CN110845301A - Production method of 1, 2-pentanediol - Google Patents
Production method of 1, 2-pentanediol Download PDFInfo
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- CN110845301A CN110845301A CN201911107004.9A CN201911107004A CN110845301A CN 110845301 A CN110845301 A CN 110845301A CN 201911107004 A CN201911107004 A CN 201911107004A CN 110845301 A CN110845301 A CN 110845301A
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- C07—ORGANIC CHEMISTRY
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- 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
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- 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
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention discloses a method for producing 1, 2-pentanediol, which comprises the steps of selectively hydrogenating furfuryl alcohol under the catalytic action of a noble metal catalyst loaded on a composite carrier to generate 1, 2-pentanediol; the composite carrier used by the noble metal catalyst loaded by the composite carrier is an oxide mixture formed by blending any one or more of silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide and molecular sieve with manganese oxide, wherein the mass fraction of the manganese oxide is 20-90%. The method can be used for reactors such as batch kettles, fixed beds, continuous slurry beds and the like, and realizes the high-efficiency catalytic conversion of the furfuryl alcohol. The adopted composite carrier loaded noble metal catalyst can be used in H2Orientation of furfuryl alcohol is realized under the conditions that the pressure is 1-10 Mpa and the temperature is 100-300 DEG CAnd (4) performing catalytic conversion. The catalyst has the characteristics of stable property and easy separation and recovery from a reaction system, catalytic products are easy to separate, main by-products have high value, the treatment is simple, and the industrial production value is high.
Description
Technical Field
The invention relates to the field of production of dihydric alcohol, and in particular relates to a production method of 1, 2-pentanediol.
Background
1, 2-pentanediol (namely 1,2-PeD) is used as an important chemical raw material and is an important intermediate for producing the propiconazole. In recent years, 1, 2-pentanediol has been found and recognized to have excellent moisturizing and antiseptic properties, and is widely used in cosmetics, as an excellent moisturizing agent, antibacterial agent and solubilizer in personal care products. Can be used in skin care products such as skin cream, eye cream, skin lotion, infant care product, sunscreen product, etc. In recent years, with the continuous development of fine chemical engineering, the domestic demand for 1, 2-pentanediol is increasing, and due to the insufficient synthetic capacity of the domestic 1, 2-pentanediol, the domestic demand needs to be met by import to a great extent.
The traditional 1, 2-pentanediol synthesis process mainly comprises an n-pentanoic acid method and an n-pentanol method. But the problems of environmental unfriendliness, unsafe industrial production and difficult industrialization exist, or the problems of difficult product separation, large increase of byproducts, reduced final yield and the like exist. At present, the main domestic method for producing 1, 2-pentanediol is a 1-pentene method, but the method also comprises the following steps: excessive formic acid, a byproduct sodium formate generated by neutralizing the excessive formic acid with alkali, high raw material cost, low economic benefit, low yield of 1, 2-pentanediol and the like.
Furfuryl alcohol is a product obtained by hydrogenating biomass furfuralThe aldehyde is generated by hydrolyzing common agricultural and sideline products such as corncobs and the like, is easy to obtain, and has obvious price advantage compared with other raw materials for producing the 1, 2-pentanediol. The method for preparing the 1, 2-pentanediol by catalytic hydrogenation of the furfuryl alcohol has the advantages of low raw material cost, simple purification process, less equipment and low investment, and is suitable for industrial large-scale production. Most of the existing hydrogenation catalysts are noble metal Pt and non-noble metal Cu and Ni, most of the Ni catalysts are Mo modified catalysts or Raney nickel, and the catalysts have high cost, short service life, difficult storage and more complex components; the Cu catalyst has low hydrogenation activity, harsh reaction conditions, generally high required pressure and difficult separation of reaction byproducts; the Pt catalyst is easy to lose active components in the hydrogenation reaction, and influences the reaction activity and the service life of the catalyst. Many studies have been made at home and abroad on the catalytic hydrogenation of furfuryl alcohol to produce 1, 2-pentanediol. Adkins et al reported a method for preparing CuCr2O4The method for generating the 1, 2-pentanediol by hydrogenolysis of furfuryl alcohol at 175 ℃ to 15Mpa under the action of the catalyst, wherein the yield of the 1, 2-pentanediol can reach 40 percent, and the yield of the 1, 5-pentanediol can reach 30 percent. However, the catalyst used in the method contains Cr, which may cause serious pollution to the environment, and the product contains a large amount of 1, 5-pentanediol, which also increases the difficulty of subsequent product separation. Lu et al developed a Pt/Co catalyst2AlO4The catalyst is used for generating 1, 5-pentanediol and 1, 2-pentanediol by carrying out hydrogenolysis on furfuryl alcohol under the conditions of 140 ℃, 1.5Mpa and water serving as a reaction solvent, although the catalytic reaction conditions are mild, the yield of the 1, 2-pentanediol obtained by the method is only 16%. Xu et al developed a Cu-Zn catalyst, which can hydrogenize furfuryl alcohol to generate 1, 2-pentanediol under the conditions of a reaction temperature of 150-160 ℃ and a reaction pressure of 7-8 Mpa, and the catalytic system has a conversion rate of furfuryl alcohol of 69.2%, a selectivity of 46.2% and a yield of 32%. Liu et Al reported that a method for producing 1, 2-pentanediol by hydrogenolysis of furfuryl alcohol at 140 ℃ and 8MPa under the catalysis of Cu-Al2O3 achieved a furfuryl alcohol conversion of 85.5%, wherein the selectivity for 1, 2-pentanediol was 48.1% and the selectivity for 1, 5-pentanediol was 22.2%. Chinese patent application CN108911949A discloses a Cu-based catalystThe method for preparing the 1, 2-pentanediol by the liquid-phase catalytic selective hydrogenolysis of the furfuryl alcohol under the action has the reaction pressure of 7Mpa, the reaction temperature of 140 ℃, the conversion rate of the furfuryl alcohol and the selectivity of the 1, 2-pentanediol are respectively 95 percent and 48 percent, and the method has the limitation that when the concentration of the furfuryl alcohol is increased to more than 80 percent, the conversion rate of the furfuryl alcohol is reduced to 23 percent, the pressure required in the reaction process reaches 7Mpa, and the reaction condition is not mild enough. Zhang et al reported a method for generating 1, 2-pentanediol by catalytic hydrogenolysis of furfuryl alcohol at 150 ℃ and 1.5Mpa under the action of a monometallic Mn-supported Ru-based catalyst, wherein the conversion rate of furfuryl alcohol can reach 100% at most, and the selectivity of 1, 2-pentanediol is 37.5%, but the method has the limitation that the method can only be used for furfuryl alcohol solution with the mass concentration of 10%, and the solvent is water, so that the separation difficulty and the energy consumption of the subsequent process are improved. Chinese patent application CN104370702B discloses a method for preparing 1, 2-pentanediol by furfuryl alcohol liquid phase catalytic selective hydrogenolysis under the action of a Cu-based catalyst, which has the advantages that high-purity furfuryl alcohol can be used as a reaction raw material, the energy loss in the product separation process is reduced, the method is easier to industrialize, the limitation is that the reaction pressure is too high and reaches 8Mpa, and the reaction condition is not mild enough.
The development of the current catalyst for generating 1, 2-pentanediol by the hydrogenolysis of furfuryl alcohol also has various problems: the non-noble metal catalyst Cu has strict requirements on reaction pressure, the pressure of more than 8Mpa is generally required, and 1, 5-pentanediol exists in byproducts, so that the difficulty of subsequent separation can be improved, and the production cost is increased. Noble metal catalysts such as Pt and the like have the problems of low catalytic activity for opening furan ring, easy loss of active components, short service life of the catalyst and the like.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide a production method of dihydric alcohol, which can solve the problems that when a non-noble metal catalyst Cu is adopted for generating 1, 2-pentanediol by hydrogenolysis of furfuryl alcohol, the reaction pressure is harsh, the cost is high due to the subsequent separation of 1, 5-pentanediol, the loss of active components is easy to occur due to the adoption of a noble metal catalyst Pt, the service life of the catalyst is short, and the like.
The purpose of the invention is realized by the following technical scheme:
the embodiment of the invention provides a method for producing 1, 2-pentanediol, which comprises the steps of selectively hydrogenating furfuryl alcohol under the catalytic action of a noble metal catalyst loaded on a composite carrier to generate 1, 2-pentanediol;
the composite carrier used by the composite carrier-loaded noble metal catalyst is an oxide mixture formed by blending any one or more of silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide and molecular sieve with manganese oxide, wherein the mass fraction of the manganese oxide is 20-90%.
According to the technical scheme provided by the invention, the production method of the dihydric alcohol provided by the embodiment of the invention has the beneficial effects that:
because furfuryl alcohol is used as a raw material, the cost is low, and compared with the existing noble metal catalyst, the noble metal catalyst loaded by the adopted composite carrier has the advantages of mild reaction conditions (the reaction conditions are 1-5Mpa, the reaction temperature is 100-200 ℃), high furfuryl alcohol conversion rate, high 1, 2-pentanediol selectivity and the like.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the specific contents of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
The embodiment of the invention provides a production method of 1, 2-pentanediol, which comprises the steps of selectively hydrogenating furfuryl alcohol under the catalytic action of a noble metal catalyst loaded on a composite carrier to generate the 1, 2-pentanediol;
the composite carrier used by the composite carrier-loaded noble metal catalyst is an oxide mixture formed by blending any one or more of silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide and molecular sieve with manganese oxide, wherein the mass fraction of the manganese oxide is 20-90%.
In the method, the oxide mixture of the composite carrier is prepared by adopting a coprecipitation-mechanical mixing combination mode.
In the method, the coprecipitation-mechanical mixing combination mode adopted for preparing the composite carrier is as follows:
preparing a manganese oxide precursor by a coprecipitation method: mixing and reacting a water-soluble nitrate solution of metal manganese with a sodium carbonate solution at a water bath temperature of 50-90 ℃ and a pH value of 5-11 to prepare a manganese oxide precursor, adding any one or more of titanium oxide, aluminum oxide, a molecular sieve, zirconium oxide and silicon oxide into the manganese oxide precursor, uniformly mixing by a machine to form a product, aging the product at 50-90 ℃ for 3-8 h, washing the aged precipitate, drying at 80-150 ℃, and roasting at 300-700 ℃ for 1-10 h to obtain the composite carrier.
In the method, the furfuryl alcohol is pure furfuryl alcohol without adding a solvent;
or the furfuryl alcohol is furfuryl alcohol water solution with the water content of 0.5-90%.
In the method, the active component of the noble metal loaded in the noble metal catalyst loaded by the composite carrier is any one or more of platinum, ruthenium, palladium, rhodium and iridium;
the loading amount of the noble metal catalyst is 1-6%.
In the method, the composite carrier loaded noble metal catalyst is prepared by the following steps: preparing a soaking solution from the noble metal active component according to 0.02-0.1 g/ml, loading the soaking solution on a pre-prepared composite carrier by a soaking method, soaking for 6-12 hours at normal temperature, drying after soaking, and roasting for 1-12 hours at 300-700 ℃ after drying to obtain the composite carrier-loaded noble metal catalyst. Preferably, the impregnation method employs: any one of a one-step impregnation method, a stepwise impregnation method, and a mixed impregnation method.
In the method, the mass ratio of furfuryl alcohol (pure furfuryl alcohol, if the furfuryl alcohol aqueous solution is adopted, the amount of the pure furfuryl alcohol is also taken as the standard) to the composite carrier-supported noble metal catalyst is 10-100: 1, the reaction temperature is 100-300 ℃, and the reaction pressure is 1-10 Mpa;
the method adopts a batch kettle type reaction to prepare the 1, 2-pentanediol or adopts a fixed bed reaction to prepare the 1, 2-pentanediol.
The method for preparing the 1, 2-pentanediol by adopting the batch kettle type reaction specifically comprises the following steps: loading the noble metal catalyst loaded by composite carrier into intermittent reactor, and adding N2And H2Replacing the batch reactor with H2Pretreating, adding furfuryl alcohol or furfuryl alcohol solution, and reacting at 100-300 ℃ under the pressure of 1-10 Mpa for 10-35 h to generate 1, 2-pentanediol.
The method for preparing the 1, 2-pentanediol by adopting the fixed bed reaction specifically comprises the following steps: loading the noble metal catalyst loaded on the composite carrier into a fixed bed, and using H2Pretreating at 200 ℃ for 3-5 h, adding furfuryl alcohol or furfuryl alcohol solution, and reacting at 100-200 ℃, under the conditions of 1-5Mpa of pressure, 0.1-0.5 of airspeed and 4-10: 1 of hydrogen-alcohol ratio to generate 1, 2-pentanediol.
The production method of the invention takes furfuryl alcohol as a raw material, has lower cost, and has the advantages of mild reaction conditions (the reaction conditions are 1-5Mpa, the reaction temperature is 100-200 ℃) and high conversion rate of furfuryl alcohol and high selectivity of 1, 2-pentanediol and the like because the noble metal catalyst loaded by the composite carrier is adopted compared with the existing noble metal catalyst.
In order to better illustrate the present invention, some specific examples of the present invention are listed below, but the present invention is not limited to only the following examples.
The embodiment of the invention provides a production method of 1, 2-pentanediol, which is characterized in that furfuryl alcohol is subjected to hydrogenolysis under the action of a noble metal catalyst loaded on a composite carrier to generate the 1, 2-pentanediol; the composite carrier loaded noble metal catalyst is expressed by N/M, wherein N is a noble metal active component, N is any one or more of platinum, ruthenium, palladium, rhodium and iridium, the mass proportion of N in the catalyst is 0.5-20%, and the preferable proportion is 1-10%; m is a composite carrier, M is an oxide mixture formed by blending any one or more of silicon oxide, zirconium oxide, titanium dioxide, aluminum oxide, a molecular sieve, activated carbon and tin oxide with manganese oxide, and the mass fraction of the manganese oxide in the composite carrier is 30-80%.
The composite carrier M is prepared by adopting a coprecipitation-mechanical mixing combination mode, and specifically comprises the following steps: mixing and reacting a water-soluble nitrate solution of metal manganese with a sodium carbonate solution at a water bath temperature of 50-90 ℃ and a pH value of 5-11 to form a manganese oxide precursor, adding any one or more of silicon oxide, zirconium oxide, titanium dioxide, aluminum oxide, a molecular sieve, activated carbon and tin oxide into the manganese oxide precursor, uniformly mixing by a machine to form a product, aging the product at a temperature of 50-90 ℃ for 3-8 h, washing the precipitate obtained after aging, and drying the precipitate in a drying oven at a temperature of 110 ℃ for 8-12 h to obtain the composite carrier. Further, roasting the prepared composite carrier for 3-7 hours at 300-700 ℃ in an air environment, and washing the composite carrier for multiple times by using deionized water to remove Na+。
The composite carrier loaded noble metal catalyst is prepared by the following method: preparing an impregnation liquid from the noble metal active component N, loading the impregnation liquid on the composite carrier M by an impregnation method (a one-step impregnation method, a step-by-step impregnation method or a mixed impregnation method can be adopted), impregnating for 6-12 h at normal temperature, drying the obtained solid for 8-12 h at 110 ℃ in a drying oven, and then roasting in a muffle furnace to obtain the noble metal catalyst loaded on the composite carrier. Preferably, the noble metal active component N is prepared into an impregnation liquid according to 0.02-0.1 g/ml, and the solid obtained by impregnation is roasted in a muffle furnace for 3-7 hours at 300-700 ℃ after being dried.
Because a large amount of unsaturated double bonds exist in furfuryl alcohol, furfuryl alcohol is easy to polymerize in the reaction, the phenomenon that the hydrogen partial pressure is reduced and the reaction temperature is increased is aggravated, and the polymerized furfuryl alcohol can adhere a catalyst in a reactor, so that the service life and the activity of the catalyst are influenced. Experiments prove that the composite carrier-loaded noble metal catalyst prepared by the coprecipitation-mechanical mixing combination method can effectively inhibit the polymerization of furfuryl alcohol, and ensures the service life and the activity of the catalyst.
The method for producing the 1, 2-pentanediol can use a batch kettle, a fixed bed and other reaction methods.
When a batch kettle reaction is adoptedThe specific operation method comprises the following steps: loading the noble metal catalyst loaded by the composite carrier into a reaction kettle, and adding N2And H2Replacement of the reactor with H2Pretreating for 3-5 h, introducing furfuryl alcohol solution with the mass concentration of 10-100%, and reacting for 8-35 h at the temperature of 100 ℃ and the temperature of 200 ℃ and under the pressure of 1-5Mpa to generate 1, 2-pentanediol.
In order to improve the utilization rate of the catalyst, the conversion rate of raw materials and the selectivity of products, the optimized reaction conditions are as follows: the mass ratio of the furfuryl alcohol to the noble metal catalyst is 10-50: 1.
The catalyst and the product are separated by a centrifugal mode, and the product obtained by the kettle type reaction is analyzed by gas chromatography.
When a fixed bed is used, the operation is specifically carried out by charging a noble metal catalyst supported on a composite carrier into the fixed bed and using H2Pretreating for 3-5 h at 200 ℃, introducing a furfuryl alcohol solution with the mass fraction of 10-100%, and reacting at 100-200 ℃, the pressure of 1-5Mpa, the airspeed of 0.1-0.5 and the hydrogen-alcohol ratio of 4-10: 1 to generate 1, 2-pentanediol.
The technical problems not described in the invention can be solved by the existing solutions.
The production method of the invention takes the noble metal catalyst loaded by the binary carrier as the hydrogenation catalyst, and has good hydrogenation stability and activity. The catalyst has higher thermal stability in a furfuryl alcohol reaction system, supports repeated utilization and can effectively inhibit the polymerization of furfuryl alcohol; the noble metal catalyst can be used for batch kettle type reaction; the method has the advantages that the furfuryl alcohol is efficiently catalyzed to be hydrogenated to generate the 1, 2-pentanediol for reaction under mild conditions, and the byproduct tetrahydrofurfuryl alcohol of the catalytic system has the characteristics of high added value, simplicity in separation, low cost of raw materials and easiness in industrial production.
The following examples are all production methods of 1, 2-pentanediol, and are methods of generating 1, 2-pentanediol by using furfuryl alcohol as a raw material and selectively hydrogenating under the catalytic action of a composite carrier supported noble metal catalyst.
Example 1
The embodiment comprises the following steps:
preparing a composite carrier M of the composite carrier loaded noble metal catalyst:
preparing 1mol/L Na2CO3And Mn (NO)3)2Each 1L; mixing Na2CO3With Mn (NO)3)2Coprecipitating in a stirring state under the condition of water bath with the pH value of 10 and the temperature of 80 ℃, and adding 2mol/L Na in the dropping process2CO3Adjusting the pH value; adding 34g of pseudo-boehmite after the dropwise addition, continuously stirring for 15min, aging for 4h under the condition of 80 ℃ water bath, and then aging for 4h at normal temperature; washing the precipitate with deionized water for several times to remove Na+And then, putting the precipitate into a drying oven for drying at 110 ℃ for 6h, and finally putting the precipitate into a muffle furnace for keeping at 500 ℃ at 1 ℃/min for 5h to obtain the composite carrier M.
Preparing a composite carrier loaded noble metal catalyst:
0.03g/ml RuCl is prepared3Soaking the aqueous solution in 10g of composite carrier 15ml of soaking solution for 6h, drying the catalyst at 110 ℃ for 6h, raising the temperature to 500 ℃ in a muffle furnace at a heating rate of 1 ℃/min for 5h, and washing the catalyst with deionized water for multiple times to remove Cl-Thus obtaining the noble metal catalyst loaded by the composite carrier.
The reaction conditions are as follows:
0.5g of the prepared composite carrier loaded noble metal catalyst is loaded into a batch type reaction kettle, and H is introduced2Reducing for 4h at 200 ℃, and introducing 100ml of furfuryl alcohol with the mass fraction of 10%; the reaction conditions are set to be 2mpa, the reaction temperature is 150 ℃, the reaction time is 10 hours, and 1, 2-pentanediol is generated.
Example 2
The embodiment comprises the following steps:
the composite carrier M of the composite carrier-supported noble metal catalyst was prepared as in example 1.
Preparing a composite carrier loaded noble metal catalyst: 0.03g/ml of H is prepared2PtCl6.6H2Soaking the O aqueous solution in 15ml of soaking solution of 10g of the composite carrier for 6h, drying the catalyst at 110 ℃ for 6h, raising the temperature to 500 ℃ in a muffle furnace at a heating rate of 1 ℃/min, keeping the temperature for 5h,multiple washes of the catalyst with deionized water to remove Cl therefrom-Thus obtaining the noble metal catalyst loaded by the composite carrier.
The reaction conditions are the same as in example 1, see example 1 and are not repeated here.
Example 3
The embodiment comprises the following steps:
the preparation of composite support M is the same as in example 1.
Preparation of the composite carrier-supported noble metal catalyst: 0.03g/ml of RhCl is prepared3Soaking the aqueous solution in 15ml of 10g of carrier for 6h, drying the catalyst at 110 deg.C for 6h, heating to 500 deg.C at 1 deg.C/min in a muffle furnace for 5h, washing the catalyst with deionized water for several times to remove Cl-Thus obtaining the noble metal catalyst loaded by the composite carrier.
The reaction conditions are as shown in example 1, see example 1 and are not repeated here.
Example 4
The embodiment comprises the following steps:
preparation of composite carrier M: preparing 1mol/L Na2CO3And Mn (NO)3)2Each 1L. Mixing Na2CO3With Mn (NO)3)2Coprecipitating in a stirring state under the condition of water bath with the pH value of 10 and the temperature of 80 ℃, and adding 2mol/L Na in the dropping process2CO3The pH value is adjusted. Adding 51g of pseudo-boehmite after the dropwise addition, continuously stirring for 15min, aging for 4h under the condition of 80 ℃ water bath, and then aging for 4h at normal temperature; washing the precipitate with deionized water for several times to remove Na+And then, putting the precipitate into a drying oven for drying at 110 ℃ for 6h, and finally putting the precipitate into a muffle furnace for keeping at 500 ℃ at 1 ℃/min for 5h to obtain the composite carrier-supported noble metal catalyst.
The preparation and reaction conditions of the composite carrier supported noble metal catalyst are the same as those of example 1, see example 1, and are not repeated here.
Example 5
The embodiment comprises the following steps:
preparation of composite carrier M: preparing 1mol/L Na2CO3And Mn (NO)3)2Each 1L. Mixing Na2CO3With Mn (NO)3)2Coprecipitating under stirring in water bath with pH 10 at 80 deg.C, adding 102g of pseudoboehmite after dropwise addition, stirring for 15min, aging in 80 deg.C water bath for 4 hr, and aging at room temperature for 4 hr. Washing the precipitate with deionized water for several times to remove Na+And then, putting the precipitate into a drying oven for drying at 110 ℃ for 6h, and finally putting the precipitate into a muffle furnace for keeping at 500 ℃ at 1 ℃/min for 5h to obtain the composite carrier-supported noble metal catalyst.
The preparation and reaction conditions of the composite carrier supported noble metal catalyst are the same as those of example 1, see example 1, and are not repeated here.
Example 6
The embodiment comprises the following steps:
preparation of composite carrier M: preparing 1mol/L Na2CO3And Mn (NO)3)2Each 1L. Mixing Na2CO3With Mn (NO)3)2Coprecipitating under stirring in water bath with pH 10 at 80 deg.C, adding 204g of pseudoboehmite after dropwise addition, stirring for 15min, aging in 80 deg.C water bath for 4 hr, and aging at room temperature for 4 hr. Washing the precipitate with deionized water for several times to remove Na+And then, putting the precipitate into a drying oven for drying at 110 ℃ for 6h, and finally putting the precipitate into a muffle furnace for keeping at 500 ℃ at 1 ℃/min for 5h to obtain the composite carrier-supported noble metal catalyst.
The preparation and reaction conditions of the catalyst are the same as those of example 1, see example 1, and are not repeated here.
Example 7
The embodiment comprises the following steps:
preparation of composite carrier M:
preparing 1mol/L Na2CO3And SnCl2Each 1L. Mixing Na2CO3With SnCl2Coprecipitating under stirring in water bath at 80 deg.C pH 10, and drippingAdding 51g of pseudo-boehmite after the addition is finished, continuing stirring for 15min, aging for 4h under the condition of 80 ℃ water bath, and then aging for 4h at normal temperature. Washing the precipitate with deionized water for several times to remove Na+And then, putting the precipitate into a drying oven for drying at 110 ℃ for 6h, and finally putting the precipitate into a muffle furnace for keeping at 500 ℃ at 1 ℃/min for 5h to obtain the composite carrier-supported noble metal catalyst.
The preparation and reaction conditions of the catalyst are the same as those of example 1, see example 1, and are not repeated here.
Example 8
The embodiment comprises the following steps:
preparation of composite carrier M:
preparing 1mol/L Na2CO3And Zr (NO)3)4.5H2O is 1L each. Mixing Na2CO3With Zr (NO)3)4.5H2Co-precipitating O under stirring in water bath with pH 10 at 80 deg.C, adding 51g of pseudoboehmite after dropwise addition, stirring for 15min, aging in 80 deg.C water bath for 4 hr, and aging at room temperature for 4 hr. Washing the precipitate with deionized water for several times to remove Na+And then, putting the precipitate into a drying oven for drying at 110 ℃ for 6h, and finally putting the precipitate into a muffle furnace for keeping at 500 ℃ at 1 ℃/min for 5h to obtain the composite carrier-supported noble metal catalyst.
The preparation and reaction conditions of the composite carrier supported noble metal catalyst are the same as those of example 1, see example 1, and are not repeated here.
Example 9
The embodiment comprises the following steps:
preparation of composite carrier M:
preparing 1mol/L Na2CO3And Mn (NO)3)2Each 1L. Mixing Na2CO3With Mn (NO)3)2Coprecipitating under stirring in a water bath condition with the pH value of 10 being 80 ℃, adding 51g of titanium dioxide after finishing dripping, continuously stirring for 15min, aging for 4h under the water bath condition with the temperature of 80 ℃, and then aging for 4h under normal temperature; washing the obtained precipitate with deionized water for several times to remove itNa in (1)+And then, putting the precipitate into a drying oven for drying at 110 ℃ for 6h, and finally putting the precipitate into a muffle furnace for keeping at 500 ℃ at 1 ℃/min for 5h to obtain the composite carrier-supported noble metal catalyst.
The preparation and reaction conditions of the composite carrier supported noble metal catalyst are the same as those of example 1, see example 1, and are not repeated here.
Example 10
The embodiment comprises the following steps:
preparation of composite carrier M:
preparing 1mol/L Na2CO3And Mn (NO)3)2Each 1L. Mixing Na2CO3With Mn (NO)3)2Coprecipitating under stirring in a water bath with pH of 6 at 80 deg.C, adding 51g acidic silica gel after dropwise addition, stirring for 15min, aging in 80 deg.C water bath for 4 hr, and aging at room temperature for 4 hr; washing the precipitate with deionized water for several times to remove Na+And then, putting the precipitate into a drying oven for drying at 110 ℃ for 6h, and finally putting the precipitate into a muffle furnace for keeping at 500 ℃ at 1 ℃/min for 5h to obtain the composite carrier-supported noble metal catalyst.
The preparation and reaction conditions of the composite carrier supported noble metal catalyst are the same as those of example 1, see example 1, and are not repeated here.
Example 11
The embodiment comprises the following steps:
the preparation of the composite carrier M and the composite carrier supported noble metal catalyst are the same as the example 1, refer to the example 1, and are not repeated here.
Reaction conditions are as follows: 0.5g of catalyst is taken and put into a reaction kettle, and H is introduced2Reducing for 4h at 200 ℃, and introducing 100ml of furfuryl alcohol with the mass fraction of 10%; the reaction conditions were set at a pressure of 1.5mpa, a reaction temperature of 150 ℃ and a reaction time of 10 hours.
Example 12
The embodiment comprises the following steps:
the preparation of the composite carrier M and the composite carrier supported noble metal catalyst are the same as the example 1, refer to the example 1, and are not repeated here.
Reaction conditions are as follows:
0.5g of catalyst is taken and put into a reaction kettle, and H is introduced2Reducing for 4h at 200 ℃, and introducing 100ml of furfuryl alcohol with the mass fraction of 10%; the reaction conditions were set at a pressure of 2.5mpa, a reaction temperature of 150 ℃ and a reaction time of 10 hours.
Example 13
The embodiment comprises the following steps:
the preparation of composite carrier M is the same as in example 1, see example 1 and will not be repeated here.
Preparation of the composite carrier-supported noble metal catalyst:
0.05g/ml RuCl is prepared3Soaking the aqueous solution in 15ml of 10g of carrier for 6h, drying the catalyst at 110 deg.C for 6h, heating to 500 deg.C at 1 deg.C/min in a muffle furnace for 5h, washing the catalyst with deionized water for several times to remove Cl-Thus obtaining the noble metal catalyst loaded by the composite carrier.
Reaction conditions are as follows:
0.5g of catalyst is taken and put into a reaction kettle, and H is introduced2Reducing for 4h at 200 ℃, and introducing 100ml of furfuryl alcohol with the mass fraction of 10%; the reaction conditions were set at a pressure of 2mpa, a reaction temperature of 150 ℃ and a reaction time of 10 hours.
Example 14
The embodiment comprises the following steps:
the preparation of the composite carrier M and the composite carrier supported noble metal catalyst are the same as the example 1, refer to the example 1, and are not repeated here.
Reaction conditions are as follows:
50g of catalyst are taken and placed in a fixed bed, H is introduced2Reducing for 4h at 200 ℃, and introducing furfuryl alcohol with the mass fraction of 10%. The reaction conditions were set at a pressure of 2mpa, a reaction temperature of 150 ℃, a space velocity of 0.15 and a hydrogen-alcohol ratio of 10: 1.
Example 15
The embodiment comprises the following steps:
the preparation of the composite carrier M and the preparation of the composite carrier supported noble metal catalyst are the same as those in example 13, see example 13, and are not repeated here.
Reaction conditions are as follows:
0.6g of catalyst is taken and put into a reaction kettle, and H is introduced2Reducing for 4h at 200 ℃, and introducing 100ml of pure furfuryl alcohol with the mass fraction of 30%; the reaction conditions were set at a pressure of 2mpa, a reaction temperature of 150 ℃ and a reaction time of 13 hours.
Example 16
The embodiment comprises the following steps:
preparation of composite carrier M and preparation of composite carrier supported noble metal catalyst are the same as in example 13, see example 13 and will not be repeated here.
Reaction conditions are as follows:
2.5g of catalyst was charged into a reaction vessel, and H was introduced2Reducing for 4h at 200 ℃, and introducing 100ml of pure furfuryl alcohol with the mass fraction of 50%; the reaction conditions were set at a pressure of 2mpa, a reaction temperature of 150 ℃ and a reaction time of 15 hours.
Example 17
The embodiment comprises the following steps:
the preparation of the composite carrier M and the preparation of the composite carrier supported noble metal catalyst are the same as those in example 13, see example 13, and are not repeated here.
Reaction conditions are as follows:
3.5g of catalyst was charged into a reaction vessel, and H was introduced2Reducing for 4h at 200 ℃, and introducing 100ml of pure furfuryl alcohol with the mass fraction of 70%; the reaction conditions were set at a pressure of 2mpa, a reaction temperature of 150 ℃ and a reaction time of 20 hours.
Example 18
The embodiment comprises the following steps:
the preparation of the composite carrier M and the preparation of the composite carrier supported noble metal catalyst are the same as those in example 13, see example 13, and are not repeated here.
Reaction conditions are as follows:
4g of catalyst is loaded into a reaction kettle, and H is introduced2Reducing for 4h at 200 ℃, and introducing 100ml of pure furfuryl alcohol with the mass fraction of 100%; the reaction conditions were set at a pressure of 2mpa, a reaction temperature of 150 ℃ and a reaction time of 30 hours.
Comparative example 19
This comparative example includes the following steps:
preparing a composite carrier M:
preparing 1mol/L Na2CO3And Mn (NO)3)2Each 1L; mixing Na2CO3With Mn (NO)3)2Coprecipitating in a stirring state under the condition of water bath with the pH value of 10 and the temperature of 80 ℃, and adding 2mol/L Na in the dropping process2CO3The pH value is adjusted. After the dropwise addition, aging for 4h under the condition of 80 ℃ water bath, and then aging for 4h at normal temperature; washing the precipitate with deionized water for several times to remove Na+And then, putting the precipitate into a drying oven for drying at 110 ℃ for 6h, and finally putting the precipitate into a muffle furnace for keeping at 500 ℃ at 1 ℃/min for 5h to obtain the composite carrier M.
The preparation of the composite supported noble metal catalyst is the same as in example 1, see example 1 and will not be repeated here.
Reaction conditions are as follows:
0.5g of catalyst is taken and put into a reaction kettle, and H is introduced2Reducing for 4h at 200 ℃, and introducing 100ml of furfuryl alcohol solution with the mass fraction of 10%; the reaction conditions were set at a pressure of 1.5mpa, a reaction temperature of 150 ℃ and a reaction time of 10 hours.
Comparative example 20
This comparative example cites the practice of a manganese-supported Ru-based catalyst disclosed in Zhang in the literature, comprising the steps of:
the preparation of the composite carrier M and the composite carrier supported noble metal catalyst are the same as in example 19, see example 19, and are not repeated here.
Reaction conditions are as follows:
5g of catalyst is loaded into a reaction kettle, and H is introduced2Reducing for 4h at 200 ℃, and introducing 100ml of furfuryl alcohol solution with the mass fraction of 100%; the reaction conditions were set at a pressure of 1.5mpa, a reaction temperature of 150 ℃ and a reaction time of 30 hours.
TABLE 1 results of furfuryl alcohol hydrogenolysis in various examples
The comparative example 19 cited the method of making the Ru-based catalyst supported by manganese carrier disclosed by Zhang in the literature, and comparing the result of the example 19 with the example 4, it can be seen that the Ru-based catalyst supported by composite carrier disclosed in the present invention is improved in both catalytic activity and selectivity to 1, 2-pentanediol.
The catalyst in comparative example 19 is used for catalytic hydrogenolysis of high-concentration furfuryl alcohol, and as a result, as shown in comparative example 20, it can be seen that the catalytic activity and the selectivity of 1, 2-pentanediol of the catalyst are reduced when the high-concentration furfuryl alcohol is subjected to hydrogenolysis, and through examples 13 and 15 to 18, it can be seen that the catalyst disclosed by the invention is also applicable to a high-concentration furfuryl alcohol solution, and the catalytic activity and the selectivity of 1, 2-pentanediol are not reduced along with the increase of the concentration of the furfuryl alcohol solution.
In conclusion, the invention adopts the composite carrier loaded noble metal catalyst, so that the catalyst can be used in H2The oriented catalytic conversion of the furfuryl alcohol is realized under the conditions that the pressure is 1-10 Mpa and the temperature is 100-300 ℃. The method can be used for reactors such as batch kettles, fixed beds, continuous slurry beds and the like, and realizes the high-efficiency catalytic conversion of the furfuryl alcohol. The catalyst has the characteristics of stable property and easy separation and recovery from a reaction system, catalytic products are easy to separate, main by-products have high value, the treatment is simple, and the catalyst has the value of industrial production.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A production method of 1, 2-pentanediol is characterized in that furfuryl alcohol is selectively hydrogenated under the catalytic action of a noble metal catalyst loaded on a composite carrier to generate the 1, 2-pentanediol;
the composite carrier used by the composite carrier-loaded noble metal catalyst is an oxide mixture formed by blending any one or more of silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide and molecular sieve with manganese oxide, wherein the mass fraction of the manganese oxide is 20-90%.
2. The method for producing 1, 2-pentanediol according to claim 1, wherein the oxide mixture of the composite carrier is prepared by a combination of co-precipitation and mechanical mixing.
3. A process for the production of pentane-1, 2-diol according to claim 2, wherein the composite support is prepared using a combination of co-precipitation and mechanical mixing:
preparing a manganese oxide precursor by a coprecipitation method: mixing and reacting a water-soluble nitrate solution of metal manganese with a sodium carbonate solution at a water bath temperature of 50-90 ℃ and a pH value of 5-11 to prepare a manganese oxide precursor, adding any one or more of titanium oxide, aluminum oxide, a molecular sieve, zirconium oxide and silicon oxide into the manganese oxide precursor, uniformly mixing by a machine to form a product, aging the product at 50-90 ℃ for 3-8 h, washing the aged precipitate, drying at 80-150 ℃, and roasting at 300-700 ℃ for 1-10 h to obtain the composite carrier.
4. A process for producing 1, 2-pentanediol according to any one of claims 1 to 3, wherein said furfuryl alcohol is pure furfuryl alcohol without adding a solvent;
or the furfuryl alcohol is furfuryl alcohol water solution with the water mass content of 0.5-90%.
5. A process for producing 1, 2-pentanediol according to any one of claims 1 to 3, wherein the noble metal active component supported in the noble metal catalyst supported on the composite carrier is any one or more of platinum, ruthenium, palladium, rhodium and iridium;
the mass loading of the noble metal active component in the composite carrier-loaded noble metal catalyst is 1-6%.
6. The process for producing 1, 2-pentanediol according to claim 6, wherein the composite carrier-supported noble metal catalyst is prepared by: preparing a soaking solution from the noble metal active component according to 0.02-0.1 g/ml, loading the soaking solution on a pre-prepared composite carrier by a soaking method, soaking for 6-12 hours at normal temperature, drying after soaking, and roasting for 1-12 hours at 300-700 ℃ after drying to obtain the composite carrier-loaded noble metal catalyst.
7. A process for the production of pentane 1, 2-diol according to claim 7, wherein the impregnation comprises: any one of a one-step impregnation method, a stepwise impregnation method, and a mixed impregnation method.
8. A process for producing 1, 2-pentanediol according to any one of claims 1 to 3, wherein the mass ratio of the furfuryl alcohol to the composite carrier-supported noble metal catalyst is 10 to 100: 1, the reaction temperature is 100-300 ℃, and the reaction pressure is 1-10 Mpa;
the method adopts a batch kettle type reaction to prepare the 1, 2-pentanediol or adopts a fixed bed reaction to prepare the 1, 2-pentanediol.
9. The method for producing 1, 2-pentanediol according to claim 8, wherein the method for producing 1, 2-pentanediol by using a batch tank reaction specifically comprises: loading the noble metal catalyst loaded by composite carrier into intermittent reactor, and adding N2And H2Replacing the batch reactor with H2Pretreating, adding furfuryl alcohol or furfuryl alcohol solution, and reacting at 100-300 ℃ under the pressure of 1-10 Mpa for 10-35 h to generate 1, 2-pentanediol.
10. As in claimThe method for producing the 1, 2-pentanediol, according to claim 8, is characterized in that the method for preparing the 1, 2-pentanediol by using a fixed bed reaction specifically comprises the following steps: loading the noble metal catalyst loaded on the composite carrier into a fixed bed, and using H2Pretreating at 200 ℃ for 3-5 h, adding furfuryl alcohol or furfuryl alcohol solution, and reacting at 100-200 ℃, under the conditions of 1-5Mpa of pressure, 0.1-0.5 of airspeed and 4-10: 1 of hydrogen-alcohol ratio to generate 1, 2-pentanediol.
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|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068986A (en) * | 2011-01-06 | 2011-05-25 | 华东理工大学 | Catalyst used in ring-opening hydrogenation reaction of furan derivative |
| US20140066666A1 (en) * | 2011-05-09 | 2014-03-06 | Symrise Ag | Method For Producing 1,2-Pentanediol |
| CN104016831A (en) * | 2013-02-28 | 2014-09-03 | 赢创工业集团股份有限公司 | Hydrogenolysis of furfuryl alcohol to 1,2-pentanediol |
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
| CN105130746A (en) * | 2015-08-05 | 2015-12-09 | 中国科学院兰州化学物理研究所 | Method for producing pentanediol through selective hydrogenolysis of furan derivative |
-
2019
- 2019-11-13 CN CN201911107004.9A patent/CN110845301B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068986A (en) * | 2011-01-06 | 2011-05-25 | 华东理工大学 | Catalyst used in ring-opening hydrogenation reaction of furan derivative |
| US20140066666A1 (en) * | 2011-05-09 | 2014-03-06 | Symrise Ag | Method For Producing 1,2-Pentanediol |
| CN104016831A (en) * | 2013-02-28 | 2014-09-03 | 赢创工业集团股份有限公司 | Hydrogenolysis of furfuryl alcohol to 1,2-pentanediol |
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
| CN105130746A (en) * | 2015-08-05 | 2015-12-09 | 中国科学院兰州化学物理研究所 | Method for producing pentanediol through selective hydrogenolysis of furan derivative |
Non-Patent Citations (1)
| Title |
|---|
| BIN ZHANG等: "Selective conversion of furfuryl alcohol to 1,2-pentanediol over a Ru/MnOx catalyst in aqueous phase", 《GREEN CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116920854A (en) * | 2023-06-08 | 2023-10-24 | 山东一诺生物质材料有限公司 | Catalyst, preparation method and production method of 1, 2-pentanediol |
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