CN110292930B - Catalyst for preparing 1, 4-butylene glycol by hydrogenation of 1, 4-butynediol and preparation method and application thereof - Google Patents

Catalyst for preparing 1, 4-butylene glycol by hydrogenation of 1, 4-butynediol and preparation method and application thereof Download PDF

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CN110292930B
CN110292930B CN201810237052.9A CN201810237052A CN110292930B CN 110292930 B CN110292930 B CN 110292930B CN 201810237052 A CN201810237052 A CN 201810237052A CN 110292930 B CN110292930 B CN 110292930B
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catalyst
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butynediol
hydrogenation
transition metal
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CN110292930A (en
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张晓昕
王宣
慕旭宏
宗保宁
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0081—Preparation by melting
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds

Abstract

The invention relates to a catalyst for preparing 1, 4-butylene glycol by hydrogenating 1, 4-butynediol, a preparation method and application thereof, wherein the catalyst is porous amorphous alloy; the catalyst contains 40-95 wt% of nickel, 0.5-50 wt% of silicon and no more than 20 wt% of transition metal calculated by elements and based on the weight of the catalyst, wherein the transition metal is at least one element selected from the group consisting of elements in IB group, IIB group, IIIB group, IVB group, VIB group, VIIB group and VIII group. When the catalyst provided by the invention is applied to hydrogenation of 1, 4-butynediol to prepare 1, 4-butenediol, the selectivity of the 1, 4-butenediol is high.

Description

Catalyst for preparing 1, 4-butylene glycol by hydrogenation of 1, 4-butynediol and preparation method and application thereof
Technical Field
The invention relates to a catalyst for preparing 1, 4-butylene glycol by hydrogenating 1, 4-butynediol, a preparation method and application thereof.
Background
1, 4-butylene glycol (BED) is an important chemical raw material, is mainly used as a plasticizer of alkyd resin, a cross-linking agent of synthetic resin, a bactericide and the like, is an important intermediate for synthesizing N-methyl pyrrolidone, and can also be used for preparing nylon, medical products and the like.
There have been many studies and reports on selective hemihydrogenation of alkynes and alkyne derivatives (i.e., requiring the product to stay selectively in the alkene phase) for a long time. Heretofore, it has been recognized that Lindlar catalysts work best and are most widely used, but Lindlar catalysts have a short life and are deactivated in the same batch only 1-2 times. Recently, the research finds that the macromolecular carrier palladium complex catalyst can be effectively applied to alkyne selective semi-hydrogenation reaction through proper poisoning, and the service life of the macromolecular carrier palladium complex catalyst is 4-5 times that of the Lindlar catalyst. For example, Zn, microorganisms and other activity inhibitors are often used in the literature to reduce the hydrogenation activity of noble metal catalysts for alkyne selective hemihydrogenation reactions. However, these methods are complicated, and the additives used not only have toxic and polluting products, but also increase the cost; the obtained catalytic material can improve the selectivity of the enol, but the reaction condition is strictly controlled to obtain a partial hydrogenation product with higher yield. The use of Lindlar catalysts as semi-hydrogenation catalysts for the production of olefin products has remained in the laboratory.
Catalysts for the selective catalytic hydrogenation of 1, 4-butynediol to 1, 4-butenediol include Pd-based and Ni-based catalysts. The supported Pd-based catalyst has high hydrogenation activity on 1, 4-butynediol, but has low selectivity on intermediate product butenediol, and the high selectivity on the butenediol is realized mainly by adding one or more toxic auxiliary agents such as Cu, Zn, Pb, Ca, Cd, Ga and the like or introducing organic substances such as pyridine, quinine and the like to poison the Pd-based catalyst. However, these measures lead to the agglomeration of Pd catalyst particles and thus to the deactivation of the catalyst, thereby significantly reducing the hydrogenation activity of 1, 4-butynediol of the catalyst, and furthermore, in order to obtain high purity 1, 4-butenediol for use in the fields of fine chemical engineering and medicine, the toxic auxiliary agents added to the catalyst must be completely removed, increasing the process difficulty and greatly increasing the operating costs. The Ni-based catalyst is commonly used for producing 1, 4-butanediol by hydrogenation of 1, 4-butynediol, the activity and the selectivity of the Ni-based catalyst are reduced due to the fact that the structure and the performance of the Ni-based catalyst are easy to change in the hydrogenation process, and meanwhile, the traditional 1, 4-butynediol hydrogenation process using the Ni-based catalyst as the catalyst needs high temperature and high pressure and easily forms byproducts.
Currently, the 1, 4-butylene glycol industrial product is not prepared by a process route adopting a Lindlar catalyst, but is basically derived from a 1, 4-butylene glycol product production process. 1, 4-Butanediol (BDO) is an important basic organic chemical and fine chemical raw material and is widely used in the aspects of solvents, medicines, plasticizers, curing agents, pesticides, rust removers, artificial leather, fibers, engineering pigments and the like. One route for producing 1, 4-butanediol is the Reppe method. The Reppe method was successfully developed in 1930 by W.Reppe et al, Farben, Germany, and was pioneered in 1940 by Pasff, Germany for industrial production. Acetylene and formaldehyde are used as raw materials, 1, 4-butynediol is synthesized by acetylene and formaldehyde under the action of a copper catalyst, and the 1, 4-butynediol is hydrogenated to generate 1, 4-butanediol.
The commercial implementation of butynediol hydrogenation to butanediol in the known Reppe process is essentially a two-stage process. The specific process for producing 1, 4-butanediol by using 1, 4-butynediol through a two-step method comprises the following steps: the first-stage hydrogenation is carried out in a suspension bed reactor or a fixed bed reactor, and respectively adopts Raney Ni, modified Raney Ni or a cobalt-aluminum catalyst prepared by a precipitation method, and the second-stage hydrogenation is carried out in the fixed bed reactor and adopts the cobalt-aluminum catalyst.
For example, U.S. Pat. No. 3,34, 445 discloses a low-pressure, high-pressure combined process for the hydrogenation of butynediol to l, 4-butanediol using Raney Ni catalyst in the low-pressure hydrogenation zone at an operating temperature of from 50 to 60 ℃. And the hydrogenation pressure of the fixed bed in the second section is between 13.7MPa and 21.64MPa, which causes the hydrogenation pressure in the second section to be too high and the power consumption to be too large.
U.S. Pat. No. 2,143,93 introduces 3-25% Mo into Raney Ni catalyst to obtain Mo modified catalyst, which is applied in slurry bed reactor to hydrogenate butynediol at 20-140 deg.C and 0-2MPa to obtain 1, 4-butanediol product.
German patent BE745225(GB1242358A) reports an atypical Raney Ni catalyst which is obtained by incomplete alkali treatment of a 35-60% Ni/40-65% Al alloy to obtain a catalyst with a residual Al fraction. The existence of Al in the catalyst enables the catalyst to have extremely high mechanical strength, and the catalyst is applied to a high-temperature and high-pressure fixed bed reactor.
These processes for producing 1, 4-butanediol using Ni as catalyst employ high pressure reaction processes and the 1, 4-butenediol as intermediate product has a very low selectivity, for example, 1, 4-butenediol selectivity is below 5% during the two-step process mentioned in German patent BE 745225. In the known low-pressure hydrogenation process, due to poor Raney Ni selectivity, a large amount of butanediol acetal product condensed aldehyde and butylene glycol isomeric product hydroxybutyraldehyde exist, the purity of 1, 4-butanediol is greatly influenced by the existence of the byproducts, and a plurality of refining and separating processes are required to remove the impurities, so that the cost of industrial production is increased. Therefore, in all of these processes for producing 1, 4-butanediol, it is difficult to obtain a 1, 4-butanediol product with high purity, and the existing hydrogenation catalysts have many disadvantages.
Disclosure of Invention
The invention aims to provide a catalyst for preparing 1, 4-butylene glycol by hydrogenating 1, 4-butynediol, a preparation method and an application thereof.
In order to achieve the above object, the present invention provides a catalyst for preparing 1, 4-butenediol by hydrogenating 1, 4-butynediol, wherein the catalyst is a porous amorphous alloy; the catalyst contains 40-95 wt% of nickel, 0.5-50 wt% of silicon and no more than 20 wt% of transition metal calculated by elements and based on the weight of the catalyst, wherein the transition metal is at least one element selected from the group consisting of IB group, IIB group, IIIB group, IVB group, VIB group, VIIB group and VIII group.
Optionally, the catalyst contains 55-90 wt% nickel, 0.5-30 wt% silicon, and 0.1-15 wt% transition metal, calculated on an elemental basis and based on the weight of the catalyst.
Optionally, the catalyst comprises 70-90 wt% nickel, 5-20 wt% silicon, and 0.5-10 wt% transition metal, calculated as elements and based on the weight of the catalyst.
Optionally, the transition metal is at least one selected from iron, copper, cobalt, molybdenum, tungsten, cerium, titanium, zirconium, chromium, platinum, ruthenium, and palladium.
Optionally, the transition metal is at least one selected from molybdenum, ruthenium, iron, cobalt, and platinum.
The invention also provides a preparation method of the provided catalyst, which comprises the following steps:
mixing and melting nickel and silicon or mixing and melting nickel, silicon and transition metal, and carrying out quenching treatment on the obtained mixed molten liquid to obtain quenched alloy;
and (3) extracting and desiliconizing the quenched alloy by adopting alkali liquor to obtain the catalyst.
Optionally, the quenching process comprises: spraying the mixed molten liquid onto a copper roller which is 600-DEG C1000 revolutions per minute and is filled with cooling water, cooling the mixed molten liquid at the cooling speed of 1000-DEG C1600 ℃/second and throwing the mixed molten liquid along the tangent line of the copper roller, and crushing the obtained flaky strip alloy to be less than 2000 microns to obtain the quenched alloy; or the quenching process comprises: and carrying out atomization, spray, deposition and cooling on the mixed molten liquid at the temperature higher than 1300 ℃ to obtain the quenched alloy.
Optionally, the conditions of the extraction desilication include: the temperature is 10-100 ℃, the time is 5-600 minutes, the alkali in the alkali liquor is at least one of barium hydroxide, sodium hydroxide and potassium hydroxide, the concentration of the alkali liquor is 2-40 wt%, and the weight ratio of the quenched alloy to the alkali in the alkali liquor is 1: (1-10).
The invention also provides a hydrogenation method of 1, 4-butynediol, which comprises the following steps: 1, 4-butynediol is contacted with the catalyst provided by the invention in a hydrogenation reactor and subjected to hydrogenation treatment to obtain 1, 4-butenediol.
Optionally, the hydrotreating is carried out in the presence or absence of a solvent, the solvent being water, methanol, ethanol or propanol, the weight ratio of the solvent to 1, 4-butynediol being 1: (0.05-5);
the hydrotreating conditions include: the reaction temperature is 30-150 ℃, the hydrogen pressure is 0.1-10 MPa, and the reaction time is 1-500 minutes; the concentration of the catalyst is 0.01-20 wt% based on the total weight of the catalyst, solvent and 1, 4-butynediol;
the hydrogenation reactor is at least one selected from a slurry bed reactor, a kettle type reactor and a fluidized bed reactor.
Optionally, the hydrotreating conditions include: the reaction temperature is 40-90 ℃, the hydrogen pressure is 0.3-8 MPa, and the reaction time is 60-200 minutes; the catalyst is present in a concentration of 0.5 to 8 weight percent, based on the total weight of catalyst, solvent and 1, 4-butynediol.
The catalyst provided by the invention can be applied to the one-step preparation of 1, 4-butylene glycol from 1, 4-butynediol under the conditions of low temperature and low pressure, and has high catalyst activity and good selectivity of 1, 4-butylene glycol.
In addition, the hydrogenation method can adopt water as a solvent, can avoid using toxic organic reagents, and is environment-friendly.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a catalyst for preparing 1, 4-butylene glycol by hydrogenating 1, 4-butynediol, which is a porous amorphous alloy; the catalyst contains 40-95 wt% of nickel, 0.5-50 wt% of silicon and no more than 20 wt% of transition metal calculated by elements and based on the weight of the catalyst, wherein the transition metal is at least one element selected from the group consisting of elements in IB group, IIB group, IIIB group, IVB group, VIB group, VIIB group and VIII group. When the catalyst provided by the invention is used for preparing 1, 4-butylene glycol by hydrogenating 1, 4-butynediol, the selectivity of 1, 4-butylene glycol is high.
According to the present invention, the catalyst preferably contains 55 to 90% by weight of nickel, 0.5 to 30% by weight of silicon and 0.1 to 15% by weight of a transition metal, further preferably 70 to 90% by weight of nickel, 5 to 20% by weight of silicon and 0.5 to 10% by weight of a transition metal, further preferably 75 to 88% by weight of nickel, 10 to 18% by weight of silicon and 0.5 to 7% by weight of a transition metal, calculated as elements and based on the weight of the catalyst.
The present invention may optionally use the above transition metal as a component of the catalyst, and the transition metal is preferably at least one selected from the group consisting of iron, copper, cobalt, molybdenum, tungsten, cerium, titanium, zirconium, chromium, platinum, ruthenium and palladium, more preferably at least one selected from the group consisting of molybdenum, ruthenium, iron, cobalt, cerium, titanium, zirconium, chromium, platinum and palladium, and further preferably at least one selected from the group consisting of molybdenum, ruthenium, iron, cobalt and platinum.
The invention also provides a preparation method of the provided catalyst, which comprises the following steps: mixing and melting nickel and silicon or mixing and melting nickel, silicon and transition metal, and carrying out quenching treatment on the obtained mixed molten liquid to obtain quenched alloy; and (3) extracting and desiliconizing the quenched alloy by adopting alkali liquor to obtain the catalyst. The catalyst prepared by the method has good activity, selectivity and stability.
In the present invention, the quenching process is well known to those skilled in the art, and means that the mixed melt is cooled at a rate of more than 1000 ℃/sec to form an amorphous alloy. For example, the quenching process may include: and spraying the mixed molten liquid onto a copper roller which is 600-DEG c/min and is filled with cooling water, cooling the mixed molten liquid at the cooling speed of 1000-DEG c/sec and throwing the mixed molten liquid along the tangent line of the copper roller, and crushing the obtained flaky strip alloy to less than 2000 microns, preferably to 8-400 meshes, further preferably to 40-200 meshes to obtain the quenched alloy. The copper roller can be a single roller or a double roller. The quenching process may also include: and carrying out atomization spray deposition cooling on the mixed molten liquid at the temperature higher than 1300 ℃ to obtain the quenched alloy, wherein the manner of atomization spray deposition cooling is well known by the person skilled in the art, and the details of the invention are not repeated.
In the present invention, extraction desilication refers to dissolving a part of silicon element in the quenched alloy with alkali solution to form a porous alloy, for example, the conditions of extraction desilication may include: the temperature is 10-100 ℃, preferably 40-90 ℃, the time is 5-600 minutes, preferably 30-120 minutes, the alkali in the alkali liquor can be soluble strong alkali, such as one or more of alkali metal and alkaline earth metal hydroxides, specifically at least one selected from barium hydroxide, sodium hydroxide and potassium hydroxide, preferably sodium hydroxide and/or potassium hydroxide, the concentration of the alkali liquor is 2-40 wt%, preferably 10-20 wt%, and the weight ratio of the alloy after quenching to the alkali in the alkali liquor is 1: (1-10), preferably 1: (1.5-4), washing the product obtained by the extraction and desilication with water until the pH value of the washing liquid is 8-10 to obtain the catalyst.
The invention also provides a hydrogenation method of 1, 4-butynediol, which comprises the following steps: 1, 4-butynediol is hydrogenated and is contacted with the catalyst provided by the invention in a hydrogenation reactor for hydrogenation treatment, and 1, 4-butenediol is obtained.
Hydrotreating is well known to those skilled in the art in light of the present disclosure and will not be described in detail herein. The hydrotreatment according to the invention can be carried out in the presence or absence of a solvent, preferably in the presence of a solvent, which can be an organic solvent such as methanol, ethanol or propanol or water, preferably water, and the weight ratio of the solvent to 1, 4-butynediol can be 1: (0.05-5), and the solvent can be used singly or in combination.
The hydrotreatment of the invention can be carried out under conventional conditions, preferably at mildly low temperature and pressure, for example, the hydrotreatment conditions can include: the reaction temperature is 30-150 ℃, preferably 40-90 ℃, the hydrogen pressure is 0.1-10 MPa, preferably 0.3-8 MPa, further preferably 2-5 MPa, the reaction time is 1-500 minutes, preferably 60-200 minutes, further preferably 100-150 minutes; the concentration of the catalyst is 0.01 to 20 wt.%, preferably 0.5 to 8 wt.%, based on the total weight of catalyst, solvent and 1, 4-butynediol.
According to the present invention, the hydrogenation reactor may be various existing reactors, for example, at least one selected from a slurry bed reactor, a tank reactor and a fluidized bed reactor, preferably a tank reactor or a fluidized bed reactor. The slurry bed reactor refers to a container for suspending solid catalyst particles in a reaction liquid material for reaction, such as a mechanical stirred tank, a gas stirred tank, and a liquid-phase suspended bed reactor for suspending a solid catalyst in a reaction container by liquid flow, and the slurry bed reactor can be a single reactor or a plurality of reactors connected in series or in parallel. The fluidized bed reactor can be a plug flow reactor, a bubbling reactor or a magnetic stabilization bed reactor, and the like, and the kettle reactor can be a batch kettle reactor.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto.
In the following examples, all reagents used were commercially available reagents unless otherwise specified.
In the following examples, the pressures are gauge pressures unless otherwise specified.
In the following examples, the composition of the liquid phase mixture obtained by the reaction was measured by a gas chromatograph including an FID detector, and quantified by a calibration normalization method, and the conversion of 1, 4-butynediol and the selectivity of 1, 4-butenediol were calculated by the following formulas:
Figure BDA0001604258950000071
Figure BDA0001604258950000081
in the following examples, the contents of the respective components in the catalyst were measured by plasma emission spectroscopy (ICP).
Examples 1-6 illustrate the catalysts and methods of making the same provided by the present invention.
Example 1
Adding 1.5kg of nickel, 1.5kg of silicon and 0.2kg of molybdenum into a graphite crucible, heating the graphite crucible in a high-frequency furnace to be molten, then spraying a mixed molten liquid onto a copper roller with the rotating speed of 900 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the molten liquid at the cooling speed of 1000-1600 ℃/second, throwing the molten liquid out along the tangent line of the copper roller to form a scaly strip alloy, and grinding the scaly strip alloy until the particle diameter is less than 70 micrometers to obtain the quenched alloy. 50g of the quenched alloy was slowly charged into a three-necked flask containing 500 g of a 20% by weight aqueous solution of sodium hydroxide, and the temperature was controlled to 80 ℃ and stirred at a constant temperature for 1 hour. After stopping heating and stirring, the liquid was decanted and washed with distilled water at 90 ℃ to a pH of 7. The catalyst obtained was identified by the number of catalyst-1, and the composition of catalyst-1 is shown in Table 1.
Example 2
Adding 1.5kg of nickel, 1.5kg of silicon and 0.01kg of ruthenium into a graphite crucible, heating the graphite crucible in a high-frequency furnace to be molten, then spraying the mixed molten liquid onto a copper roller with the rotating speed of 900 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the molten liquid at the cooling speed of 1000-1600 ℃/second, then throwing the molten liquid out along the tangent line of the copper roller to form a scaly strip alloy, and grinding the scaly strip alloy until the particle diameter is below 70 micrometers to obtain the quenched alloy. 50g of the quenched alloy was slowly charged into a three-necked flask containing 500 g of a 20% by weight aqueous solution of sodium hydroxide, and the temperature was controlled to 80 ℃ and stirred at a constant temperature for 1 hour. After stopping heating and stirring, the liquid was decanted and washed with distilled water at 80 ℃ to a pH of 7. The catalyst obtained was identified by the number of catalyst-2, and the composition of catalyst-2 is shown in Table 1.
Example 3
Adding 1.5kg of nickel, 1.5kg of silicon and 0.05kg of cobalt into a graphite crucible, heating the graphite crucible in a high-frequency furnace to be molten, spraying mixed molten liquid onto a copper roller with the rotating speed of 900 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the molten liquid at the cooling speed of 1000 plus materials per second and throwing out along the tangent line of the copper roller to form a scaly strip alloy, and grinding the scaly strip alloy until the particle diameter is less than 70 micrometers to obtain the quenched alloy. 50g of the quenched alloy was slowly charged into a three-necked flask containing 500 g of a 20% by weight aqueous solution of sodium hydroxide, and the temperature was controlled to 60 ℃ and stirred at a constant temperature for 1 hour. After stopping heating and stirring, the liquid was decanted and washed with distilled water at 80 ℃ to a pH of 7. The catalyst obtained was identified by the number of catalyst-3, and the composition of catalyst-3 is shown in Table 1.
Example 4
Adding 1.5kg of nickel, 1.5kg of silicon and 0.15kg of iron into a graphite crucible, heating the graphite crucible in a high-frequency furnace to be molten, spraying mixed molten liquid onto a copper roller with the rotating speed of 900 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the molten liquid at the cooling speed of 1000-plus-one 1600 ℃/second, throwing the molten liquid out along the tangent line of the copper roller to form a scaly strip alloy, and grinding the scaly strip alloy until the particle diameter is below 70 micrometers to obtain the quenched alloy. 50g of the quenched alloy was slowly charged into a three-necked flask containing 500 g of a 20% by weight aqueous solution of sodium hydroxide, and the temperature was controlled to 60 ℃ and stirred at a constant temperature for 1 hour. After stopping heating and stirring, the liquid was decanted and washed with distilled water at 80 ℃ to a pH of 7. The catalyst obtained was identified by the number of catalyst-4, and the composition of catalyst-4 is shown in Table 1.
Example 5
Adding 1.5kg of nickel, 1.5kg of silicon and 0.01kg of platinum into a graphite crucible, heating the graphite crucible in a high-frequency furnace to be molten, spraying mixed molten liquid onto a copper roller with the rotating speed of 900 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the molten liquid at the cooling speed of 1000-plus-one 1600 ℃/second, throwing the molten liquid out along the tangent line of the copper roller to form a scaly strip alloy, and grinding the scaly strip alloy until the particle diameter is below 70 micrometers to obtain the quenched alloy. 50g of the quenched alloy was slowly charged into a three-necked flask containing 500 g of a 20% by weight aqueous solution of sodium hydroxide, and the temperature was controlled to 60 ℃ and stirred at a constant temperature for 1 hour. After stopping heating and stirring, the liquid was decanted and washed with distilled water at 80 ℃ to a pH of 7. The catalyst obtained was identified by the number of catalyst-5, and the composition of catalyst-5 is shown in Table 1.
Example 6
Adding 1.5kg of nickel and 1.5kg of silicon into a graphite crucible, heating the graphite crucible in a high-frequency furnace until the graphite crucible is melted, then spraying the mixed molten liquid onto a copper roller with the rotating speed of 900 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the molten liquid at the cooling speed of 1000-1600 ℃/second, and throwing the molten liquid along the tangent line of the copper roller to form a scaly strip alloy, and grinding the scaly strip alloy until the particle diameter is less than 70 micrometers to obtain the quenched alloy. 50g of the quenched alloy was slowly charged into a three-necked flask containing 500 g of a 20% by weight aqueous solution of sodium hydroxide, and the temperature was controlled to 80 ℃ and stirred at a constant temperature for 1 hour. After stopping heating and stirring, the liquid was decanted and washed with distilled water at 90 ℃ to a pH of 7. The catalyst obtained was identified by the number of catalyst-6, and the composition of catalyst-6 is shown in Table 1.
Application examples 1 to 6
This example illustrates the use of the catalyst of the present invention in a stirred tank reactor to produce 1, 4-butenediol.
A500 mL autoclave was charged with 150g of an aqueous solution having a mass fraction of 1, 4-butynediol of 40% and 1g of the catalyst prepared in examples 1 to 6, sealed, replaced three times with 1 MPa hydrogen, and then charged with hydrogen to a hydrogen pressure of 2.0 MPa. The reaction was carried out at 50 ℃ for 2h with 600 rpm stirring, the catalyst was separated off by pressure relief, and the product was analyzed by gas chromatography, the results of which are shown in Table 2.
As can be seen from Table 2, the catalyst of the present invention is used for preparing 1, 4-butenediol, the 1, 4-butenediol selectivity is good, and the conversion rate of 1, 4-butynediol is high.
TABLE 1
Examples Catalyst numbering CatalysisComposition of the agent (subscripts indicate the weight percent of the element)
1 Catalyst-1 Ni85.0Si13.8Mo1.2
2 Catalyst-2 Ni87.2Si12.0Ru0.8
3 Catalyst-3 Ni85.0Si13.0Co2.0
4 Catalyst-4 Ni75.0Si15.0Fe10.0
5 Catalyst-5 Ni82.0Si17.4Pt0.6
6 Catalyst-6 Ni86.8Si13.2
TABLE 2
Figure BDA0001604258950000111

Claims (8)

1. A process for the hydrogenation of 1, 4-butynediol, the hydrogenation process comprising: 1, 4-butynediol is contacted with a catalyst in a hydrogenation reactor and subjected to hydrogenation treatment to obtain 1, 4-butenediol;
the hydrotreating is carried out in the presence or absence of a solvent, the solvent being water, methanol, ethanol or propanol, the weight ratio of the solvent to 1, 4-butynediol being 1: (0.05-5);
the hydrotreating conditions include: the reaction temperature is 30-150 ℃, the hydrogen pressure is 0.1-10 MPa, and the reaction time is 1-500 minutes; the concentration of the catalyst is 0.01-20 wt% based on the total weight of the catalyst, solvent and 1, 4-butynediol;
the catalyst is porous amorphous alloy; the catalyst contains 40-95 wt% of nickel, 0.5-50 wt% of silicon and no more than 20 wt% of transition metal calculated by elements and based on the weight of the catalyst, wherein the transition metal is at least one element selected from IB group, IIB group, IIIB group, IVB group, VIB group, VIIB group and VIII group;
the preparation method of the catalyst comprises the following steps: mixing and melting nickel and silicon or mixing and melting nickel, silicon and transition metal, and carrying out quenching treatment on the obtained mixed molten liquid to obtain quenched alloy; and (3) extracting and desiliconizing the quenched alloy by adopting alkali liquor to obtain the catalyst.
2. The process of claim 1 wherein the catalyst comprises 55 to 90 wt.% nickel, 0.5 to 30 wt.% silicon, and 0.1 to 15 wt.% transition metal, calculated as elements and based on the weight of the catalyst.
3. The process of claim 1 wherein the catalyst comprises 70 to 90 wt.% nickel, 5 to 20 wt.% silicon, and 0.5 to 10 wt.% transition metal, calculated as the elements and based on the weight of the catalyst.
4. The method according to claim 1, wherein the transition metal is at least one selected from the group consisting of iron, copper, cobalt, molybdenum, tungsten, cerium, titanium, zirconium, chromium, platinum, ruthenium, and palladium.
5. The method according to claim 1, wherein the transition metal is at least one selected from molybdenum, ruthenium, iron, cobalt, and platinum.
6. The method of claim 1, wherein the quenching process comprises: spraying the mixed molten liquid onto a copper roller which is 600-DEG C1000 revolutions per minute and is filled with cooling water, cooling the mixed molten liquid at the cooling speed of 1000-DEG C1600 ℃/second and throwing the mixed molten liquid along the tangent line of the copper roller, and crushing the obtained flaky strip alloy to be less than 2000 microns to obtain the quenched alloy; or
The quenching process comprises: and carrying out atomization, spray, deposition and cooling on the mixed molten liquid at the temperature higher than 1300 ℃ to obtain the quenched alloy.
7. The process of claim 1, wherein the conditions for extractive desilication comprise: the temperature is 10-100 ℃, the time is 5-600 minutes, the alkali in the alkali liquor is at least one of barium hydroxide, sodium hydroxide and potassium hydroxide, the concentration of the alkali liquor is 2-40 wt%, and the weight ratio of the quenched alloy to the alkali in the alkali liquor is 1: (1-10).
8. The method of claim 1, wherein the hydrogenation reactor is at least one selected from a slurry bed reactor, a tank reactor, and a fluidized bed reactor.
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