CN111170840B - Application of supported bifunctional catalyst in preparation of 3-acetyl propanol from furfural - Google Patents

Application of supported bifunctional catalyst in preparation of 3-acetyl propanol from furfural Download PDF

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CN111170840B
CN111170840B CN201811339418.XA CN201811339418A CN111170840B CN 111170840 B CN111170840 B CN 111170840B CN 201811339418 A CN201811339418 A CN 201811339418A CN 111170840 B CN111170840 B CN 111170840B
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CN111170840A (en
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王爱琴
刘菲
刘巧云
张涛
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Dalian Institute of Chemical Physics of CAS
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    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

Abstract

The invention relates to application of a supported bifunctional catalyst in preparation of 3-acetyl propanol from furfural. The catalyst disclosed by the invention is an ammonium molecular sieve supported ruthenium dual-function catalyst, and has both acidity and catalytic hydrogenation performance. The method can efficiently catalyze furfural to selectively hydrogenate to prepare furfuryl alcohol, and can simultaneously catalyze furfuryl alcohol to highly selectively prepare 3-acetyl propanol by in-situ acid catalysis. The method has the advantages of cheap and easily obtained raw materials, simple catalyst preparation method, simple and convenient recovery, easy product separation, high reaction activity and selectivity for preparing the 3-acetyl propanol from the furfural and the like.

Description

Application of supported bifunctional catalyst in preparation of 3-acetyl propanol from furfural
Technical Field
The invention belongs to the field of pharmaceutical chemicals, and relates to a catalyst for preparing 3-acetyl propanol from furfural, in particular to a supported ruthenium catalyst taking an ammonium molecular sieve as a carrier.
The invention relates to a preparation method and application of the catalyst, in particular to a method for preparing an ammonium type molecular sieve carrier by adopting an ion exchange method, a dipping method is adopted to carry an active component Ru, and the activity, selectivity and stability of the catalyst in the preparation of 3-acetyl propanol by furfural under different preparation and reaction conditions are investigated.
Background
Furfural (furfuryl alcohol) is one of the important biomass-based platform compounds and is currently the only important industrial raw material that can be completely extracted from agricultural and forestry wastes. Since the chemical property of the furfural is very active, a plurality of high value-added chemicals can be derived through reactions such as oxidation, hydrogenation, chlorination, esterification, condensation and the like.
3-acetyl propanol, an important medical intermediate and an organic synthetic intermediate, is a key intermediate for synthesizing downstream medical products such as cyclopropyl methyl ketone, vitamin B1, 5-chloro-2-pentanone and the like, and 5-chloro-2-pentanone is a raw material for synthesizing anti-AIDS drugs such as efluoroviral, illimine and the like and bactericides such as cyprodinil, cyproconazole and the like. The preparation method of 3-acetyl propanol reported in the prior art is as follows: 1) 2-methylfuran or acetylbutyrolactone is used as a raw material and is prepared by a catalytic hydrogenation process in an acid system (Chinese patent CN 102140058A); 2) the method comprises the steps of taking plant cellulose hydrolysate or xylose as a raw material, reacting for several hours in a two-phase solvent under the action of an acid catalyst and a hydrogenation catalyst, concentrating and extracting to obtain 1, 4-pentanediol, and carrying out catalytic dehydrogenation or oxidative dehydrogenation in a fixed bed reactor to obtain the 3-acetyl propanol (Chinese patent CN 107353187A). The two processes are complex and the treatment process is complicated, which increases the production cost of the 3-acetyl propanol. In literature reports, the synthesis of 3-acetyl propanol can be realized by selective oxidation of dihydric alcohol or alkyne hydration, and metal complexes such as gold, ruthenium, platinum and the like are mainly used as catalysts (ACS Catal.,2016,6, 7363; Chemistry,2014,20, 1918; Eur.J.Inorg.Chem.,2004,810; Organometallics,2013,32, 2814; Dalton Trans,2010,39, 10601). Because the catalyst is difficult to recover, the concentration of reaction substrates is low, the raw material alkyne is expensive, and the like, the catalyst is in operationThe wide range of applications is limited in industry. In addition, there is a literature that Ru catalyst is supported by an ordered mesoporous carbon material in CO2/H2The furfural can be converted into 3-acetyl propanol under an O system (Green chem.,2018,20,1770), but the catalyst is extremely unstable in an acidic environment and cannot be recycled.
Therefore, it is important to develop a new catalyst with high activity and good stability to produce 3-acetyl propanol from a wide source of cheap raw materials through an environment-friendly synthesis process route.
Disclosure of Invention
The invention aims to develop a supported bifunctional catalyst for preparing 3-acetyl propanol from furfural. The catalyst is an ammonium molecular sieve supported ruthenium dual-function catalyst, has acidity and catalytic hydrogenation performance, and can efficiently catalyze selective hydrogenation of furfural to prepare furfuryl alcohol, and simultaneously, in-situ acid catalysis of furfuryl alcohol to prepare 3-acetyl propanol with high selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
preparing a supported bifunctional catalyst with an ammonium molecular sieve as a carrier and an active component of ruthenium metal; wherein the content of Ru is 0.5-10wt%, preferably 0.5-5wt%, based on the weight of the catalyst.
The carrier modified ammonium molecular sieve is prepared by an ion exchange method, and the specific process comprises the following steps: firstly, roasting the molecular sieve in a muffle furnace at the temperature of 400-600 ℃ for 6-12 hours, adding the roasted molecular sieve catalyst into an ammonia water solution with the mass concentration of 10% -35% (preferably 15-25 wt%) (the mass ratio of the ammonia water solution to the molecular sieve catalyst is 10:1-30:1 (preferably 15:1-25:1)), stirring at room temperature for more than 12 hours, then filtering, washing, and drying in an oven at the temperature of 50-80 ℃ to prepare the ammonium type molecular sieve.
The molecular sieve is any one or more of H-beta, H-MWW and H-MOR molecular sieves with the pore diameter larger than 0.5nm (preferably 0.5-1.0 nm); preferably H-beta molecular sieve, and the molar ratio of silicon to aluminum is 20-60.
Preparing the bifunctional catalyst by adopting an impregnation method: adding the ammonium type molecular sieve into an equal volume of ruthenium chloride solution, stirring for 0.5-2h, evaporating the solvent to dryness at 50-80 ℃, drying in an oven, then placing in a muffle furnace for roasting at 300-600 ℃ for 3-5 h, and then placing the roasted catalyst in a hydrogen atmosphere for reduction for 0.5-2h at 200-300 ℃ to prepare the ammonium type molecular sieve supported ruthenium dual-function catalyst.
The catalyst is used in the reaction for preparing 3-acetyl propanol from furfural, the reaction raw material is furfural aqueous solution, the reaction is carried out in a closed intermittent stirring reaction kettle at the reaction temperature of 60-150 ℃, the reaction time of 2-36 hours and the hydrogen pressure of 0.1-5 MPa, wherein the mass concentration of the furfural aqueous solution is 1-10%.
The reaction temperature is preferably 60 to 120 ℃, the hydrogen pressure is preferably 0.5 to 3MPa, and the reaction time is preferably 5 to 15 hours.
The ammonium type molecular sieve supported ruthenium dual-function catalyst has both acidity and catalytic hydrogenation performance. The method can efficiently catalyze furfural to selectively hydrogenate to prepare furfuryl alcohol, and can simultaneously catalyze furfuryl alcohol to highly selectively prepare 3-acetyl propanol by in-situ acid catalysis. Under mild conditions, furfural is directly converted into a high value-added chemical 3-acetyl propanol.
The method has the obvious advantages of cheap and easily obtained raw materials, simple catalyst preparation method, simple and convenient recovery, easy product separation, high reaction activity and selectivity for preparing the 3-acetyl propanol from the furfural and the like. And the acid content of the modified ammonium type molecular sieve is higher than that of the unmodified molecular sieve, which is more favorable for the generation of 3-acetyl propanol. (see Table 10)
Drawings
FIG. 1 is a graph showing the results of the stability test of the catalyst of example 21.
Detailed Description
The following examples will help to understand the present invention, but the scope of the present invention is not limited to these examples.
The following specific preparation process of the modified ammonium type molecular sieve carrier takes the preparation process of the modified ammonium type H-beta molecular sieve as an example: firstly, roasting the carrier in a muffle furnace at 550 ℃ for 6H, adding the roasted H-beta molecular sieve catalyst into an ammonia water solution with the mass concentration of 25% (the mass ratio of the ammonia water solution to the molecular sieve catalyst is 30:1), stirring overnight at room temperature for 15H, then filtering, washing and drying in an oven at 60 ℃ to prepare the ammonium type H-beta molecular sieve carrier which is expressed by H-beta-N.
The preparation process of the supported bifunctional catalyst is as follows: dissolving ruthenium trichloride trihydrate in distilled water to prepare a ruthenium chloride solution with the mass fraction of 0.8 wt%, impregnating the modified ammonium type molecular sieve in the same volume, stirring for 1h at 80 ℃, drying the solvent by evaporation at 80 ℃, placing the dried solvent in a drying oven at 60 ℃ and then roasting the dried catalyst in a muffle furnace at 400 ℃ for 4 hours, and then placing the roasted catalyst in a hydrogen atmosphere at 250 ℃ for reduction for 2 hours to prepare the ruthenium dual-function catalyst.
Comparative examples 1 to 6
0.1g of furfural and 5g of water are added into a 50ml high-pressure reaction kettle, 50mg of unmodified molecular sieve ruthenium-loaded bifunctional catalyst (the mass loading amount of Ru is 2 wt%) is added into the reaction kettle, 1.0MPa of hydrogen is introduced, the Parr kettle is sealed, the autoclave is heated to 80 ℃ for reaction after 25 minutes, the reaction is stopped after 10 hours of reaction, the temperature is reduced to room temperature, a liquid product and the catalyst are centrifugally separated, and the liquid product is analyzed by gas chromatography.
The product yield was (mole of carbon of 3-acetylpropanol)/(total mole of carbon charged into raw material) × 100%, and other products were furfuryl alcohol, cyclopentanone, cyclopentanol, 1, 4-pentanediol, and humus, and the yield was not calculated. The results of the reaction are shown in Table 1 below.
Comparative examples 7 to 10
0.1g of furfural and 5g of water are added into a 50ml high-pressure reaction kettle, 50mg of metal oxide supported ruthenium dual-function catalyst (the mass loading amount of Ru is 2 wt%) is added into the reaction kettle, 1.0MPa of hydrogen is introduced, the Parr kettle is sealed, the autoclave is heated to 80 ℃ for reaction after 25 minutes, the reaction is stopped after 10 hours of reaction, the temperature is reduced to room temperature, a liquid product and the catalyst are centrifugally separated, and the liquid product is analyzed by gas chromatography. The product yield was (mole of carbon of 3-acetopropanol)/(total mole of carbon charged in raw materials) × 100%, and the other products were mainly furfuryl alcohol, and the yield thereof was not calculated. The results of the reaction are shown in Table 1 below.
Figure BDA0001862143060000051
As can be seen from Table 1, in the reaction of preparing 3-acetyl propanol from furfural, the selectivity of the target product of the dual-function catalyst of the H-beta, H-MCM and H-MOR molecular sieve loaded ruthenium with the pore channel larger than 0.5nm (the mass loading of ruthenium is 2 wt%) is superior to that of the dual-function catalyst of the oxide carrier and the small pore molecular sieve loaded ruthenium.
Examples 1 to 3
0.1g of furfural and 5g of water are added into a 50ml high-pressure reaction kettle, 50mg of ammonium molecular sieve ruthenium-loaded bifunctional catalyst (the mass loading of Ru is 2 wt%) is added into the reaction kettle, 1.0MPa of hydrogen is introduced, the Parr kettle is sealed, the autoclave is heated to 80 ℃ for reaction after 25 minutes, the reaction is stopped after 10 hours of reaction, the temperature is reduced to room temperature, a liquid product and the catalyst are centrifugally separated, and the liquid product is analyzed by gas chromatography. The product yield was (mole of carbon of 3-acetylpropanol)/(total mole of carbon charged as raw material) × 100%, and other products included furfuryl alcohol, cyclopentanone, cyclopentanol, 1, 4-pentanediol, and the yield thereof was not calculated. The reaction results are shown in Table 2.
Figure BDA0001862143060000052
Figure BDA0001862143060000061
From table 2, it can be seen that, in the reaction of preparing 3-acetyl propanol from furfural, the catalytic activity and selectivity of the ammonium molecular sieve supported ruthenium bifunctional catalyst (the mass loading of ruthenium is 2 wt%) are superior to those of the unmodified molecular sieve supported ruthenium bifunctional catalyst.
Examples 4 to 7
0.1g of furfural and 5g of water are added into a 50ml high-pressure reaction kettle, 50mg of Ru/H-Beta-N catalyst (the mass loading of Ru is 2%) is added into the reaction kettle, 0.5MPa of hydrogen is introduced, the Parr kettle is sealed, the high-pressure kettle is heated to a certain temperature for reaction for 25 minutes, the reaction is stopped after 10 hours of reaction, the temperature is reduced to the room temperature, a liquid product and the catalyst are centrifugally separated, and the liquid product is analyzed by gas chromatography. The reaction results are shown in Table 3 below.
Figure BDA0001862143060000062
As can be seen from Table 3, the selective preparation of 3-acetyl propanol by furfural is facilitated at the reaction temperature of 60-120 ℃ by taking Ru/H-Beta-N as a catalyst.
Examples 8 to 9
Adding 0.1g of furfural and 5g of water into a 50ml high-pressure reaction kettle, simultaneously adding 50mg of Ru/H-Beta-N catalyst (the mass loading of Ru is 2%), introducing 0.5-3MPa of hydrogen, sealing a Parr kettle, heating the high-pressure kettle to 80 ℃ for reaction after 25 minutes, stopping the reaction after 10 hours of reaction, cooling to room temperature, centrifugally separating a liquid product and the catalyst, and analyzing the liquid product by adopting gas chromatography. The results of the reaction are shown in Table 4 below.
Figure BDA0001862143060000071
As can be seen from Table 4, 3-acetylpropanol can be obtained with high selectivity by using Ru/H-Beta-N as a catalyst and furfural under the reaction hydrogen pressure of 0.5-3.0 MPa.
Examples 10 to 12
0.1g of furfural and 5g of water are added into a 50ml high-pressure reaction kettle, 50mg of Ru/H-Beta-N catalyst (the mass loading of Ru is 2%) is added into the reaction kettle, 1.0MPa of hydrogen is introduced, the Parr kettle is sealed, the autoclave is heated to 80 ℃ for reaction after 25 minutes, the reaction is stopped after 5 to 30 hours of reaction, the temperature is reduced to the room temperature, a liquid product and the catalyst are centrifugally separated, and the liquid product is analyzed by gas chromatography. The results of the reaction are shown in Table 5 below.
Figure BDA0001862143060000072
As can be seen from Table 5, with Ru/H-Beta-N as the catalyst, the complete conversion of furfural can be realized within 5H of reaction time, and the selectivity of the obtained 3-acetyl propanol is higher than 85%.
Examples 13 to 15
Adding 0.1g of furfural and 5g of water into a 50ml high-pressure reaction kettle, simultaneously adding 50mg of Ru/H-Beta-N catalyst into the reaction kettle, introducing 1.0MPa of hydrogen, sealing a Parr kettle, heating the high-pressure kettle to 80 ℃ for reaction after 25 minutes, stopping the reaction after 10 hours of reaction, cooling to room temperature, centrifugally separating a liquid product and the catalyst, and analyzing the liquid product by adopting gas chromatography. The results of the reaction are shown in Table 6 below.
Figure BDA0001862143060000081
As can be seen from Table 6, Ru/H-Beta-N with different loading amounts shows better catalytic activity and selectivity in the reaction of preparing 3-acetyl propanol from furfural.
Examples 16 to 18
0.1g of furfural and 5g of water are added into a 50ml high-pressure reaction kettle, 50mg of Ru/H-Beta-N catalyst (the mass loading of Ru is 2%) is added into the reaction kettle, 1.0MPa of hydrogen is introduced, the Parr kettle is sealed, the autoclave is heated to 80 ℃ for reaction after 25 minutes, the reaction is stopped after 10 hours of reaction, the temperature is reduced to room temperature, liquid products and the catalyst are centrifugally separated, and the liquid products are analyzed by gas chromatography. The reaction results are shown in Table 7 below.
Figure BDA0001862143060000082
As can be seen from Table 7, when the Si/Al content in the H-Beta-N molecular sieve is less than 100, the Ru/H-Beta-N catalyst (with the mass loading of Ru being 2 wt%) can show good catalytic activity and selectivity in the reaction of preparing 3-acetyl propanol from furfural.
Examples 19 to 20
Adding 5ml of furfural aqueous solution with different concentrations into a 50ml high-pressure reaction kettle, simultaneously adding a Ru/H-Beta-N catalyst (the mass loading of ruthenium is 2 wt%), controlling the molar ratio of furfural to active component ruthenium to be 1:0.01, introducing 1.0MPa hydrogen, sealing a Parr kettle, heating the high-pressure kettle to 80 ℃ for reaction after 25 minutes, stopping the reaction after 10 hours of reaction, cooling to room temperature, centrifugally separating a liquid product and the catalyst, and analyzing the liquid product by adopting gas chromatography. The reaction results are shown in Table 8 below.
Figure BDA0001862143060000091
It can be seen from table 8 that the Ru/H-beta-N catalyst (with a mass loading of ruthenium of 2 wt%) achieves better catalytic performance in this reaction when the furfural concentration is within 10 wt%.
Example 21 catalyst stability testing
0.1g of furfural and 5g of water are added into a 50ml high-pressure reaction kettle, 50mg of Ru/H-Beta-N catalyst (the mass loading of Ru is 2%) is added into the reaction kettle, 1.0MPa of hydrogen is introduced, the Parr kettle is sealed, the autoclave is heated to 80 ℃ for reaction after 25 minutes, the reaction is stopped after 10 hours of reaction, the temperature is reduced to the room temperature, and liquid products and the catalyst are centrifugally separated. Drying the centrifuged catalyst, reducing the catalyst for 1 hour at 250 ℃ in a hydrogen atmosphere, and repeating the operation process. The liquid product was analyzed by gas chromatography. The reaction results are shown in FIG. 1 below.
As can be seen from the figure 1, the ammonium type H-beta molecular sieve supported ruthenium dual-function catalyst (the mass loading of ruthenium is 2 wt%) can keep good stability in the reaction and conversion process of preparing 3-acetyl propanol from furfural, and the catalyst does not have any deactivation phenomenon after being recycled for 4 times.
TABLE 9 acid content comparison of dual-function catalyst for loading ruthenium on H-beta molecular sieve before and after modification
Catalyst and process for preparing same Amount of acid (mmol/g)
2％Ru/H-beta 843
2％Ru/H-beta-N 1035
As can be seen from the results of the NH3-TPD test, the acid content of the modified ammonium molecular sieve is higher than that of the unmodified molecular sieve, so that the generation of 3-acetyl propanol is more favorable.

Claims (7)

1. The application of the supported bifunctional catalyst in the preparation of 3-acetyl propanol by furfural is characterized in that: the catalyst takes an ammonium molecular sieve as a carrier, and the active component is metal ruthenium; wherein the content of Ru is 0.5-10wt% of the weight of the catalyst;
the carrier modified ammonium molecular sieve is prepared by an ion exchange method,
the specific process is as follows: firstly, the molecular sieve is placed in a muffle furnace 400-oC, roasting at high temperature for 6-12h, adding the roasted molecular sieve catalyst into an ammonia water solution with the mass concentration of 10-35%, wherein the mass ratio of the ammonia water solution to the molecular sieve catalyst is 10:1-30:1, stirring at room temperature for more than 12 hours, then filtering, washing, and drying in an oven at 50-80 ℃ to obtain the ammonium type molecular sieve;
the molecular sieve is any one or more of H-beta, H-MWW and H-MOR molecular sieves with the pore diameter larger than 0.5nm, and the molar ratio of silicon to aluminum is 20-60.
2. Use according to claim 1, characterized in that:
the content of Ru is 0.5-5wt% of the weight of the catalyst.
3. Use according to claim 1, characterized in that:
adding the calcined molecular sieve catalyst into an ammonia water solution with the mass concentration of 15-25wt%, wherein the mass ratio of the ammonia water solution to the molecular sieve catalyst is 15:1-25: 1; the molecular sieve is an H-beta molecular sieve.
4. Use according to claim 1, characterized in that: preparing the bifunctional catalyst by adopting an impregnation method:
adding ammonium type molecular sieve into equal volume of ruthenium chloride solution, stirring for 0.5-2h, 60-80%oC drying the solvent by distillation, drying in an oven at 50-80 ℃, and placing in a muffle furnace for 300-600-oC roasting for 3-5 hours, and then putting the roasted catalyst into 200-300oAnd C, reducing for 0.5-2 hours in a hydrogen atmosphere to prepare the ammonium molecular sieve supported ruthenium bifunctional catalyst.
5. Use according to claims 1-4, characterized in that: the catalyst is used in the reaction of preparing 3-acetyl propanol from furfural, the reaction raw material is furfural aqueous solution, and the reaction is carried out in a closed batch type stirring reaction kettle at the reaction temperature of 60-150 ℃, the reaction time of 2-36 hours and the hydrogen pressure of 0.1-5 MPa.
6. Use according to claim 5, characterized in that: the reaction temperature is 60-120 ℃, the hydrogen pressure is 0.5-3MPa, and the reaction time is 5-15 hours.
7. Use according to claim 5, characterized in that: wherein the mass concentration of the furfural aqueous solution is 1-10%.
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