CN107597116B - Method for preparing 1, 4-pentanediol by directly hydrogenating levulinic acid by using copper-based catalyst - Google Patents
Method for preparing 1, 4-pentanediol by directly hydrogenating levulinic acid by using copper-based catalyst Download PDFInfo
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Abstract
A method for preparing 1, 4-pentanediol by directly hydrogenating levulinic acid by using a copper-based catalyst is characterized by comprising the following steps of: directly mixing a reaction solvent with a reactant levulinic acid in the presence of a copper-based catalyst of 1, 4-pentanediol, introducing hydrogen to carry out one-pot hydrogenation reaction, and obtaining 1, 4-pentanediol after the reaction is finished; compared with the prior art, the cheap non-noble metal novel copper-based catalyst prepared by the invention has the advantages of simple synthesis method, low cost, no toxicity, no harm, convenience for large-scale production, magnetism, and easiness for recycling and reusing after use; the catalyst can efficiently realize the direct hydrogenation of levulinic acid into 1, 4-pentanediol, has good selectivity, and the total yield of the 1, 4-pentanediol can reach 85 percent, indicating that the synthesis process method has higher potential economic value.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a composition and a preparation method of a novel copper-based hydrogenation reaction catalyst for synthesizing 1, 4-pentanediol, and a preparation method for directly synthesizing 1, 4-pentanediol from levulinic acid by adopting the catalyst.
Background
As an important material basis for human survival and development, fossil resources support the progress of human civilization and the development of economic society in the last 200 years of the 19 th century to the 20 th century. They are not only the most important energy sources for human consumption, but also raw materials for various chemicals that meet the daily needs of human beings. However, the non-renewable nature of fossil resources and the enormous human consumption thereof are making fossil energy sources gradually going to exhaustion. In order to solve the energy crisis, numerous scientific research workers are dedicated to developing new energy sources such as solar energy, wind energy and nuclear energy, but cannot solve the problem of resource. By developing and utilizing biomass, the energy crisis can be solved by using biomass energy, and the biomass resource can also be used as a basic raw material of various chemical products instead of petrochemical resources such as petroleum and the like.
1, 4-pentanediol is a potential polyester polymer monomer, and can prepare polyester materials by reacting with diacid, so that the demand is huge. At present, the production of 1, 4-pentanediol is difficult, and a feasible production route is mainly obtained by catalytic hydrogenation of levulinic acid, levulinate ester and gamma valerolactone. Levulinic acid esters and gamma-valerolactone are mainly produced from biomass hydrolysate levulinic acid, and the production process of separation increases the manufacturing cost of 1, 4-pentanediol. The method for producing the 1, 4-pentanediol by directly carrying out catalytic hydrogenation on the levulinic acid has extremely harsh reaction conditions, only a noble metal catalyst can be adopted at present, and the large-scale production of the 1, 4-pentanediol is restricted due to the limitation of the reaction conditions and the expensive cost of the noble metal catalyst. However, the use of highly efficient, recyclable and inexpensive non-noble metal catalysts for the production of 1, 4-pentanediol has not been reported to date. It is therefore important to develop new and cost-effective catalysts for the direct production of 1, 4-pentanediol from levulinic acid.
Disclosure of Invention
The invention aims to provide a method for preparing 1, 4-pentanediol by directly hydrogenating levulinic acid by using a copper-based catalyst, a method for preparing 1, 4-pentanediol by hydrogenation by using the copper-based catalyst, and a novel method for efficiently preparing 1, 4-pentanediol by directly hydrogenating the levulinic acid on the catalyst.
The invention relates to a method for preparing a copper-based catalyst of 1, 4-pentanediol by hydrogenation, which is characterized in that a main active component of the copper-based catalyst is copper, iron and boron are taken as cocatalyst components, and the weight percentages of three elements in the catalyst are as follows: the copper content is 50-99%, the iron content is 0.9-40%, and the boron content is 0.1-10%. The copper-based catalyst is prepared by adopting a liquid-phase chemical reduction method, and the preparation steps are as follows: preparing a salt solution A containing copper and iron with the total metal concentration of 0.01-2mol/L, introducing nitrogen for protection, placing in an ice water bath, and mechanically and violently stirring; dropwise adding the prepared reducing agent mixed solution B into a salt solution by using a peristaltic pump, wherein the dropwise adding time is 1-2 h; after the dropwise addition is finished, continuing the reaction for 2 hours to wait for full reduction; carrying out suction filtration on a product after reaction, carrying out suction filtration for 5 times by using deionized water, and carrying out suction filtration for 3 times by using absolute ethyl alcohol; the obtained catalyst was stored in absolute ethanol.
The total concentration of the metal salt solution of the salt solution A is preferably 0.1 mol/L; the molar ratio of iron to the total metal is controlled within 50%.
The salt solution solvent is water, ethanol, methanol or glycol, preferably water; the metal salt is a nitrate or chloride salt, preferably a nitrate.
The reducing agent of the reducing agent mixed liquid B is sodium borohydride or potassium borohydride, preferably sodium borohydride; the concentration of the reducing agent in the mixed solution B is 2mol/L, and the solvent is water; the molar ratio of the total reducing agent to the metal in the salt solution A is controlled to be 4: 1; and adding a sodium hydroxide solution into the mixed solution B to adjust the pH value to 12-14, wherein the concentration of the sodium hydroxide solution is 0.2 mol/L.
The invention relates to a method for preparing 1, 4-pentanediol by directly hydrogenating levulinic acid by using a copper-based catalyst, which comprises the following steps of: under the condition that the copper-based catalyst prepared under the conditions exists, directly mixing a reaction solvent with a reactant levulinic acid, introducing hydrogen to carry out one-pot hydrogenation reaction, and obtaining the 1, 4-pentanediol after the reaction is finished.
The reaction solvent comprises one or more than two of water, methanol, ethanol, dodecane, diethyl ether or 1, 4-dioxane, and preferably 1, 4-dioxane. The preparation conditions are as follows: the concentration of the levulinic acid is controlled to be 0.1-0.5 mol/L, the reaction temperature is 60-250 ℃, the hydrogen pressure is 0.1-6Mpa, and the reaction time is 0.1-24 h.
The invention has the technical effects that: compared with the prior art, the cheap non-noble metal novel copper-based catalyst is prepared, has simple synthesis method, low cost, no toxicity and harm, is convenient for large-scale production, has magnetism, and is easy to recycle and reuse after use; the catalyst can efficiently realize the direct hydrogenation of levulinic acid into 1, 4-pentanediol, has good selectivity, and the total yield of the 1, 4-pentanediol can reach 85 percent, indicating that the synthesis process method has higher potential economic value.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a catalyst of the present invention.
FIG. 2 is a nitrogen desorption adsorption (BET) spectrum of the catalyst of the present invention.
FIG. 3 is a Transmission Electron Microscope (TEM) image of the catalyst of the present invention, in which (a) is the overall morphology and (b) is the particle morphology.
Detailed Description
The invention will be better understood from the following examples. The description of the embodiments is intended to be illustrative of the invention and should not, nor should it be taken to limit the invention to the details set forth in the claims.
Example 1.
Preparation of catalyst 30% FeCuB: 30% represents that the molar ratio of iron to the total metals (iron + copper) is 30%, and a salt solution A containing 1.01g of ferric nitrate nonahydrate, 5.45g of cupric nitrate trihydrate and 250ml of water is prepared. Introducing nitrogen for protection, placing in an ice water bath, and mechanically stirring vigorously. A reducing agent mixture B containing 3.79g of sodium borohydride, 0.4g of sodium hydroxide and 50ml of water was prepared. And (3) dropwise adding the prepared reducing agent mixed solution B into the salt solution A by using a peristaltic pump, wherein the dropwise adding time is 1.5h, and continuously reacting for 2h after the dropwise adding is finished to wait for full reduction. And (3) carrying out suction filtration on the product after reaction, carrying out suction filtration for 5 times by using deionized water, and carrying out suction filtration for 3 times by using absolute ethyl alcohol. The obtained catalyst, 30% FeCuB, was stored in absolute ethanol.
And (3) analysis: by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), with N2Physical adsorption (BET) a 30% FeCuB sample was characterized. As shown in FIG. 1, a clear diffraction peak of copper metal and cuprous oxide can be observed for the 30% FeCuB sample, which indicates that the active component copper of the catalyst is in a crystalline structure. The diffraction peak of the iron species is not found, and may be beyond the range identified by XRD due to the small size of the iron species, or in an amorphous structure. As can be seen from FIG. 2, the specific surface area of the 30% FeCuB sample is 100.3m by BET characterization2(ii) in terms of/g. From the image of a transmission electron microscope, the catalyst can be observed to be distributed in fine particles and uniformly wrapped in another light-colored substance in FIG. 3 (a). FIG. 3 (b) observes that individual catalyst particles are between about 10nm and 40 nm.
Levulinic acid hydrogenation activity test: 0.3g levulinic acid, 0.1g30% FeCuB catalyst, 15ml1, 4-dioxane was charged to a high pressure autoclave polytetrafluoroethylene liner. The autoclave was sealed and then replaced 5 times with hydrogen to remove the air in the autoclave. Pre-charging hydrogen, heating to reaction temperature, keeping constant hydrogen pressure, and reacting at 200 deg.C and 5Mpa at stirring speed of 800 rpm for 6 h. After the reaction is finished, cooling to room temperature, starting the reaction kettle, and detecting a product by using GC/MS. The conversion rate of levulinic acid is 100 percent, and the yield of 1,4 pentanediol is 85.1 percent. The remaining product is gamma-valerolactone.
Example 2.
Preparation of catalyst 20% FeCuB: a salt solution A containing 4.04g of ferric nitrate nonahydrate, 9.67g of cupric nitrate trihydrate and 500ml of water was prepared. Introducing nitrogen for protection, placing in an ice water bath, and mechanically stirring vigorously. A reducing agent mixture B containing 7.57g of sodium borohydride, 0.8g of sodium hydroxide and 100ml of water was prepared. And (3) dropwise adding the prepared reducing agent mixed solution B into the salt solution A by using a peristaltic pump, wherein the dropwise adding time is 1.5h, and continuously reacting for 2h after the dropwise adding is finished to wait for full reduction. And (3) carrying out suction filtration on the product after reaction, carrying out suction filtration for 5 times by using deionized water, and carrying out suction filtration for 3 times by using absolute ethyl alcohol. The obtained catalyst 20% FeCuB is stored in absolute ethyl alcohol.
Levulinic acid hydrogenation activity test: 0.3g levulinic acid, 0.1g20% FeCuB catalyst, 15ml ethanol were loaded into a polytetrafluoroethylene liner in an autoclave. The autoclave was sealed and then replaced 5 times with hydrogen to remove the air in the autoclave. Pre-charging hydrogen, heating to reaction temperature, keeping constant hydrogen pressure, and reacting at 200 deg.C and 5Mpa at stirring speed of 800 rpm for 6 h. After the reaction is finished, cooling to room temperature, starting the reaction kettle, and detecting a product by using GC/MS. The conversion of levulinic acid was 100%, and the yield of 1,4 pentanediol was 42.1%. The remaining products are gamma-valerolactone and ethyl levulinate.
Example 3.
Preparation of catalyst 40% FeCuB: a salt solution A containing 4.03g of ferric nitrate nonahydrate, 3.62g of cupric nitrate trihydrate and 250ml of water was prepared. Introducing nitrogen for protection, placing in an ice water bath, and mechanically stirring vigorously. A reducing agent mixture B containing 3.78g of sodium borohydride, 0.4g of sodium hydroxide and 50ml of water was prepared. And (3) dropwise adding the prepared reducing agent mixed solution B into the salt solution A by using a peristaltic pump, wherein the dropwise adding time is 1.5h, and continuously reacting for 2h after the dropwise adding is finished to wait for full reduction. And (3) carrying out suction filtration on the product after reaction, carrying out suction filtration for 5 times by using deionized water, and carrying out suction filtration for 3 times by using absolute ethyl alcohol. The obtained catalyst 40% FeCuB is stored in absolute ethyl alcohol.
Levulinic acid hydrogenation activity test: 0.3g levulinic acid, 0.1g40% FeCuB catalyst, 15ml1, 4-dioxane was charged to a high pressure autoclave polytetrafluoroethylene liner. The autoclave was sealed and then replaced 5 times with hydrogen to remove the air in the autoclave. Pre-charging hydrogen, heating to reaction temperature, keeping constant hydrogen pressure, and reacting at 200 deg.C and 5Mpa at stirring speed of 800 rpm for 6 h. After the reaction is finished, cooling to room temperature, starting the reaction kettle, and detecting a product by using GC/MS. The conversion of levulinic acid was 100%, and the yield of 1,4 pentanediol was 73.8%. The remaining product is gamma-valerolactone.
Example 4.
Preparation of catalyst 20% FeCuB: a salt solution A containing 2.02g of ferric nitrate nonahydrate, 4.835g of cupric nitrate trihydrate and 250ml of water was prepared. Introducing nitrogen for protection, placing in an ice water bath, and mechanically stirring vigorously. A reducing agent mixture B containing 3.79g of sodium borohydride, 0.4g of sodium hydroxide and 50ml of water was prepared. And (3) dropwise adding the prepared reducing agent mixed solution B into the salt solution A by using a peristaltic pump, wherein the dropwise adding time is 1.5h, and continuously reacting for 2h after the dropwise adding is finished to wait for full reduction. And (3) carrying out suction filtration on the product after reaction, carrying out suction filtration for 5 times by using deionized water, and carrying out suction filtration for 3 times by using absolute ethyl alcohol. The obtained catalyst 20% FeCuB is stored in absolute ethyl alcohol.
Levulinic acid hydrogenation activity test: 0.3g levulinic acid, 0.1g20% FeCuB catalyst, 15ml1, 4-dioxane was charged to a high pressure autoclave polytetrafluoroethylene liner. The autoclave was sealed and then replaced 5 times with hydrogen to remove the air in the autoclave. Pre-charging hydrogen, heating to reaction temperature, keeping constant hydrogen pressure, and reacting at 120 deg.C under 3Mpa at stirring speed of 800 rpm for 6 h. After the reaction is finished, cooling to room temperature, starting the reaction kettle, and detecting a product by using GC/MS. The conversion of levulinic acid was 100%, and the yield of 1,4 pentanediol was 0.5%. The remaining product was gamma valerolactone (yield > 99%).
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (3)
1. A method for preparing 1, 4-pentanediol by directly hydrogenating levulinic acid by using a copper-based catalyst is characterized by comprising the following steps of: under the condition of existence of a copper-based catalyst, directly mixing a reaction solvent and a reactant levulinic acid, introducing hydrogen to carry out one-pot hydrogenation reaction, and obtaining 1, 4-pentanediol after the reaction is finished;
the reaction solvent is one or more than two of water, methanol, ethanol, dodecane, diethyl ether or 1, 4-dioxane; controlling the concentration of the levulinic acid to be 0.1-0.5 mol/L, controlling the reaction temperature to be 60-250 ℃, controlling the hydrogen pressure to be 0.1-6MPa, and controlling the reaction time to be 0.1-24 h;
the main active component of the copper-based catalyst is copper, iron and boron are taken as cocatalyst components, and the weight percentages of the three elements in the catalyst are as follows: copper content is 50% -99%, iron content is 0.9% -40%, boron content is 0.1% -10%; the preparation steps are as follows: preparing a salt solution A containing copper and iron with the total metal concentration of 0.01-2mol/L, introducing nitrogen for protection, placing in an ice water bath, and mechanically and violently stirring; dropwise adding the prepared reducing agent mixed solution B into the salt solution A by using a peristaltic pump, wherein the dropwise adding time is 1-2 h; after the dropwise addition is finished, continuing the reaction for 2 hours to wait for full reduction; carrying out suction filtration on a product after reaction, carrying out suction filtration for 5 times by using deionized water, and carrying out suction filtration for 3 times by using absolute ethyl alcohol; storing the obtained catalyst in absolute ethyl alcohol;
the reducing agent of the reducing agent mixed liquid B is sodium borohydride or potassium borohydride; the concentration of the reducing agent in the reducing agent mixed solution B is 2mol/L, and the solvent is water; the molar ratio of the total amount of the reducing agent to the total metals in the salt solution A is controlled to be 4: 1; and adding a sodium hydroxide solution into the reducing agent mixed solution B to adjust the pH value to 12-14, wherein the concentration of the sodium hydroxide solution is 0.2 mol/L.
2. The process according to claim 1, wherein the salt solution A has a total metal salt solution concentration of 0.1 mol/L.
3. The method for preparing 1, 4-pentanediol through the direct hydrogenation of levulinic acid by using a copper-based catalyst according to claim 1, wherein the solvent of the salt solution A is water, ethanol, methanol or ethylene glycol; the metal salt is nitrate or chloride.
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| CN101445426A (en) * | 2008-12-19 | 2009-06-03 | 上海工程技术大学 | Method for preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
| CN102976883A (en) * | 2012-11-26 | 2013-03-20 | 金骄特种新材料（集团）有限公司 | Preparation method of bio-based polyalkyl cyclopentane synthetic oil |
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| CN101445426A (en) * | 2008-12-19 | 2009-06-03 | 上海工程技术大学 | Method for preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
| CN102976883A (en) * | 2012-11-26 | 2013-03-20 | 金骄特种新材料（集团）有限公司 | Preparation method of bio-based polyalkyl cyclopentane synthetic oil |
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