carbon atoms, which has a higher octane number than a straight-chain alcohol and is more suitable as a high-quality fuel blend.
In the invention, the chain growth of the small molecular alcohol is a multi-step reaction catalyzed by two different catalytic active sites, including alcohol dehydrogenation, aldehyde hydrogenation and aldol condensation reaction. The small molecular alcohol is firstly dehydrogenated under the catalysis of a metal active site of an alloy phase catalyst to generate an aldehyde intermediate, the aldehyde and the alcohol in the system are further catalyzed under an alkaline condition to generate aldol condensation and spontaneous dehydration reaction to realize chain growth, and finally, the long-chain alcohol is generated through hydrogenation, and the reaction is completed under the synergistic catalysis of the alloy phase catalyst and alkali.
In the invention, the small molecular alcohol can be obtained by hydrogenolysis of cellulose, thereby avoiding the additional cost of alcohol separation and purification.
In the invention, the reaction device is a steel reaction kettle of a slurry bed;
before the reaction, the method further comprises the following steps: sealing the steel reaction kettle of the slurry bed, keeping the pressure of the steel reaction kettle at 6MPa for leak detection, and repeatedly replacing gas in the kettle by using high-purity hydrogen after the normal sealing is confirmed until the air in the kettle is completely removed;
after the reaction is finished, the method further comprises the following steps: cooling the steel reactor to room temperature, centrifuging and filtering to obtain a liquid phase and a solid phase, wherein the liquid phase is centrifuged, standing and layering to obtain an organic phase and a water phase as shown in figure 1, the main product in the organic phase is higher alcohol, the water phase is water and unreacted small molecular alcohol and can be continuously recycled, and the solid phase is cleaned and dried to obtain the used alloy phase catalyst. The reaction also produces gaseous hydrogen, methane, carbon dioxide, and the like. The alloy phase catalyst can be recovered only by simple filtration and separation, can be reused after being dried, and has no corrosiveness.
Preferably, the reaction temperature is 150-280 ℃, preferably 250 ℃, the reaction time is 12-72h, preferably 24h, and the initial pressure of the reaction is 0.1-2MPa, preferably 0.1 MPa.
Preferably, the alkaline source providing the alkaline conditions is NaOH or KOH;
the molar ratio of the basic compound to the small molecule alcohol is 1/25-1/8, more preferably 1/25.
According to the technical scheme, the invention has the following advantages:
the invention provides an alloy phase catalyst which is a heterogeneous catalyst, is easy to separate and recover in the synthesis of higher alcohol by catalyzing small molecular alcohol with a water phase, and can be recycled after recovery.
The invention also provides a preparation method of the alloy phase catalyst, the preparation method can obtain the alloy phase catalyst by adopting an impregnation method, the operation is convenient and simple, and the preparation method is suitable for industrial production.
The invention also provides a method for preparing the high alcohol by the small molecular alcohol, the alloy phase catalyst provided by the invention can be used for synthesizing the high alcohol by one-step aqueous phase catalysis of the small molecular alcohol, the small molecular alcohol raw material can be directly prepared into an alcohol aqueous solution, and compared with the traditional alcohol conversion, the method avoids the alcohol separation and purification process with high energy consumption. From experimental data, the main product of the reaction product obtained by catalysis of the catalyst in the organic phase is C5-C16 higher alcohol, and the branching degree is more than 90%. Therefore, the higher isomeric alcohol has higher value compared with small molecular alcohol and non-isomeric higher alcohol, and can be widely used for plasticizers, surfactants, solvents and the like. The higher isomeric alcohol obtained in the invention is more excellent than ethanol as the engine fuel, can be mixed with diesel oil, has high heat value and good hydrophobicity, can effectively reduce the emission of pollutants in the combustion tail gas of the traditional fuel oil, and is a potential engine alternative fuel.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a process flow diagram of a method for preparing higher alcohol from small molecule alcohol according to the present invention.
FIG. 2 shows SnNi provided in embodiment 1 of the present invention3XRD diffraction pattern of alloy phase catalyst (Sn/Ni mass ratio of 1/10);
Detailed Description
The embodiment of the invention provides an alloy phase catalyst, a preparation method thereof and a method for preparing higher alcohol by using small molecular alcohol, which are used for solving the problems that the existing catalyst for preparing higher alcohol is difficult to separate and corrode equipment.
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
（1）SnNi3Preparing an alloy phase catalyst.
Wherein the Sn/Ni mass ratio is 1/10. The preparation process adopts SnCl4Impregnating Raney Ni at room temperature (20 deg.C) for 8h, removing water at 100 deg.C under protection of hydrogen atmosphere, and soaking for 3000h-1Reducing the obtained product for 4 hours at 500 ℃ in hydrogen flow to obtain SnNi3An alloy phase catalyst.
As shown in FIG. 2, the XRD diffraction pattern can determine that SnNi prepared by the embodiment of the invention3An alloy phase catalyst.
(2) And (3) preparing higher alcohol.
The reaction raw materials are mixed solution of ethanol and water, wherein the mass ratio of ethanol to water is =1, and 15g of the mixed solution is taken in each experiment; NaOH is taken as an alkali source, the molar ratio of alkali to alcohol is 1/25, and the experiment is carried out0.5g；SnNi3The mass ratio of the alloy phase catalyst to the raw material alcohol is 1/30, and 0.5g is taken in the experiment;
the reaction is carried out in a 60ml steel reaction kettle, ethanol water solution, alkali source and SnNi3After the alloy phase catalyst is added into a slurry bed reaction kettle, the kettle body is sealed, the pressure is held back for 6MPa leak detection, and after the normal sealing is confirmed, high-purity hydrogen is used for repeatedly replacing the gas in the kettle until the air in the kettle is completely removed. The initial reaction pressure is 0.1MPa, the reaction temperature is 250 ℃, the stirring speed is 600rpm, and the reaction time is 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging and filtering to obtain a liquid phase and a solid phase, collecting gas phase and liquid phase products, centrifuging the liquid phase products, standing and layering to obtain an organic phase and a water phase, wherein the main product of the organic phase is higher alcohol.
Example 2
（1）SnNi3The preparation of the alloy phase catalyst was the same as in example 1.
(2) And (3) preparing higher alcohol.
The reaction raw material is a mixed solution of n-propanol and water, wherein the mass ratio of n-propanol to water is =1, and 15g of the raw material is taken in each experiment; NaOH is taken as an alkali source, the molar ratio of alkali to alcohol is 1/25, and 0.4g is taken in an experiment; the mass ratio of the Sn-Ni catalyst to the raw material alcohol is 1/30, and 0.5g is taken in the experiment;
the reaction is carried out in a 60ml steel reaction kettle, after the aqueous solution of the n-propanol, the alkali source and the catalyst are added into the slurry bed reaction kettle, the kettle body is sealed and leak detection is carried out under the pressure of 6MPa, and after the normal sealing is confirmed, the gas in the kettle is repeatedly replaced by high-purity hydrogen until the air in the kettle is completely removed. The initial reaction pressure is 0.1MPa, the reaction temperature is 250 ℃, the stirring speed is 600rpm, and the reaction time is 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging and filtering to obtain a liquid phase and a solid phase, collecting gas phase and liquid phase products, centrifuging the liquid phase products, standing and layering to obtain an organic phase and a water phase, wherein the main product of the organic phase is higher alcohol.
Example 3
(1) The Sn — Ni alloy phase catalyst was prepared as in example 1.
(2) And (3) preparing higher alcohol.
The reaction raw material is a mixed solution of n-butanol and water, wherein the mass ratio of n-butanol to water is =1, and 15g of the mixed solution is taken in each experiment; NaOH is taken as an alkali source, the molar ratio of alkali to alcohol is 1/25, and 0.33g is taken in an experiment; the mass ratio of the Sn-Ni catalyst to the raw material alcohol is 1/30, and 0.5g is taken in the experiment;
the reaction is carried out in a 60ml steel reaction kettle, after the aqueous solution of the n-butyl alcohol, the alkali source and the catalyst are added into the slurry bed reaction kettle, the kettle body is sealed and leak detection is carried out under the pressure of 6MPa, and after the normal sealing is confirmed, the gas in the kettle is repeatedly replaced by high-purity hydrogen until the air in the kettle is completely removed. The initial reaction pressure is 0.1MPa, the reaction temperature is 250 ℃, the stirring speed is 600rpm, and the reaction time is 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging and filtering to obtain a liquid phase and a solid phase, collecting gas phase and liquid phase products, centrifuging the liquid phase products, standing and layering to obtain an organic phase and a water phase, wherein the main product of the organic phase is higher alcohol.
Example 4
(1) The Sn — Ni alloy phase catalyst was prepared as in example 1.
(2) And (3) preparing higher alcohol.
The reaction raw material is a mixed solution of ethanol, n-propanol and water, wherein the mass ratio of the ethanol to the n-propanol to the water is 1:1:1, and in the experiment, 10g of each of the ethanol, the n-propanol and the water is taken; NaOH is taken as an alkali source, the molar ratio of alkali to alcohol is 1/25, and 0.61g is taken in an experiment; the mass ratio of the Sn-Ni catalyst to the raw material alcohol is 1/30, and 0.67g is taken in the experiment;
the reaction is carried out in a 60ml steel reaction kettle, after the aqueous solution of ethanol and n-propanol, an alkali source and a catalyst are added into the slurry bed reaction kettle, the kettle body is sealed and leak detection is carried out under the pressure of 6MPa, and after the normal sealing is confirmed, the gas in the kettle is repeatedly replaced by high-purity hydrogen until the air in the kettle is completely removed. The initial reaction pressure is 0.1MPa, the reaction temperature is 250 ℃, the stirring speed is 600rpm, and the reaction time is 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging and filtering to obtain a liquid phase and a solid phase, collecting gas phase and liquid phase products, centrifuging the liquid phase products, standing and layering to obtain an organic phase and a water phase, wherein the main product of the organic phase is higher alcohol.
Example 5
(1) The Sn — Ni alloy phase catalyst was prepared as in example 1.
(2) And (3) preparing higher alcohol.
The reaction raw material is a mixed solution of ethanol, n-butanol and water, wherein the mass ratio of the ethanol to the n-butanol to the water is 1:1:1, and in the experiment, 10g of the ethanol, the n-butanol and the water are respectively taken; NaOH is taken as an alkali source, the molar ratio of alkali to alcohol is 1/25, and 0.56g is taken in an experiment; the mass ratio of the Sn-Ni catalyst to the raw material alcohol is 1/30, and 0.67g is taken in the experiment;
the reaction is carried out in a 60ml steel reaction kettle, after the aqueous solution of ethanol and n-butanol, an alkali source and a catalyst are added into the slurry bed reaction kettle, the kettle body is sealed and leak detection is carried out under the pressure of 6MPa, and after the normal sealing is confirmed, the gas in the kettle is repeatedly replaced by high-purity hydrogen until the air in the kettle is completely removed. The initial reaction pressure is 0.1MPa, the reaction temperature is 250 ℃, the stirring speed is 600rpm, and the reaction time is 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging and filtering to obtain a liquid phase and a solid phase, collecting gas phase and liquid phase products, centrifuging the liquid phase products, standing and layering to obtain an organic phase and a water phase, wherein the main product of the organic phase is higher alcohol.
Example 6
(1) The Sn — Ni alloy phase catalyst was prepared as in example 1.
(2) And (3) preparing higher alcohol.
The reaction raw material is a mixed solution of n-propanol, n-butanol and water, wherein the mass ratio of the n-propanol to the n-butanol to the water is 1:1:1, and 10g of the n-propanol, the n-butanol and the water are taken in an experiment respectively; NaOH is taken as an alkali source, the molar ratio of alkali to alcohol is 1/25, and 0.48g is taken in an experiment; the mass ratio of the Sn-Ni catalyst to the raw material alcohol is 1/30, and 0.67g is taken in the experiment;
the reaction is carried out in a 60ml steel reaction kettle, after the aqueous solution of the n-propyl alcohol and the n-butyl alcohol, an alkali source and a catalyst are added into the slurry bed reaction kettle, the kettle body is sealed, the pressure is held back for 6MPa leak detection, and after the sealing is confirmed to be normal, the gas in the kettle is repeatedly replaced by high-purity hydrogen until the air in the kettle is completely removed. The initial reaction pressure is 0.1MPa, the reaction temperature is 250 ℃, the stirring speed is 600rpm, and the reaction time is 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging and filtering to obtain a liquid phase and a solid phase, collecting gas phase and liquid phase products, centrifuging the liquid phase products, standing and layering to obtain an organic phase and a water phase, wherein the main product of the organic phase is higher alcohol.
Example 7
(1) The Sn — Ni alloy phase catalyst was prepared as in example 1.
(2) And (3) preparing higher alcohol.
The reaction raw material is a mixed solution of ethanol, n-propanol, n-butanol and water, wherein the mass ratio of the ethanol to the n-propanol to the n-butanol to the water is 1:1:1:1, and in the experiment, 7.5g of the ethanol to the n-propanol to the n-butanol to the water is taken respectively; NaOH is taken as an alkali source, the molar ratio of alkali to alcohol is 1/25, and 0.62g is taken in an experiment; the mass ratio of the Sn-Ni catalyst to the raw material alcohol is 1/30, and 0.75g is taken in the experiment;
the reaction is carried out in a 60ml steel reaction kettle, after the aqueous solution of ethanol, n-propanol and n-butanol, an alkali source and a catalyst are added into a slurry bed reaction kettle, the kettle body is sealed, the pressure is held back for 6MPa leakage detection, and after the sealing is confirmed to be normal, high-purity hydrogen is used for repeatedly replacing the gas in the kettle until the air in the kettle is completely removed. The initial reaction pressure is 0.1MPa, the reaction temperature is 250 ℃, the stirring speed is 600rpm, and the reaction time is 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging and filtering to obtain a liquid phase and a solid phase, collecting gas phase and liquid phase products, centrifuging the liquid phase products, standing and layering to obtain an organic phase and a water phase, wherein the main product of the organic phase is higher alcohol.
Example 8
This example differs from example 1 only in that the Sn/Ni mass ratio is 1/20, and the rest of the steps are the same.
Comparative example 1
(1) Preparing the AlNi alloy phase catalyst.
Wherein the Al/Ni mass ratio is 1/10. The preparation process adopts Al (NO)3)3·9H2Soaking Raney Ni in O at room temperature (20 deg.C) for 8h, removing water at 100 deg.C under protection of hydrogen atmosphere, and soaking for 3000h-1Reducing the obtained product for 4 hours at 500 ℃ in hydrogen flow to obtain the AlNi alloy phase catalyst.
(2) And (3) preparing higher alcohol.
The reaction raw material is a mixed solution of ethanol and water, wherein the mass ratio of ethanol to water is = 1:1, taking 15g of each sample in the experiment; NaOH is taken as an alkali source, the molar ratio of alkali to alcohol is 1/25, and 0.5g is taken in an experiment; the mass ratio of the AlNi alloy phase catalyst to the raw material alcohol is 1/30, and 0.5g is taken in the experiment;
the reaction is carried out in a 60ml steel reaction kettle, after the aqueous solution of ethanol, an alkali source and an AlNi alloy phase catalyst are added into the slurry bed reaction kettle, the kettle body is sealed and leak detection is carried out under the pressure of 6MPa, and after the normal sealing is confirmed, the gas in the kettle is repeatedly replaced by high-purity hydrogen until the air in the kettle is completely removed. The initial reaction pressure is 0.1MPa, the reaction temperature is 250 ℃, the stirring speed is 600rpm, and the reaction time is 24 hours. After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging and filtering to obtain a liquid phase and a solid phase, collecting gas phase and liquid phase products, centrifuging the liquid phase products, standing the liquid phase products without layering, and only generating water phase and no oil phase higher alcohol.
Example 9
The organic phases of examples 1 to 7 were examined for conversion of the raw material alcohol, yield of the organic phase, content of higher alcohol having 5 or more carbon atoms and content of isomeric alcohol having 5 or more carbon atoms by gas chromatography GC and mass-coupled GCMS, respectively. The results are shown in Table 1.
Table 1 shows the results of the test analysis of example 9
From the results in table 1, it is clear that in examples 1 to 8, all of the aqueous solutions of ethanol, propanol and butanol can be catalyzed by the alloy phase catalyst to form C5+ higher alcohols, C3 and C4 alcohols are more likely to undergo C-C bond condensation than C2 ethanol, the reaction conversion rate is higher, and the selectivity of C5-C16 alcohols is higher. GCMS analysis results show that the product is mainly a product with carbon chain dimerization, trimerization, tetramerization and heteropolymerization growth, and statistical calculation of the branching degree of the product respectively shows that the minimum isomerization rate of C5+ alcohol is 89.8 percent and the maximum isomerization rate is 97.8 percent, namely the higher alcohol product generated by the reaction is mainly branched isomeric alcohol. In comparative example 1, the AlNi alloy phase catalyst had only an aqueous phase and no oil phase higher alcohols were produced.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing higher alcohol from small molecular alcohol is characterized by comprising the following steps:
reacting aqueous solution of small molecular alcohol with an alloy phase catalyst under an alkaline condition to obtain higher alcohol;
the number of carbon atoms of the small molecular alcohol is 2-4, and the number of carbon atoms of the higher alcohol is at least 5;
the alloy phase catalyst includes: a metal M and a metal Ni, the metal M and the metal Ni forming MNixAn alloy phase;
the metal M is Sn, Cu or Mg, and x is 3, 1 and 1.5 respectively;
the MNixThe alloy phase is prepared by adopting a dipping in-situ reduction method.
2. The method of claim 1, wherein the mass ratio of the metal M to the metal Ni is 1/20-1/2.
3. The method according to any one of claims 1 or 2, wherein the preparation of the alloy phase catalyst comprises the steps of:
soaking Raney nickel powder in the salt solution of M, removing water, and carrying out in-situ reduction reaction to obtain the alloy phase catalyst;
and M in the salt solution of M is Sn, Cu or Mg.
4. The method according to claim 3, wherein the time of the impregnation is 6h to 12h and the temperature of the impregnation is 20 ℃ to 60 ℃.
5. The method according to claim 3, characterized in that said removing of water is in particular: the water was removed at 100-120 ℃ under a hydrogen atmosphere.
6. The method of claim 3, wherein the in situ reduction reaction is carried out in a hydrogen gas stream;
the space velocity of the reduction reaction is 2000h-1-5000h-1。
7. The method according to claim 1, wherein the reaction temperature is 150 ℃ to 280 ℃, the reaction time is 12h to 72h, and the initial pressure of the reaction is 0.1MPa to 2 MPa.
8. The method of claim 1, wherein the alkali source providing the alkaline conditions is NaOH or KOH;
the molar ratio of the basic compound to the small molecule alcohol is 1/25-1/8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910105480.0A CN109794255B (en) | 2019-02-01 | 2019-02-01 | Alloy phase catalyst and preparation method thereof, and method for preparing higher alcohol from micromolecular alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910105480.0A CN109794255B (en) | 2019-02-01 | 2019-02-01 | Alloy phase catalyst and preparation method thereof, and method for preparing higher alcohol from micromolecular alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109794255A CN109794255A (en) | 2019-05-24 |
| CN109794255B true CN109794255B (en) | 2022-05-10 |
Family
ID=66561934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910105480.0A Active CN109794255B (en) | 2019-02-01 | 2019-02-01 | Alloy phase catalyst and preparation method thereof, and method for preparing higher alcohol from micromolecular alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109794255B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1456369A (en) * | 1972-11-30 | 1976-11-24 | Stamicarbon | Catalyst preparation |
| CN104884159A (en) * | 2012-12-19 | 2015-09-02 | 国际人造丝公司 | Catalysts and processes for producing butanol |
| WO2016078261A1 (en) * | 2014-11-20 | 2016-05-26 | 北京化工大学 | Supported high dispersion nickel-based alloy catalyst preparation method and catalytic application thereof |
| CN106242991A (en) * | 2016-08-03 | 2016-12-21 | 江苏大学 | A kind of method of synthesis 3 amino 4 p-methoxyacetanilides |
| CN107445995A (en) * | 2017-08-08 | 2017-12-08 | 清华大学 | The method that a kind of new manganese catalysis ethanol condensation prepares butanol |
| CN108355661A (en) * | 2018-01-03 | 2018-08-03 | 东南大学 | A kind of threadiness Cu-Ni alloy nanometer crystals and its synthetic method |
-
2019
- 2019-02-01 CN CN201910105480.0A patent/CN109794255B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1456369A (en) * | 1972-11-30 | 1976-11-24 | Stamicarbon | Catalyst preparation |
| CN104884159A (en) * | 2012-12-19 | 2015-09-02 | 国际人造丝公司 | Catalysts and processes for producing butanol |
| WO2016078261A1 (en) * | 2014-11-20 | 2016-05-26 | 北京化工大学 | Supported high dispersion nickel-based alloy catalyst preparation method and catalytic application thereof |
| CN106242991A (en) * | 2016-08-03 | 2016-12-21 | 江苏大学 | A kind of method of synthesis 3 amino 4 p-methoxyacetanilides |
| CN107445995A (en) * | 2017-08-08 | 2017-12-08 | 清华大学 | The method that a kind of new manganese catalysis ethanol condensation prepares butanol |
| CN108355661A (en) * | 2018-01-03 | 2018-08-03 | 东南大学 | A kind of threadiness Cu-Ni alloy nanometer crystals and its synthetic method |
Non-Patent Citations (1)
| Title |
|---|
| Raney Ni-Sn Catalyst for H2 Production from Biomass-Derived Hydrocarbons;G. W. Huber et al.;《Science》;20030627;第300卷(第5628期);Supplementary Online Material * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109794255A (en) | 2019-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113145155B (en) | Nitrogen-doped carbon-coated nickel catalyst applied to assembly of bioethanol to synthesize high-carbon alcohol and preparation method thereof | |
| CN110102309B (en) | NiSn composite nano catalyst, preparation method and application thereof | |
| CN107304367B (en) | Preparation method of branched alkane in range of gasoline, aviation kerosene or diesel oil | |
| CN101565353B (en) | Preparation method for 2-propyl enanthol | |
| CN110538669B (en) | Copper-cobalt metal carbide catalyst for preparing oxygen-containing chemicals from synthesis gas and preparation method thereof | |
| CN104815659A (en) | Iron-based catalyst used for Fischer-Tropsch synthesis, preparation method and application | |
| CN113385171A (en) | Metal-based catalyst protected by few-layer carbon and application thereof in ethylene oxide carbonylation | |
| CN101747152B (en) | Citral liquid-phase hydrogenation method for synthesizing unsaturated alcohols | |
| CN102091629A (en) | Catalyst for methanation of carbon dioxide | |
| RU2446010C2 (en) | Method of producing hydrogen via direct decomposition of natural gas and lpg | |
| CN109794255B (en) | Alloy phase catalyst and preparation method thereof, and method for preparing higher alcohol from micromolecular alcohol | |
| WO2012134493A1 (en) | Catalysts for the conversion of synthesis gas to alcohols | |
| WO2012134492A1 (en) | Catalysts for the conversion of synthesis gas to alcohols | |
| CN111215079B (en) | Method for preparing alcohol by hydrogenation of aldehydes by adopting nickel-based heterogeneous catalyst | |
| EP3023479A1 (en) | Process for the deoxygenation of alcohols and use thereof | |
| Bratt | Catalytic CO2 Hydrogenation-Literature Review: Technology Development since 2014 | |
| Zhang et al. | Chemoselective transfer hydrogenation of cinnamaldehyde over activated charcoal supported Pt/Fe3O4 catalyst | |
| JP2008019176A (en) | Method for synthesizing methanol and dimethyl ether | |
| CN110590860B (en) | Method for preparing lignin oligomer by selective reductive degradation | |
| CN114522738A (en) | Method for preparing 1, 3-propylene glycol from 3-acetoxy propionaldehyde through one-step hydrogenation | |
| Gahtori et al. | Advances in Direct Thermocatalytic CO 2 Conversion to Chemicals and Hydrocarbons | |
| JP4845530B2 (en) | Methanol synthesis catalyst, method for producing the catalyst, and method for producing methanol | |
| CN113713817B (en) | Method for preparing n-propanol by catalyzing propanal hydrogenation by nickel-based catalyst | |
| CN110079355B (en) | Aviation fuel oil synthesized by methyl isobutyl ketone aldol condensation and synthesis method | |
| CN112892543B (en) | Catalyst for co-production of synthetic gas oil and alcohol and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |