CN110483242B - Method for synthesizing 1, 4-butanediol by hydrogenation of 1, 4-butynediol - Google Patents
Method for synthesizing 1, 4-butanediol by hydrogenation of 1, 4-butynediol Download PDFInfo
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C07C29/172—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 with the obtention of a fully saturated alcohol
Abstract
The invention discloses a method for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol. The method comprises the following steps: 1, 4-butynediol is subjected to hydrogenation reaction in a first-stage hydrogenation reactor on a modified Ni-based catalyst, and the first-stage hydrogenation product is obtained through pressure relief and separation; the active component of the modified Ni-based catalyst is Ni, and the auxiliary agent is at least one of Ru, K or Mg; carrying out second-stage hydrogenation reaction on the obtained first-stage hydrogenation product and a Ru-based catalyst in a second-stage hydrogenation reactor, and carrying out pressure relief separation to obtain 1, 4-butanediol; the active component of the Ru-based catalyst is Ru. The invention combines the modified Ni-based catalyst and the Ru-based catalyst, so that the conversion rate of 1, 4-butynediol reaches 100%, the selectivity of 1, 4-butanediol reaches 98%, and the invention has the advantages of good catalytic activity, high selectivity, mild reaction conditions, few by-product types and easy separation.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering. More particularly, relates to a method for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol.
Background
1, 4-butanediol is an important organic chemical raw material, can be used for producing polybutylene succinate, polybutylene terephthalate, tetrahydrofuran and the like, and can also be used as a solvent, a chain extender, a cross-linking agent and the like.
The Reppe synthesis method is a widely used method for industrially producing 1, 4-butanediol. Acetylene and formaldehyde are used as raw materials, the acetylene and the formaldehyde are firstly synthesized into 1, 4-butynediol under the action of a copper catalyst, and the 1, 4-butynediol is subjected to catalytic hydrogenation to produce the 1, 4-butanediol. The hydrogenation process is usually carried out by a two-step method, and the first-stage hydrogenation is usually carried out in a suspension bed reactor or a fixed bed reactor and adopts Raney nickelThe second-stage hydrogenation of the nickel-based catalyst prepared by the modified Raney nickel or the precipitation method is carried out in a fixed bed reactor, and a nickel catalyst is mostly adopted. The processes for the production of 1, 4-butanediol, which have been used to date in industrial applications, have the disadvantage of a very high demand for nickel, which is used as hydrogenation catalyst in these processes in the form of Raney. Nickel catalysts in the form of particles are generally used in continuous processes, which are introduced into the reactor as inactive precursor and activated in situ by leaching the aluminium. The bulk density of these catalysts is usually greater than 1.5kg/L, for filling 5-50 m with catalyst3The reactor of (1) uses 8 to 100 tons of nickel, according to the conventional activity of these catalysts required to obtain a sufficient yield. While nickel is present in the earth's crust in a limited amount of about 0.01% by weight, which is one of the more rare metals.
U.S. Pat. No. 5, 3449445,78,89 reports a method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol, which adopts low-pressure hydrogenation in one section and high-pressure hydrogenation in the second section, the hydrogenation pressure is more than 13MPa, the pressure is too high, and the energy consumption is high.
British patent document GB 1242358A adopts Mo modified nickel catalyst to realize hydrogenation of 1, 4-butynediol to prepare 1, 4-butanediol at high temperature and high pressure.
Based on the above analysis, low pressure hydrogenation processes typically produce large amounts of condensed aldehydes and also result in isomerization of butylene glycol to produce large amounts of hydroxybutyraldehyde, which increases separation costs, while high pressure hydrogenation reduces the production of by-products, but consumes large amounts of energy and requires high equipment and increases fixed capital investment.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol. The method adopts a two-stage hydrogenation process, has the advantages of good catalytic activity, high selectivity, mild reaction conditions, few by-product types and easy separation, and meets the requirement of green chemical development.
The above purpose of the invention is realized by the following technical scheme:
a method for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol comprises the following steps:
s1, enabling 1, 4-butynediol to contact a modified Ni-based catalyst in a first-stage hydrogenation reactor, carrying out a first-stage hydrogenation reaction, and carrying out pressure relief separation to obtain a first-stage hydrogenation product; the modified Ni-based catalyst is prepared from an active component, an auxiliary agent and a carrier, wherein the active component is Ni, and the auxiliary agent is at least one of Ru, K or Mg;
s2, contacting the first-stage hydrogenation product obtained in the step S2 with a Ru-based catalyst in a second-stage hydrogenation reactor, carrying out second-stage hydrogenation reaction, and carrying out pressure relief separation to obtain 1, 4-butanediol; the Ru-based catalyst is prepared from an active component, an auxiliary agent and a carrier, wherein the active component is Ru, and the auxiliary agent is K or Mg.
The invention adopts a mode of combining the modified Ni-based catalyst and the Ru-based catalyst, so that the conversion rate of 1, 4-butynediol reaches 100 percent, the selectivity of 1, 4-butanediol reaches 98 percent, and the invention has the advantages of good catalytic activity, high selectivity, mild reaction conditions, few by-product types and easy separation, and meets the requirement of green chemical development.
Preferably, S1, in the modified Ni-based catalyst, the mass percentage of the active component is 2-50%, the mass percentage of the auxiliary agent is 0.1-5%, and the mass percentage of the carrier is 45-97.9% by mass.
More preferably, S1, in the modified Ni-based catalyst, the mass percentage of the active component, the mass percentage of the auxiliary agent and the mass percentage of the carrier are respectively 10-20%, 0.5-4% and 76-89.5%, respectively.
Preferably, S2, in the Ru-based catalyst, the mass percentage of the active component, the mass percentage of the auxiliary agent and the mass percentage of the carrier are respectively 0.5-10%, 0.5-5% and 85-98.5%, respectively, in terms of the mass of the metal element.
More preferably, in the Ru-based catalyst, the mass percentage of the active component, the mass percentage of the auxiliary agent and the mass percentage of the carrier are respectively 1-4%, 1-5% and 91-98% in terms of the mass of the metal element.
Preferably, the carrier in the modified Ni-based catalyst and the Ru-based catalyst is one or more of vermiculite, montmorillonite, attapulgite, diatomite, hydrotalcite, aluminum oxide, silicon dioxide or active carbon.
Preferably, the preparing steps of the modified Ni-based catalyst and the Ru-based catalyst include: preparing a mixed solution from the active component and soluble salt of the auxiliary agent, adding the carrier, and stirring for 1-24 hours; and then adding an alkaline solution to adjust the pH value to 9-10, continuously stirring for 0.5-24 h, standing overnight, performing suction filtration, washing with deionized water, drying, roasting, and reducing to obtain the catalyst.
More preferably, adding a carrier, and stirring for 2-3 h; and then adding an alkaline solution, and continuously stirring for 4-6 h.
Preferably, the alkali of the alkaline solution is selected from at least one of ammonia, urea, potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate solution; the concentration of the alkaline solution is 1-2 mol/L.
More preferably, the alkali of the alkaline solution is ammonia or urea solution.
Preferably, the conditions of the calcination include: the roasting atmosphere is argon or air, the roasting temperature is 200-700 ℃, and the roasting time is 2-6 h.
More preferably, the roasting temperature is 500-700 ℃, and the roasting time is 4-6 h.
Preferably, the reducing conditions include: the reducing agent is hydrogen or a mixed gas of hydrogen and argon, the reducing temperature is 200-700 ℃, and the reducing time is 2-10 h.
More preferably, the reduction temperature is 300-600 ℃, and the reduction time is 3-8 h.
Preferably, the drying temperature of the modified Ni-based catalyst is 60-120 ℃; the Ru-based catalyst is dried at the room temperature of 20-30 ℃.
Preferably, the conditions of the one-stage hydrogenation reaction include: the pressure of the hydrogen is 2-8 MPa, and the temperature is 60-130 ℃.
More preferably, the conditions of the first stage hydrogenation reaction include: the pressure of the hydrogen is 2.5-4.5 MPa, and the temperature is 70-100 ℃.
Preferably, the conditions of the second-stage hydrogenation reaction include: the pressure of the hydrogen is 0.5-3 MPa, and the temperature is 30-90 ℃.
More preferably, the conditions of the secondary hydrogenation reaction include: the pressure of the hydrogen is 1-2 MPa, and the temperature is 35-50 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention combines the modified Ni-based catalyst and the Ru-based catalyst, so that two-stage hydrogenation reaction is carried out under mild conditions, higher catalytic activity and lower byproduct distribution are kept, the separation cost is reduced, the conversion rate of 1, 4-butynediol reaches 100%, the selectivity of 1, 4-butanediol reaches 98%, and the invention has the advantages of good catalytic activity, high selectivity, mild reaction conditions, few byproduct types and easy separation, and meets the requirement of green chemical development.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
EXAMPLES 1-8 preparation of catalysts for Primary hydrogenation reaction 1-8
The compositions of the first-stage hydrogenation catalysts 1-8 are shown in table 1.
Respectively weighing a certain amount of soluble salts of ruthenium trichloride, nickel nitrate and an auxiliary agent, dissolving the soluble salts in 50mL of water, then adding 3g of a carrier, and continuously stirring for 6 hours; adding 1mol/L ammonia water to adjust the pH value to 9-10, continuously stirring for 4 hours, and standing overnight; and (2) carrying out suction filtration, washing with deionized water, drying at 120 ℃, roasting at 700 ℃ for 2h in argon, and reducing for 3h in a hydrogen atmosphere at 300 ℃ to obtain a first-stage hydrogenation catalyst 1-8 (see table 1).
Examples 9 to 16 preparation of catalysts 9 to 16 for two-stage hydrogenation reaction
The compositions of the two-stage hydrogenation catalysts 9-16 are shown in Table 1.
Dissolving a certain amount of ruthenium trichloride and soluble salt of an auxiliary agent in 30mL of deionized water, then adding 5g of a carrier, and continuously stirring for 2 hours; adding 1mol/L sodium hydroxide solution to adjust the pH value to 9-10, continuously stirring for 4 hours, and standing overnight; and (2) carrying out suction filtration, washing with deionized water, drying at room temperature, roasting at 200 ℃ for 6h in argon, and reducing at 600 ℃ for 8h in hydrogen atmosphere to obtain a second-stage hydrogenation catalyst 9-16 (see table 1).
EXAMPLE 171 Synthesis of 1, 4-butanediol by hydrogenation of 4-butynediol
A first-stage hydrogenation step: adding 100mL of 40% 1, 4-butynediol aqueous solution into a 250mL autoclave, adding any one of 1-8 first-stage hydrogenation catalysts, sealing, filling nitrogen for replacing for 4 times, filling hydrogen to 2MPa, heating to 130 ℃, continuously stirring until the pressure in the autoclave does not change, releasing pressure, and separating out the catalyst to obtain a first-stage hydrogenation product.
A second-stage hydrogenation step: adding the first-stage hydrogenation product into a 250mL high-pressure kettle, adding any one of the two-stage hydrogenation catalysts 9-16, sealing, filling nitrogen for replacing for 4 times, filling hydrogen to 1MPa, heating to 90 ℃, continuously stirring until the pressure in the reaction kettle is not changed, releasing pressure and separating out the catalyst to obtain the final hydrogenation product 1, 4-butanediol. The distribution of the products after the reaction is shown in Table 2.
Example 181, 4-Butynediol hydrogenation method for synthesizing 1, 4-butanediol
A first-stage hydrogenation step: adding 100mL of 40% 1, 4-butynediol aqueous solution into a 250mL autoclave, adding any one of 1-8 first-stage hydrogenation catalysts, sealing, filling nitrogen for replacement for 4 times, filling hydrogen to 8MPa, heating to 60 ℃, continuously stirring until the pressure in the autoclave is not changed, releasing pressure, and separating out the catalyst to obtain a first-stage hydrogenation product.
A second-stage hydrogenation step: adding the first-stage hydrogenation product into a 250mL high-pressure kettle, adding any one of the two-stage hydrogenation catalysts 9-16, sealing, filling nitrogen for replacing for 4 times, filling hydrogen to 3MPa, heating to 40 ℃, continuously stirring until the pressure in the reaction kettle is not changed, releasing pressure and separating out the catalyst to obtain the final hydrogenation product 1, 4-butanediol. The product distribution after the reaction is shown in Table 3.
Example 191, 4-Butynediol hydrogenation to 1, 4-butanediol
A first-stage hydrogenation step: adding 100mL of 40% 1, 4-butynediol aqueous solution into a 250mL autoclave, adding any one of 1-8 first-stage hydrogenation catalysts, sealing, filling nitrogen for replacing for 4 times, filling hydrogen to 2.5MPa, heating to 100 ℃, continuously stirring until the pressure in the autoclave does not change, releasing pressure, and separating out the catalysts to obtain a first-stage hydrogenation product.
A second-stage hydrogenation step: adding the first-stage hydrogenation product into a 250mL high-pressure kettle, adding any one of the second-stage hydrogenation catalysts 9-16, sealing, filling nitrogen for replacement for 4 times, filling hydrogen to 1MPa, heating to 50 ℃, continuously stirring until the pressure in the reaction kettle is not changed, releasing pressure and separating out the catalyst to obtain the final hydrogenation product 1, 4-butanediol. The product distribution after the reaction is shown in Table 4.
Example 201 method for synthesizing 1, 4-butanediol by hydrogenating butynediol
A first-stage hydrogenation step: adding 100mL of 40% 1, 4-butynediol aqueous solution into a 250mL autoclave, adding any one of 1-8 first-stage hydrogenation catalysts, sealing, filling nitrogen for replacing for 4 times, filling hydrogen to 4.5MPa, heating to 70 ℃, continuously stirring until the pressure in the autoclave does not change, releasing pressure, and separating out the catalysts to obtain a first-stage hydrogenation product.
A second-stage hydrogenation step: adding the first-stage hydrogenation product into a 250mL high-pressure kettle, adding any one of the two-stage hydrogenation catalysts 9-16, sealing, filling nitrogen for replacing for 4 times, filling hydrogen to 2MPa, heating to 35 ℃, continuously stirring until the pressure in the reaction kettle is not changed, releasing pressure and separating out the catalyst to obtain the final hydrogenation product 1, 4-butanediol. The product distribution after the reaction is shown in Table 5.
TABLE 1 compositions of first-stage hydrogenation catalysts 1 to 8 and second-stage hydrogenation catalysts 9 to 16
Table 2 results of example 17
Table 3 example 18 results
Table 4 results of example 19
Table 5 example 20 results
From the above examples, it can be seen that the combination of the modified Ni-based catalyst and the Ru-based catalyst of the present invention enables both of the two hydrogenation reactions to be performed under mild conditions, and maintains high catalytic activity and low byproduct distribution, and reduces the separation cost, and the conversion rate of 1, 4-butynediol can reach 100%, and the selectivity of 1, 4-butanediol can reach 98%, and the present invention has the advantages of good catalytic activity, high selectivity, mild reaction conditions, few byproduct species, and easy separation, and meets the requirements of green chemistry development.
In addition, as is clear from tables 2 to 5, under the same conditions, the conversion of 1, 4-butynediol and the yield of 1, 4-butanediol in examples 19 and 20 were slightly better than in examples 17 and 18, indicating that when the hydrogenation reaction is carried out in one stage: the pressure of hydrogen is 2.5-4.5 MPa, and the temperature is 70-100 ℃; and (3) second-stage hydrogenation reaction: the hydrogen pressure is 1-2 MPa, and the conversion rate of the 1, 4-butynediol and the yield of the 1, 4-butanediol are higher when the temperature is 35-50 ℃.
The above detailed description is of the preferred embodiment for the convenience of understanding the present invention, but the present invention is not limited to the above embodiment, that is, it does not mean that the present invention must be implemented by the above embodiment. It will be apparent to those skilled in the art that any modifications to the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific forms, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. A method for synthesizing 1, 4-butanediol by hydrogenating 1, 4-butynediol is characterized by comprising the following steps:
s1, enabling 1, 4-butynediol and a modified Ni-based catalyst to contact in a first-stage hydrogenation reactor, carrying out a first-stage hydrogenation reaction, and carrying out pressure relief separation to obtain a first-stage hydrogenation product; the modified Ni-based catalyst is prepared from an active component, an auxiliary agent and a carrier, wherein the active component is Ni, and the auxiliary agent is at least one of Ru, K or Mg;
s2, contacting the first-stage hydrogenation product obtained in the step S2 with a Ru-based catalyst in a second-stage hydrogenation reactor, carrying out a second-stage hydrogenation reaction, and carrying out pressure relief separation to obtain 1, 4-butanediol; the Ru-based catalyst is prepared from an active component, an auxiliary agent and a carrier, wherein the active component is Ru, and the auxiliary agent is K or Mg;
the mass percent of nickel in the modified Ni-based catalyst is 25-45 wt%;
the conditions of the first-stage hydrogenation reaction comprise: the pressure of hydrogen is 2-8 MPa, and the temperature is 60-130 ℃; the conditions of the two-stage hydrogenation reaction comprise: the pressure of the hydrogen is 0.5-3 MPa, and the temperature is 30-90 ℃.
2. The method according to claim 1, wherein S1, in the modified Ni-based catalyst, the mass percentage of the active component, the mass percentage of the auxiliary agent and the mass percentage of the carrier are respectively 2-50%, 0.1-5% and 45-97.9%, respectively, based on the mass of the metal element.
3. The method according to claim 2, wherein S1, in the modified Ni-based catalyst, the mass percentage of the active component, the mass percentage of the auxiliary agent and the mass percentage of the carrier are respectively 10-20%, 0.5-4% and 76-89.5%, respectively.
4. The method according to claim 1, wherein S2, in the Ru-based catalyst, the mass percentage of the active component, the mass percentage of the auxiliary agent and the mass percentage of the carrier are respectively 0.5-10%, 0.5-5% and 85-98.5%, respectively, based on the mass of the metal element.
5. The method according to claim 4, wherein S2, in the Ru-based catalyst, the mass percentage of the active component, the mass percentage of the auxiliary agent and the mass percentage of the carrier are respectively 1-4%, 1-5% and 91-98%, respectively, based on the mass of the metal element.
6. The method according to claim 1, wherein the carrier in the modified Ni-based catalyst and the Ru-based catalyst is one or more of vermiculite, montmorillonite, attapulgite, diatomaceous earth, hydrotalcite, alumina, silica, or activated carbon.
7. The method according to any one of claims 1 to 6, wherein the step of preparing the modified Ni-based catalyst and the Ru-based catalyst comprises:
preparing a mixed solution from the active component and soluble salt of the auxiliary agent, adding a carrier, and stirring for 1-24 hours; and then adding an alkaline solution to adjust the pH value to 9-10, continuously stirring for 0.5-24 h, standing overnight, performing suction filtration, washing with deionized water, drying, roasting, and reducing to obtain the catalyst.
8. The method of claim 7, wherein the base of the alkaline solution is selected from at least one of ammonia, urea, potassium hydroxide, sodium hydroxide, potassium carbonate, or sodium carbonate solution; the concentration of the alkaline solution is 1-2 mol/L.
9. The method of claim 7, wherein the firing conditions include: the roasting atmosphere is argon or air, the roasting temperature is 200-700 ℃, and the roasting time is 2-6 h; the reduction conditions include: the reducing agent is hydrogen or a mixed gas of hydrogen and argon, the reducing temperature is 200-700 ℃, and the reducing time is 2-10 h.
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| CN108993592A (en) * | 2018-06-13 | 2018-12-14 | 厦门大学 | A kind of efficient hydrogenation catalyst and the preparation method and application thereof of butynediols butanediol |
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