CN109317156B - Catalyst for preparing propiolic alcohol by cracking butynediol and preparation method thereof - Google Patents

Catalyst for preparing propiolic alcohol by cracking butynediol and preparation method thereof Download PDF

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CN109317156B
CN109317156B CN201811326624.7A CN201811326624A CN109317156B CN 109317156 B CN109317156 B CN 109317156B CN 201811326624 A CN201811326624 A CN 201811326624A CN 109317156 B CN109317156 B CN 109317156B
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catalyst
butynediol
mass
active component
carrier
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CN109317156A (en
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谭平华
全学军
唐聪明
李新利
曹平
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Chongqing University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/843—Arsenic, antimony or bismuth
    • B01J23/8437—Bismuth
    • 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
    • B01J23/72—Copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The invention belongs to the field of industrial catalysis, and particularly relates to a catalyst for preparing propiolic alcohol by cracking butynediol and a preparation method thereof. The catalyst is solid superbase prepared by loading a main active component and an active assistant on a carrier, wherein the main active component is one or more of alkali metal and alkaline earth metal, and the active assistant is copper and/or bismuth. The method can be used for preparing the propiolic alcohol by directly catalytically cracking the butynediol in the aqueous solution of the butynediol. The invention also provides a process condition for catalytically cracking the butynediol by using the catalyst, and the conversion rate of the butynediol can be improved to 46.3% and the selectivity of the propiolic alcohol can be improved to 57.4% in a tubular reaction.

Description

Catalyst for preparing propiolic alcohol by cracking butynediol and preparation method thereof
Technical Field
The invention belongs to the field of industrial catalysis, and particularly relates to a catalyst for preparing propiolic alcohol by cracking butynediol and a preparation method thereof.
Background
Propiolic alcohol, also known as 2-propin-1-ol, ethynyl methanol and propargyl alcohol, is a flammable liquid, is easily dissolved in organic solvents such as water, alcohol, ether and the like, and is also an important chemical intermediate. The propiolic alcohol can be used for synthesizing fosfomycin sodium, fosfomycin calcium, sulfadiazine, acrolein, vitamin A and the like, can also be used as a brightening agent in the electroplating industry, and can also be used as a rust remover or a preservative. The propiolic alcohol has unique performance in inhibiting corrosion of acidic substances such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid and the like to metals such as iron, copper, nickel and the like, and is widely used as an acidification corrosion inhibitor under high-temperature high-pressure and high-concentration hydrochloric acid in oil and gas wells abroad.
The common preparation method of propyne is an alkyne-aldehyde method, and patents US2007112226a1, US3087970A, US3218362A, GB1232257A, WO2005019144a1, CN104387236B, CN105017016B and CN108069830A all adopt the alkyne-aldehyde method, namely acetylene and formaldehyde are taken as raw materials and are catalytically synthesized under the action of a catalyst taking copper as an active component. In the process, the yield of the propargyl alcohol is 37%, the rest is a byproduct 1, 4-Butynediol (BYD) (hereinafter referred to as butynediol or BYD), and the market capacity of the 1, 4-butynediol is limited, so that the yield of the propargyl alcohol in the process seriously influences the economic benefit of enterprises.
Other methods for preparing propargyl alcohol are disclosed in patents CN103896737A, US3383427A, etc., which are high in cost or low in yield, for example, CN103896737A provides a method for preparing propargyl alcohol by using a microstructure reactor, which uses grignard reagent, acetylene and aldehyde or ketone as raw materials to prepare the propargyl alcohol, and the method adopts the microstructure reactor to ensure intrinsic safety, but the grignard reagent is high in cost.
In addition, patent CN108503505A selects a synthetic catalyst of 1, 4-butynediol as a catalyst, and catalytically cracks 1, 4-butynediol to prepare propiolic alcohol, but the method has the problems of low yield, slow reaction rate, and difficult separation of the catalyst and the need of adding a reaction solvent, and the whole process needs to be operated under the protection of acetylene gas, which not only results in high production cost, but also has potential operation risk.
Disclosure of Invention
In order to solve the above problems, the present invention provides a catalyst for producing propiolic alcohol by cracking butynediol, which can catalytically crack butynediol in a raw material aqueous solution to produce propiolic alcohol.
The catalyst is solid superbase prepared by loading a main active component and an active assistant on a carrier, wherein the main active component is one or more of alkali metal and alkaline earth metal, and the active assistant is copper and/or bismuth.
Preferably, the main active component accounts for 5-30% of the total catalyst mass based on the mass of the metal oxide, the active assistant accounts for 0.1-5% of the total catalyst mass based on the mass of the metal element, and the balance is the carrier.
Preferably, the main active component accounts for 18-22% of the total catalyst mass based on the mass of the metal oxide, the active additive accounts for 0.1-2% of the total catalyst mass based on the mass of the metal element, and the balance is the carrier.
Preferably, the carrier is one or more of pseudo-boehmite, a molecular sieve and zirconia.
The carrier is a mature product directly purchased from commercial channels for sale.
Preferably, the main active component is alkali metal potassium or cesium.
The invention also provides a preparation method of the catalyst, which is simple and easy to implement and has mild conditions.
The preparation method of the catalyst for cracking propargyl alcohol by butynediol comprises the following steps:
(1) dissolving soluble salt of the main active component in deionized water to prepare a main active component solution;
(2) weighing a carrier, adding a forming aid accounting for 1-5% of the mass of the carrier, uniformly mixing, adding a main active component solution according to the content of a main active component in the prepared target catalyst into the carrier, kneading, forming, drying, and roasting at 300-600 ℃ for 2-6 hours to obtain a catalyst precursor;
(3) weighing soluble salt solution of the active additive to prepare active additive solution;
(4) and (3) immersing the catalyst precursor into the active assistant solution, soaking for 4-8 h at normal temperature, drying, and roasting for 2-6 h at 300-600 ℃ to obtain the catalyst.
The catalyst precursor is impregnated in the solution of the active assistant by an isovolumetric impregnation method.
Preferably, the soluble salt of the main active ingredient is one or more of soluble salts of alkali metals and alkaline earth metals, and can be one or more selected from alkali metal nitrate, alkali metal acetate, alkaline earth metal nitrate and alkaline earth metal acetate. Soluble salts of the alkali metals potassium and cesium may be preferred.
Preferably, the soluble salt of the co-agent is any one or more selected from the group consisting of soluble nitrates, oxalates and carbonates of copper and bismuth.
Preferably, the forming aid is one or more of sesbania powder, graphite, polyvinyl alcohol, hydroxymethyl cellulose and the like.
The catalyst can catalyze the cracking of the butynediol to prepare the propiolic alcohol, and the invention also provides the process conditions for preparing the propiolic alcohol by utilizing the catalyst to catalyze the cracking of the butynediol.
The process conditions for preparing the propiolic alcohol by using the catalyst for catalytic cracking of the butynediol comprise the following steps:
(1) the reaction process is carried out under normal pressure or low pressure, the pressure is 0.1-1.0MPa, and the reaction temperature is 280-420 ℃.
(2) Butynediol is fed in an aqueous solution, the mass concentration of the butynediol is 5-30%, and the liquid space velocity is 0.1-0.8h-1。
Preferably, the mass concentration of the butynediol is 15-22%, and the space velocity of the feeding liquid is 0.3-0.6h-1。
Preferably, the reaction process pressure is 0.1-0.5MPa, and the reaction temperature is 320-350 ℃.
The invention has the beneficial effects that:
the catalyst of the invention uses a carrier to load main active component alkali metal or alkaline earth metal and active auxiliary agent copper or bismuth, so that the catalyst can directly catalyze and crack butynediol in aqueous solution, the conversion rate of the butynediol is up to 46.3%, and the selectivity of the propiolic alcohol is up to 57.4%; the process for catalytically cracking butynediol by using the catalyst provided by the invention only needs to introduce raw material aqueous solution into the reactor, has simple and mild process conditions, does not need to react under the harsh conditions such as no water and the like, does not need to add other organic solvents, is suitable for tubular continuous reaction, is convenient for mass production, and effectively reduces the production cost of enterprises.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention as described above, according to the common technical knowledge and conventional means in the field, and the scope of the invention is covered. The materials and reagents used in the present invention can be purchased from commercially available sources unless otherwise specified.
Example 1
The catalyst for preparing propiolic alcohol by cracking butynediol is prepared from 16% of potassium nitrate, 0.1% of bismuth nitrate, 1% of auxiliary agent copper nitrate and 82.9% of pseudo-boehmite carrier. The preparation method is as follows: (1) weighing 16.3g of potassium nitrate, adding deionized water to dissolve, and preparing an aqueous solution; (2) weighing 82.9g of pseudo-boehmite and 2g of sesbania powder, uniformly mixing, adding the solution prepared in the step (1), kneading, extruding into strips, drying at 100 ℃ for 4h, and roasting at 500 ℃ for 4h to obtain a catalyst precursor; (3) weighing 1.1g of copper nitrate and 1.0g of bismuth nitrate, and dissolving with deionized water to prepare a solution; (4) weighing 100g of the catalyst precursor prepared in the step (2), immersing into the aqueous solution prepared in the step (3), immersing at normal temperature for 8h, drying at 100 ℃ for 4h, and calcining at 500 ℃ for 3h to obtain the catalyst of the embodiment. The catalyst is prepared by adding butynediol into aqueous solution with the mass concentration of 10% and the space velocity of feeding liquid at the pressure of 0.2MPa, the reaction temperature of 390 ℃ and the air velocity of the feeding liquid of 0.3h-1The conversion of butynediol was 51.6% and the selectivity of propiolic alcohol was 23.5%, as measured under the conditions.
Example 2
The catalyst of the embodiment is prepared from 32% of active component potassium nitrate, 0.1% of auxiliary agent bismuth nitrate, 5% of auxiliary agent copper nitrate, 60% of pseudo-boehmite and other carriers of zirconia. The preparation method is as follows: (1) weighing 32.0g of potassium acetate, adding deionized water, and dissolving to prepare an aqueous solution; (2) weighing 60.2g of pseudo-boehmite, 3.1g of zirconia and 5g of hydroxymethyl cellulose, uniformly mixing, adding the solution prepared in the step (1), kneading, extruding into strips, forming, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 6 hours to obtain a catalyst precursor; (3) weighing 0.1g of bismuth nitrate and 5.0g of copper nitrate, and dissolving the bismuth nitrate and the copper nitrate in deionized water to prepare a solution; (4) weighing 100g of the catalyst precursor prepared in the step (2), immersing the catalyst precursor into the aqueous solution prepared in the step (3), immersing the catalyst precursor for 6h at normal temperature, drying the catalyst for 3h at 120 ℃ and roasting the catalyst for 3h at 550 ℃ to obtain the catalyst of the embodiment, carrying out catalytic cracking on the catalyst prepared in the embodiment, and testing the catalyst under the conditions that the pressure is 0.1MPa, the reaction temperature is 280 ℃, the mass concentration of butynediol is 5% of the aqueous solution, and the airspeed of a feeding liquid is 0.8h < -1 >, wherein the conversion rate of the butynediol is 7.5% and the selectivity of the propiolic alcohol is 65.8%.
Example 3
The catalyst prepared in example 2 is used for catalytic cracking, and the pressure is 0.5MPa, the reaction temperature is 330 ℃, the mass concentration of butynediol is 22 percent, and the airspeed of feeding liquid is 0.5h-1The conversion rate of butynediol was 26.3% and the selectivity of propiolic alcohol was 57.4% when tested under the conditions.
Example 4
The catalyst of the embodiment is prepared from 25% of sodium nitrate as an active component, 2% of copper nitrate as an auxiliary agent, 60% of pseudo-boehmite and the balance of a molecular sieve carrier. The preparation method is as follows: (1) weighing 25.0g of sodium acetate, adding deionized water, and dissolving to prepare an aqueous solution; (2) weighing 60.2g of pseudo-boehmite, 15.3g of molecular sieve and 4g of polyethylene glycol, uniformly mixing, adding the solution prepared in the step (1), kneading, extruding into strips, forming, drying at 100 ℃ for 4h, and roasting at 600 ℃ for 8h to obtain a catalyst precursor; (3) weighing 2.0g of copper nitrate, and dissolving the copper nitrate in deionized water to prepare a solution; (4) weighing 100g of the catalyst precursor prepared in the step (2), immersing the catalyst precursor into the aqueous solution prepared in the step (3), immersing the catalyst precursor for 6 hours at normal temperature, drying the catalyst precursor for 3 hours at 120 ℃, and roasting the catalyst precursor for 4 hours at 600 ℃ to obtain the catalyst of the embodiment.
Under the conditions that the pressure is 0.1MPa, the reaction temperature is 420 ℃, the mass concentration of butynediol is 10 percent of the water solution, and the space velocity of the feeding liquid is 0.1h-1The conversion rate of butynediol was 87.0% and the selectivity of propiolic alcohol was 12.8%, as tested under the conditions.
Example 5
The catalyst of the embodiment is prepared by 18 percent of active component calcium nitrate, 2 percent of auxiliary agent copper nitrate, 50 percent of pseudo-boehmite and the balance of molecular sieve carrier. The preparation method is as follows: (1) weighing 18.0g of calcium nitrate, adding deionized water, and dissolving to prepare an aqueous solution; (2) weighing 50.7g of pseudo-boehmite, 22.3g of molecular sieve and 5g of hydroxymethyl cellulose, uniformly mixing, adding the solution prepared in the step (1), kneading, extruding into strips, forming, drying at 100 ℃ for 4h, and roasting at 500 ℃ for 6 hours to obtain a catalyst precursor; (3) weighing 2.0g of copper nitrate, and dissolving the copper nitrate in deionized water to prepare a solution; (4) weighing 100g of the catalyst precursor prepared in the step (2), immersing into the aqueous solution prepared in the step (3), immersing at normal temperature for 6h, drying at 120 ℃ for 3h, and calcining at 500 ℃ for 3h to obtain the catalyst of the embodiment.
Prepared according to the catalyst preparation method. Under the conditions that the pressure is 0.1MPa, the reaction temperature is 380 ℃, the mass concentration of butynediol is 12 percent of aqueous solution, and the space velocity of feeding liquid is 0.3h-1The conversion rate of butynediol was 38.0% and the selectivity of propiolic alcohol was 7.8% when tested under the conditions.
Example 6
The catalyst of the embodiment is prepared by 15% of active component cesium acetate, 0.2% of auxiliary agent bismuth nitrate, 2% of auxiliary agent copper nitrate, 70% of pseudo-boehmite and a zirconia carrier. The preparation method is as follows: (1) weighing 15.0g of cesium acetate, and adding deionized water to dissolve the cesium acetate to prepare an aqueous solution; (2) weighing 70.8g of pseudo-boehmite, 14.6g of zirconia and 5g of sesbania powder, uniformly mixing, adding the solution prepared in the step (1), kneading, extruding into strips, forming, drying at 120 ℃ for 4h, and roasting at 550 ℃ for 6 hours to obtain a catalyst precursor; (3) weighing 0.2g of bismuth nitrate and 2.0g of copper nitrate, and dissolving the bismuth nitrate and the copper nitrate in deionized water to prepare a solution; (4) weighing 100g of the catalyst precursor prepared in the step (2), immersing the catalyst precursor into the aqueous solution prepared in the step (3), immersing the catalyst precursor for 8 hours at normal temperature, drying the catalyst for 4 hours at 100 ℃, and roasting the catalyst for 4 hours at 550 ℃, so as to obtain the catalyst of the embodiment, wherein the conversion rate of the butynediol is 23.7 percent and the selectivity of the propiolic alcohol is 57.7 percent when the catalyst is tested under the conditions that the pressure is 1.0MPa, the reaction temperature is 330 ℃, the mass concentration of the butynediol is 30 percent, and the space velocity of a feeding liquid is 0.4h < -1 >.
Example 7
The catalyst of the embodiment is prepared from 17% of active component sodium acetate, 2% of auxiliary agent copper nitrate, 68% of pseudoboehmite and zirconia carrier. The preparation method is as follows: (1) weighing 17.0g of sodium nitrate, adding deionized water, and dissolving to prepare an aqueous solution; (2) weighing 68.4g of pseudo-boehmite, 14.8g of zirconia and 7g of graphite powder, uniformly mixing, adding the solution prepared in the step (1), kneading, extruding into strips, forming, drying at 120 ℃ for 3h, and roasting at 600 ℃ for 8 hours to obtain a catalyst precursor; (3) weighing 2.0g of copper nitrate, and dissolving the copper nitrate in deionized water to prepare a solution; (4) weighing 100g of the catalyst precursor prepared in the step (2), immersing into the aqueous solution prepared in the step (3), immersing at normal temperature for 8h, drying at 120 ℃ for 4h, and calcining at 600 ℃ for 5h to obtain the catalyst of the embodiment. The conversion rate of the butynediol is 28.1 percent and the selectivity of the propiolic alcohol is 14.7 percent when the pressure is 0.5MPa, the reaction temperature is 380 ℃, the mass concentration of the butynediol is 12 percent, and the space velocity of a feeding liquid is 0.6h < -1 >.
Example 8
The catalyst of the embodiment is prepared from 6% of active component potassium acetate, 0.1% of auxiliary agent bismuth nitrate, 2.5% of auxiliary agent copper nitrate, 60% of pseudo-boehmite and a carrier of a molecular sieve. Prepared according to the catalyst preparation method. The preparation method is as follows: (1) weighing 6.0g of potassium acetate, adding deionized water for dissolving, and preparing an aqueous solution; (2) weighing 80.0g of pseudo-boehmite, 13.8g of molecular sieve and 5g of hydroxymethyl cellulose, uniformly mixing, adding the solution prepared in the step (1), kneading, extruding into strips, forming, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 6 hours to obtain a catalyst precursor; (3) weighing 0.1g of bismuth nitrate and 2.5g of copper nitrate, and dissolving the bismuth nitrate and the copper nitrate in deionized water to prepare a solution; (4) weighing 100g of the catalyst precursor prepared in the step (2), immersing the catalyst precursor into the aqueous solution prepared in the step (3), immersing the catalyst precursor for 6 hours at normal temperature, drying the catalyst precursor for 3 hours at 120 ℃, and roasting the catalyst precursor for 3 hours at 550 ℃, thus obtaining the catalyst of the embodiment. The catalyst prepared in the example is used for catalytic cracking, and the airspeed of feeding liquid is 0.1h at the pressure of 1.0MPa, the reaction temperature of 280 ℃, the aqueous solution of butynediol with the mass concentration of 5 percent-1The conversion rate of butynediol was 5.3% and the selectivity of propiolic alcohol was 48.6% when tested under the conditions.
Example 9
The catalyst prepared in the example 8 is used for catalytic cracking, and the airspeed of feeding liquid is 0.3h at the pressure of 0.5MPa, the reaction temperature of 330 ℃, and the mass concentration of butynediol as 18% aqueous solution-1The conversion rate of butynediol was 14.8% and the selectivity of propiolic alcohol was 34.4% when tested under the conditions.
Example 10
The catalyst of this example comprises 20% of magnesium nitrate as an active component, 0.5% of bismuth nitrate as an auxiliary agent, and 2% of an auxiliary agentCopper nitrate, 60% molecular sieve and alumina carrier. The preparation method is as follows: (1) weighing 20.0g of magnesium nitrate, adding deionized water for dissolving, and preparing into an aqueous solution; (2) weighing 62.3g of molecular sieve, 18.1g of alumina and 5g of hydroxymethyl cellulose, uniformly mixing, adding the solution prepared in the step (1), kneading, extruding into strips, forming, drying at 120 ℃ for 3h, and roasting at 600 ℃ for 6 hours to obtain a catalyst precursor; (3) weighing 0.5g of bismuth nitrate and 2.0g of copper nitrate, and dissolving the bismuth nitrate and the copper nitrate in deionized water to prepare a solution; (4) weighing 100g of the catalyst precursor prepared in the step (2), immersing into the aqueous solution prepared in the step (3), immersing at normal temperature for 6h, drying at 120 ℃ for 3h, and calcining at 600 ℃ for 3h to obtain the catalyst of the embodiment. The catalyst prepared in the example was used, and the pressure was 0.1MPa, the reaction temperature was 320 ℃, the butynediol mass concentration was 30%, and the space velocity of the feed liquid was 0.1h-1The conversion rate of butynediol was 10.3% and the selectivity of propiolic alcohol was 5.5%, as tested under the conditions.
Example 11
The catalyst prepared in example 10 was used for catalytic cracking at a pressure of 0.5MPa, a reaction temperature of 350 ℃, a butynediol mass concentration of 14% and a feed liquid space velocity of 0.3h-1The conversion rate of butynediol was 13.7% and the selectivity of propiolic alcohol was 6.8%, as tested under the conditions.

Claims (8)

1. The catalyst for preparing the propiolic alcohol by cracking the butynediol is characterized in that the catalyst is solid superbase prepared by loading a main active component and an active auxiliary agent on a carrier, wherein the main active component is alkali metal potassium or cesium, and the active auxiliary agent is copper and/or bismuth; the carrier is one or more of pseudo-boehmite, a molecular sieve and zirconia; the main active component accounts for 5-30% of the total catalyst mass according to the mass of the metal oxide, the active auxiliary accounts for 0.1-5% of the total catalyst mass according to the mass of the metal element, and the balance is a carrier.
2. The catalyst according to claim 1, wherein the main active component accounts for 18 to 22% of the total catalyst mass in terms of the mass of the metal oxide, the coagent accounts for 0.1 to 2% of the total catalyst mass in terms of the mass of the metal element, and the balance is the carrier.
3. A process for preparing a catalyst according to claim 1 or 2, comprising the steps of:
(1) dissolving soluble salt of the main active component in deionized water to prepare a main active component solution;
(2) weighing a carrier, adding a forming aid accounting for 1-5% of the mass of the carrier, uniformly mixing, adding a main active component solution according to the content of a main active component in the prepared target catalyst into the carrier, kneading, forming, drying, and roasting at 300-600 ℃ for 2-6 hours to obtain a catalyst precursor;
(3) weighing soluble salt solution of the active additive to prepare active additive solution;
(4) and (3) immersing the catalyst precursor into an active assistant solution, immersing for 4-8 h at normal temperature, drying, and roasting for 2-6 h at 300-600 ℃ to obtain the catalyst for preparing the propiolic alcohol by cracking the butynediol.
4. The method of claim 3, wherein the soluble salt of the primary active ingredient is potassium nitrate, potassium acetate or cesium acetate.
5. The method of claim 3, wherein the soluble salt of the co-agent is any one or more selected from the group consisting of soluble nitrates, oxalates, and carbonates of copper and bismuth.
6. The method of claim 3, wherein the forming aid is one or more of sesbania powder, graphite, polyvinyl alcohol, and hydroxymethyl cellulose.
7. A process for the preparation of propargyl alcohol by catalytic cracking of butynediol using a catalyst according to claim 1 or 2, comprising the steps of: (1) the reaction process is carried out under normal pressure or low pressure, the pressure is 0.1-1.0MPa, the reaction temperature is 280-420 DEG C(ii) a (2) Butynediol is fed in an aqueous solution, the mass concentration of the butynediol is 5-30%, and the liquid space velocity is 0.1-0.8h-1。
8. The process according to claim 7, wherein the butynediol mass concentration is 15-22% and the space velocity of the feed liquid is 0.3-0.6h-1The pressure in the reaction process is 0.1-0.5MPa, and the reaction temperature is 320-350 ℃.
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