Catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of synthesis of polyester materials, in particular to a catalyst and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: S1) dropwise adding a tungsten-containing precursor solution onto a metal oxide carrier, and carrying out isovolumetric mixing; s2) performing auxiliary impregnation by adopting a strengthening means, aging at room temperature, drying, and crushing to obtain powder A; s3) roasting in an air atmosphere to obtain powder B; s4) dropwise adding a chloroplatinic acid precursor solution onto the powder B, performing isovolumetric mixing, performing auxiliary impregnation by adopting the strengthening means, and performing aging and drying at room temperature to obtain powder C; s5) roasting in an air atmosphere to obtain powder D; and S6) carrying out reduction treatment in a hydrogen atmosphere to obtain the catalyst. The catalyst has high catalytic activity and selectivity, can efficiently catalyze glycerol hydrogenolysis to prepare 1, 3-propylene glycol and co-produce n-propanol, and is mild in reaction condition, few in by-product and easy to separate and purify.

Description

Technical Field

[0001] The invention relates to the technical field of polyester material synthesis, and in particular to a catalyst, a preparation method and application thereof. Background Art

[0002] In recent years, the direct hydrogenolysis of glycerol has gradually entered the field of vision of researchers due to its excellent economic and environmental benefits, and has been used to produce polyester monomers - 1,3-propylene glycol. This method not only solves the practical problem of oversupply of crude glycerol, but also the price of the product is about 10 times that of the raw material, and the economic value is extremely high. From the perspective of atomic economy, glycerol can obtain 1,3-propylene glycol by removing the intermediate hydroxyl group through a one-step hydrogenolysis reaction, which is green and economical. Therefore, the preparation of high-value-added 1,3-propylene glycol by catalytic conversion of excess glycerol is a synthetic route that has received great attention from academia and industry.

[0003] Compared with the biological fermentation method, the glycerol hydrogenolysis method has a higher tolerance for the raw material glycerol, and its salt resistance is about several times that of the biological method. However, the technical difficulty of preparing 1,3-propylene glycol by glycerol hydrogenolysis lies in the design and development of catalysts. How to inhibit the excessive hydrogenolysis reaction, protect the primary hydroxyl group from being broken by hydrogenolysis, and improve the selectivity of the target product while increasing the glycerol hydrogenolysis activity has become a problem that needs to be solved urgently. Therefore, it is urgent to develop a catalyst for the hydrogenation preparation of 1,3-propylene glycol with mild reaction conditions, high efficiency, and few by-products. Summary of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a catalyst, a preparation method and application thereof. The catalyst prepared by the present invention has high catalytic activity and selectivity, can efficiently catalyze the hydrogenolysis of glycerol to prepare 1,3-propylene glycol and co-produce n-propanol at a high glycerol concentration, and has the characteristics of high efficiency, mild reaction conditions, few by-products, and easy separation and purification.

[0005] The present invention provides a method for preparing a catalyst, comprising the following steps:

[0006] S1) dropping a tungsten-containing precursor solution onto a metal oxide support and mixing them in equal volumes; the tungsten-containing precursor is selected from at least one of ammonium tungstate, ammonium metatungstate, tungstic acid, sodium tungstate and phosphotungstic acid;

[0007] S2) after auxiliary impregnation by strengthening means, aging at room temperature, drying, and crushing to obtain powder A; the strengthening means is selected from at least one of microwave irradiation, ultraviolet irradiation and ultrasonic irradiation;

[0008] S3) calcining the powder A in an air atmosphere to obtain powder B;

[0009] S4) dropping the chloroplatinic acid precursor solution onto the powder B, mixing them in equal volumes, and using the strengthening means to assist in impregnation, aging at room temperature, and drying to obtain powder C;

[0010] S5) calcining the powder C in an air atmosphere to obtain powder D;

[0011] S6) reducing the powder D in a hydrogen atmosphere to obtain a catalyst.

[0012] Preferably, in step S1), the metal oxide carrier is a nano-scale oxide powder, selected from at least one of nano-aluminum oxide, nano-silicon oxide and nano-zirconium oxide.

[0013] Preferably, in step S1), the tungsten-containing precursor solution is obtained by dissolving a tungsten-containing precursor in deionized water; and the concentration of the tungsten-containing precursor solution is 0.005-0.5 mol / L.

[0014] Preferably, in step S2), the frequency of the microwave irradiation is 2000-3000 MHz; the wavelength of the ultraviolet irradiation is ≤400 nm, and the light intensity is 4-16 mW / cm 2 ; The frequency of the ultrasonic irradiation is 30 to 50 KHz, and the power is 70 to 150 W;

[0015] The auxiliary impregnation time is 0.5 to 2 hours; the aging time is 2 to 10 hours.

[0016] Preferably, in step S3), the calcination temperature is 300-600°C and the calcination time is 4-6h;

[0017] After the calcination, the process further comprises cooling.

[0018] Preferably, in step S4), the chloroplatinic acid precursor solution is obtained by dissolving chloroplatinic acid in deionized water; the concentration of the chloroplatinic acid precursor solution is 0.01 to 0.5 g / mL;

[0019] The frequency of the microwave irradiation is 2000-3000 MHz; the wavelength of the ultraviolet irradiation is ≤400 nm, and the light intensity is 4-16 mW / cm 2 ; The frequency of the ultrasonic irradiation is 30 to 50 KHz, and the power is 70 to 150 W;

[0020] The auxiliary impregnation time is 0.5 to 2 hours; the aging time is 2 to 10 hours.

[0021] Preferably, in step S5), the calcination temperature is 400-600°C and the calcination time is 4-6 hours;

[0022] After the calcination, the process further comprises cooling.

[0023] Preferably, in step S6), the reduction treatment is carried out at a temperature of 300 to 500° C. for a time of 1 to 5 hours;

[0024] After the reduction treatment, the method further comprises cooling.

[0025] The present invention also provides a catalyst prepared by the preparation method described above.

[0026] The present invention also provides a use of the catalyst described above in a catalytic hydrogenation synthesis reaction.

[0027] The present invention also provides a method for preparing 1,3-propylene glycol and / or n-propanol, comprising the following steps:

[0028] Carrying out a catalytic hydrogenation reaction of glycerol, water and a catalyst under a hydrogen atmosphere at 160 to 220° C. to obtain 1,3-propylene glycol and / or n-propanol;

[0029] The catalyst is the catalyst described above.

[0030] The catalyst prepared by the present invention has high catalytic activity and selectivity, can efficiently catalyze the hydrogenolysis of glycerol to prepare 1,3-propylene glycol and co-produce n-propanol at a high glycerol concentration, has the characteristics of high efficiency, mild reaction conditions, few by-products, easy separation and purification, etc., and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Pt / WO prepared in Example 8 of the present invention x / Transmission electron microscopy image (TEM image) of Al2O3-UV catalyst;

[0032] Figure 2 Pt / WO prepared in Example 8 of the present invention x / X-ray diffraction pattern (XRD pattern) of Al2O3-UV catalyst;

[0033] Figure 3 This is the liquid chromatogram of the solution after the reaction in step 2) of Application Example 4. DETAILED DESCRIPTION

[0034] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] The present invention provides a method for preparing a catalyst, comprising the following steps:

[0036] S1) dropping a tungsten-containing precursor solution onto a metal oxide support and mixing them in equal volumes;

[0037] S2) after auxiliary impregnation by strengthening means, aging at room temperature, drying, and crushing to obtain powder A;

[0038] S3) calcining powder A in an air atmosphere to obtain powder B;

[0039] S4) dropping the chloroplatinic acid precursor solution onto powder B, mixing them in equal volumes, and using a strengthening method to assist impregnation, aging at room temperature, and drying to obtain powder C;

[0040] S5) calcining powder C in an air atmosphere to obtain powder D;

[0041] S6) The powder D is subjected to reduction treatment in a hydrogen atmosphere to obtain a catalyst.

[0042] Regarding step S1):

[0043] The tungsten-containing precursor solution is dropped onto the metal oxide support and mixed in equal volumes.

[0044] The tungsten-containing precursor is selected from at least one of ammonium tungstate, ammonium metatungstate, tungstic acid, sodium tungstate and phosphotungstic acid.

[0045] The tungsten-containing precursor solution is obtained by dissolving a tungsten-containing precursor in deionized water. The concentration of the tungsten-containing precursor solution is 0.005-0.5 mol / L, such as 0.067 g / mL.

[0046] The metal oxide carrier is nano-scale oxide powder, which is selected from at least one of nano-aluminum oxide, nano-silicon oxide and nano-zirconium oxide.

[0047] The dropping is dropwise addition.

[0048] Regarding step S2):

[0049] After auxiliary impregnation by enhanced means, aging at room temperature, drying and pulverization were performed to obtain powder A.

[0050] The strengthening means is selected from at least one of microwave irradiation, ultraviolet irradiation and ultrasonic irradiation.

[0051] The frequency of the microwave irradiation is 2000-3000 MHz; the wavelength of the ultraviolet irradiation is ≤400 nm, and the light intensity is 4-16 mW / cm 2 The frequency of the ultrasonic irradiation is 30-50 KHz, and the power is 70-150 W. The auxiliary immersion time is 0.5-2 h, such as 0.5 h, 1 h, 1.5 h or 2 h.

[0052] The aging time is 2 to 10 hours, such as 2 hours, 6 hours or 10 hours.

[0053] The drying temperature is 70-110° C., such as 70° C., 90° C., 110° C.; the drying time is 4-14 hours, such as 12 hours.

[0054] Regarding step S3):

[0055] Powder A is calcined in an air atmosphere to obtain powder B.

[0056] The calcination temperature is 300-600° C., such as 300° C., 450° C. or 600° C., and the calcination time is 4-6 hours, such as 4 hours or 6 hours. The calcination is carried out in a muffle furnace.

[0057] After the calcination, the method further comprises cooling, wherein the cooling may be natural cooling to room temperature.

[0058] Regarding step S4):

[0059] The chloroplatinic acid precursor solution is added dropwise onto powder B, and equal volumes are mixed. After auxiliary impregnation is performed using strengthening means, the powder is aged at room temperature and dried to obtain powder C.

[0060] The chloroplatinic acid precursor solution is obtained by dissolving chloroplatinic acid in deionized water. The concentration of the chloroplatinic acid precursor solution is 0.01-0.5 g / mL.

[0061] The dropping is dropwise addition.

[0062] The strengthening means is selected from at least one of microwave irradiation, ultraviolet irradiation and ultrasonic irradiation.

[0063] The frequency of the microwave irradiation is 2000-3000 MHz; the wavelength of the ultraviolet irradiation is ≤400 nm, and the light intensity is 4-16 mW / cm 2 The frequency of the ultrasonic irradiation is 30-50 KHz, and the power is 70-150 W. The auxiliary immersion time is 0.5-2 h, such as 0.5 h, 1 h, 1.5 h or 2 h.

[0064] The aging time is 2 to 10 hours, such as 2 hours, 6 hours or 10 hours.

[0065] The drying temperature is 70-110° C., such as 70° C., 90° C., 110° C.; the drying time is 4-14 hours, such as 12 hours.

[0066] Regarding step S5):

[0067] Powder C was calcined in an air atmosphere to obtain powder D.

[0068] The calcination temperature is 400-600° C., such as 400° C., 500° C. or 600° C., and the calcination time is 4-6 hours, such as 4 hours or 6 hours. The calcination is carried out in a muffle furnace.

[0069] After the calcination, the method further comprises cooling, wherein the cooling may be natural cooling to room temperature.

[0070] Regarding step S6):

[0071] The powder D was subjected to reduction treatment in a hydrogen atmosphere to obtain a catalyst.

[0072] The reduction treatment is performed at a temperature of 300 to 500° C., such as 300° C., 400° C. or 500° C., for 1 to 5 hours, such as 1 hour, 3 hours or 5 hours. The reduction is performed in a tubular furnace.

[0073] After the reduction treatment, the process further includes cooling, which may be natural cooling to room temperature.

[0074] The present invention also provides a catalyst prepared by the preparation method described above.

[0075] The present invention also provides an application of the above-mentioned catalyst in a catalytic hydrogenation synthesis reaction, specifically, the catalyst can be used as a catalyst for preparing 1,3-propylene glycol by hydrogenolysis of glycerol.

[0076] The present invention also provides a method for preparing 1,3-propylene glycol, comprising the following steps:

[0077] Glycerol, water and a catalyst are subjected to a catalytic hydrogenation reaction at 160 to 220° C. under a hydrogen atmosphere to obtain 1,3-propylene glycol;

[0078] The catalyst is the catalyst described above.

[0079] The mass ratio of the glycerol, water and catalyst is 1.8-120:10-180:1, such as 120:30:1, 60:15:1, 30:45:1, 60:90:1.

[0080] The catalytic hydrogenation reaction time is 3 to 48 hours. The catalytic hydrogenation reaction is carried out in a high-pressure reactor. The catalytic hydrogenation reaction is carried out under stirring conditions, and the stirring speed is 200 to 1000 r / min.

[0081] After the catalytic hydrogenation reaction, the method further comprises: purification.

[0082] Before the purification, the process also includes: naturally cooling to room temperature.

[0083] The purification comprises:

[0084] The filtrate is filtered and separated by rectification to obtain 1,3-propylene glycol.

[0085] The filtrate includes isopropanol, n-propanol, 1,2-propylene glycol, 1,3-propylene glycol and unreacted glycerol. After distillation separation, isopropanol, 1,2-propylene glycol and unreacted glycerol can be removed, and 1,3-propylene glycol and n-propanol can be separated at the same time.

[0086] The present invention has no particular limitation on the distillation separation method, and any distillation separation method well known to those skilled in the art may be used.

[0087] The present invention has no particular limitation on the sources of the raw materials used above, and they can be generally commercially available.

[0088] Beneficial effects:

[0089] 1. The catalyst prepared by the present invention can realize efficient catalytic hydrogenolysis of glycerol to produce 1,3-propylene glycol and co-produce n-propanol by rationally selecting active components with specific proportions and appropriate catalyst carriers, and can be recycled for multiple times.

[0090] 2. In the catalyst preparation process of the present invention, microwave, ultraviolet, ultrasonic and other methods are selected for enhanced impregnation, which greatly improves the preparation efficiency. On the basis of the traditional impregnation method, the catalyst preparation time is shortened and the catalyst performance is improved.

[0091] 3. The present invention can efficiently catalyze the hydrogenolysis of glycerol to prepare 1,3-propylene glycol at high glycerol concentrations, and has the characteristics of high efficiency, few by-products, and easy separation and purification.

[0092] In order to further illustrate the present invention, a catalyst provided by the present invention, its preparation method and application are described in detail below in conjunction with examples, but it should not be understood as limiting the scope of protection of the present invention.

[0093] Comparative Example 1

[0094] Pt / WO x / Al2O3 catalyst preparation:

[0095] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0096] S2. After immersion for 0.5 h, age at room temperature for 6 h, dry at 90°C for 12 h, and grind to obtain powder A.

[0097] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0098] S4. Take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (aqueous solution of chloroplatinic acid), add it dropwise onto powder B, mix them in equal volumes, soak for 2 hours, age at room temperature for 6 hours, and dry at 90°C for 12 hours to obtain powder C.

[0099] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0100] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0101] Example 1

[0102] Preparation of Pt / NaW / Al2O3-MW catalyst:

[0103] S1. Dissolve 0.6 g of sodium tungstate in deionized water to obtain a solution with a concentration of 0.1 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0104] S2. Microwave irradiation (frequency is 2500 MHz) is used to assist the impregnation for 2 hours, aged at room temperature for 6 hours, dried at 90° C. for 12 hours, and powder A is obtained after crushing.

[0105] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0106] S4. Take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (aqueous solution of chloroplatinic acid), add it dropwise onto powder B, mix them in equal volumes, use microwave irradiation (frequency of 2500 MHz) to assist in impregnation for 2 hours, age at room temperature for 6 hours, and dry at 90°C for 12 hours to obtain powder C.

[0107] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0108] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0109] Example 2

[0110] Preparation of Pt / NaW / ZrO2-MW catalyst:

[0111] S1. Dissolve 0.6 g of sodium tungstate in deionized water to obtain a solution with a concentration of 0.1 g / mL, and add it dropwise onto 2.5 g of nano zirconium oxide carrier until the cup stands upright and equal volumes are mixed.

[0112] S2. Microwave irradiation (frequency is 2500 MHz) is used to assist the impregnation for 2 hours, aged at room temperature for 6 hours, dried at 90° C. for 12 hours, and powder A is obtained after crushing.

[0113] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0114] S4. Take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (aqueous solution of chloroplatinic acid), add it dropwise onto powder B, mix them in equal volumes, use microwave irradiation (frequency of 2500 MHz) to assist in impregnation for 2 hours, age at room temperature for 6 hours, and dry at 90°C for 12 hours to obtain powder C.

[0115] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0116] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0117] Example 3

[0118] Preparation of Pt / NaW / SiO2-MW catalyst:

[0119] S1. Dissolve 0.6 g of sodium tungstate in deionized water to obtain a solution with a concentration of 0.1 g / mL, and add it dropwise onto 2.5 g of nano-silica carrier until the cup stands upright and equal volumes are mixed.

[0120] S2. Microwave irradiation (frequency is 2500 MHz) is used to assist the impregnation for 2 hours, aged at room temperature for 6 hours, dried at 90° C. for 12 hours, and powder A is obtained after crushing.

[0121] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0122] S4. Take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (aqueous solution of chloroplatinic acid), add it dropwise onto powder B, mix them in equal volumes, use microwave irradiation (frequency of 2500 MHz) to assist in impregnation for 2 hours, age at room temperature for 6 hours, and dry at 90°C for 12 hours to obtain powder C.

[0123] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0124] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0125] Example 4

[0126] Pt / WO x / Al2O3-MW catalyst preparation:

[0127] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0128] S2. Microwave irradiation (frequency is 2500 MHz) is used to assist the impregnation for 2 hours, aged at room temperature for 6 hours, dried at 90° C. for 12 hours, and powder A is obtained after crushing.

[0129] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0130] S4. Take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (aqueous solution of chloroplatinic acid), add it dropwise onto powder B, mix them in equal volumes, use microwave irradiation (frequency of 2500 MHz) to assist in impregnation for 2 hours, age at room temperature for 6 hours, and dry at 90°C for 12 hours to obtain powder C.

[0131] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0132] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0133] Example 5

[0134] Preparation of Pt / PW / Al2O3 catalyst:

[0135] S1. Take 0.5 g of phosphotungstic acid and dissolve it in deionized water to obtain a solution with a concentration of 0.083 g / mL, and add it dropwise onto 2.5 g of nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0136] S2. Microwave irradiation (frequency is 2500 MHz) is used to assist the impregnation for 2 hours, aged at room temperature for 6 hours, dried at 90° C. for 12 hours, and powder A is obtained after crushing.

[0137] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0138] S4. Take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (aqueous solution of chloroplatinic acid), add it dropwise onto powder B, mix them in equal volumes, use microwave irradiation (frequency of 2500 MHz) to assist in impregnation for 2 hours, age at room temperature for 6 hours, and dry at 90°C for 12 hours to obtain powder C.

[0139] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0140] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0141] Example 6

[0142] Preparation of Pt / W / Al2O3-MW catalyst:

[0143] S1. Take 0.5g of tungstic acid and dissolve it in deionized water to obtain a solution with a concentration of 0.083g / mL, and add it dropwise onto 2.5g of nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0144] S2. Microwave irradiation (frequency is 2500 MHz) is used to assist the impregnation for 2 hours, aged at room temperature for 6 hours, dried at 90° C. for 12 hours, and powder A is obtained after crushing.

[0145] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0146] S4. Take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (aqueous solution of chloroplatinic acid), add it dropwise onto powder B, mix them in equal volumes, use microwave irradiation (frequency of 2500 MHz) to assist in impregnation for 2 hours, age at room temperature for 6 hours, and dry at 90°C for 12 hours to obtain powder C.

[0147] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0148] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0149] Example 7

[0150] Pt / WO x / Al2O3-US catalyst preparation:

[0151] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0152] S2. Ultrasonic irradiation (frequency of 40 KHz, power of 100 W) was used to assist the impregnation for 0.5 h, aged at room temperature for 6 h, dried at 90° C. for 12 h, and powder A was obtained after crushing.

[0153] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0154] S4. Take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (aqueous solution of chloroplatinic acid), add it dropwise onto powder B, mix them in equal volumes, use microwave irradiation (frequency of 2500 MHz) to assist in impregnation for 2 hours, age at room temperature for 6 hours, and dry at 90°C for 12 hours to obtain powder C.

[0155] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0156] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0157] Example 8

[0158] Pt / WO x / Al2O3-UV catalyst preparation:

[0159] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0160] S2, using ultraviolet radiation (the wavelength of ultraviolet radiation is 350nm, the light intensity is 8mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, dried at 90°C for 12 h, and powder A was obtained after crushing.

[0161] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0162] S4, take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (chloroplatinic acid aqueous solution), add it dropwise onto powder B, mix them in equal volumes, and irradiate with ultraviolet light (the wavelength of ultraviolet light is 350 nm, the light intensity is 8 mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, and dried at 90°C for 12 h to obtain powder C.

[0163] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0164] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0165] Figure 1 Pt / WO prepared in Example 8 of the present invention x / Transmission electron microscopy image (TEM image) of Al2O3-UV catalyst;

[0166] Figure 2 Pt / WO prepared in Example 8 of the present invention x / Al2O3-UV catalyst X-ray diffraction pattern (XRD pattern).

[0167] Example 9

[0168] Pt / WO x / Al2O3-UV catalyst preparation:

[0169] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0170] S2, using ultraviolet radiation (the wavelength of ultraviolet radiation is 350nm, the light intensity is 8mW / cm 2 ) was used as an auxiliary means for impregnation for 2 h, aged at room temperature for 6 h, dried at 90°C for 12 h, and powder A was obtained after crushing.

[0171] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0172] S4, take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (chloroplatinic acid aqueous solution), add it dropwise onto powder B, mix them in equal volumes, and irradiate with ultraviolet light (the wavelength of ultraviolet light is 350 nm, the light intensity is 8 mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, and dried at 90°C for 12 h to obtain powder C.

[0173] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0174] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0175] Example 10

[0176] Pt / WO x / Al2O3-UV catalyst preparation:

[0177] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0178] S2, using ultraviolet radiation (the wavelength of ultraviolet radiation is 350nm, the light intensity is 8mW / cm 2 ) was used as an auxiliary means for impregnation for 1 hour, aged at room temperature for 6 hours, dried at 90°C for 12 hours, and powder A was obtained after crushing.

[0179] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0180] S4, take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (chloroplatinic acid aqueous solution), add it dropwise onto powder B, mix them in equal volumes, and irradiate with ultraviolet light (the wavelength of ultraviolet light is 350 nm, the light intensity is 8 mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, and dried at 90°C for 12 h to obtain powder C.

[0181] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0182] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0183] Embodiment 11

[0184] Pt / WO x / Al2O3-UV catalyst preparation:

[0185] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0186] S2, using ultraviolet radiation (the wavelength of ultraviolet radiation is 350nm, the light intensity is 8mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, dried at 90°C for 12 h, and powder A was obtained after crushing.

[0187] S3. Powder A is placed in a muffle furnace, calcined at 450° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0188] S4, take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (chloroplatinic acid aqueous solution), add it dropwise onto powder B, mix them in equal volumes, and irradiate with ultraviolet light (the wavelength of ultraviolet light is 350 nm, the light intensity is 8 mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, and dried at 90°C for 12 h to obtain powder C.

[0189] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0190] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0191] Example 12

[0192] Pt / WO x / Al2O3-UV catalyst preparation:

[0193] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0194] S2, using ultraviolet radiation (the wavelength of ultraviolet radiation is 350nm, the light intensity is 8mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, dried at 90°C for 12 h, and powder A was obtained after crushing.

[0195] S3. Powder A is placed in a muffle furnace, calcined at 300° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0196] S4, take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (chloroplatinic acid aqueous solution), add it dropwise onto powder B, mix them in equal volumes, and irradiate with ultraviolet light (the wavelength of ultraviolet light is 350 nm, the light intensity is 8 mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, and dried at 90°C for 12 h to obtain powder C.

[0197] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0198] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 5 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0199] Embodiment 13

[0200] Pt / WO x / Al2O3-UV catalyst preparation:

[0201] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0202] S2, using ultraviolet radiation (the wavelength of ultraviolet radiation is 350nm, the light intensity is 8mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, dried at 90°C for 12 h, and powder A was obtained after crushing.

[0203] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0204] S4, take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (chloroplatinic acid aqueous solution), add it dropwise onto powder B, mix them in equal volumes, and irradiate with ultraviolet light (the wavelength of ultraviolet light is 350 nm, the light intensity is 8 mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, and dried at 90°C for 12 h to obtain powder C.

[0205] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0206] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 1 h under a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0207] Embodiment 14

[0208] Pt / WO x / Al2O3-UV catalyst preparation:

[0209] S1. Dissolve 0.4 g of ammonium metatungstate in deionized water to obtain a solution with a concentration of 0.067 g / mL, and add it dropwise onto 2.5 g of the nano-alumina carrier until the cup stands upright and equal volumes are mixed.

[0210] S2, using ultraviolet radiation (the wavelength of ultraviolet radiation is 350nm, the light intensity is 8mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, dried at 90°C for 12 h, and powder A was obtained after crushing.

[0211] S3. Powder A is placed in a muffle furnace, calcined at 600° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder B.

[0212] S4, take 2.5 mL of the prepared 0.1 g / mL chloroplatinic acid precursor solution (chloroplatinic acid aqueous solution), add it dropwise onto powder B, mix them in equal volumes, and irradiate with ultraviolet light (the wavelength of ultraviolet light is 350 nm, the light intensity is 8 mW / cm 2 ) was used as an auxiliary means for impregnation for 0.5 h, aged at room temperature for 6 h, and dried at 90°C for 12 h to obtain powder C.

[0213] S5. Powder C is placed in a muffle furnace, calcined at 400° C. for 4 h in an air atmosphere, and naturally cooled to room temperature to obtain powder D.

[0214] S6. Powder D was transferred into a tube furnace and subjected to reduction treatment at 300° C. for 3 h in a hydrogen atmosphere, and then naturally cooled to room temperature to obtain a catalyst.

[0215] Application Example 1

[0216] Synthesis of 1,3-propylene glycol:

[0217] 1) Mix 12 g of glycerol, 3 g of water and 0.1 g of catalyst in an autoclave, seal the autoclave and replace with hydrogen 4 times;

[0218] 2) Turn on the stirrer and adjust the speed to 200r / min. When the temperature of the high-pressure reactor rises to the reaction temperature of 180°C, adjust the speed to 1000r / min to carry out catalytic hydrogenation reaction for 48h;

[0219] 3) After the reaction is completed, the mixture is naturally cooled to room temperature, the catalyst is taken out and filtered out to obtain isopropanol, n-propanol, 1,2-propylene glycol, 1,3-propylene glycol and unreacted glycerol filtrate, and 1,3-propylene glycol product is obtained after distillation and separation.

[0220] Application Example 2

[0221] Synthetic n-propanol:

[0222] 1) Mix 12g of glycerol, 3g of water and 0.2g of catalyst in an autoclave, seal the autoclave and replace with hydrogen 4 times;

[0223] 2) Turn on the stirrer and adjust the speed to 200r / min. When the temperature of the high-pressure reactor rises to the reaction temperature of 180°C, adjust the speed to 1000r / min to carry out catalytic hydrogenation reaction for 48h;

[0224] 3) After the reaction is completed, the mixture is naturally cooled to room temperature, the catalyst is taken out and filtered out to obtain isopropanol, n-propanol, 1,2-propylene glycol, 1,3-propylene glycol and unreacted glycerol filtrate, and n-propanol is obtained after distillation and separation.

[0225] Application Example 3

[0226] Synthesis of 1,3-propylene glycol:

[0227] 1) Mix 6 g of glycerol, 9 g of water and 0.2 g of catalyst in an autoclave, seal the autoclave and replace with hydrogen 4 times;

[0228] 2) Turn on the stirrer and adjust the speed to 200r / min. When the temperature of the high-pressure reactor rises to the reaction temperature of 180°C, adjust the speed to 1000r / min to carry out catalytic hydrogenation reaction for 24h;

[0229] 3) After the reaction is completed, the mixture is naturally cooled to room temperature, the catalyst is taken out and filtered out to obtain isopropanol, n-propanol, 1,2-propylene glycol, 1,3-propylene glycol and unreacted glycerol filtrate, and 1,3-propylene glycol product is obtained after distillation and separation.

[0230] Application Example 4

[0231] Synthetic n-propanol:

[0232] 1) Mix 6 g of glycerol, 9 g of water and 0.1 g of catalyst in an autoclave, seal the autoclave and replace with hydrogen 4 times;

[0233] 2) Turn on the stirrer and adjust the speed to 200r / min. When the temperature of the high-pressure reactor rises to the reaction temperature of 180°C, adjust the speed to 1000r / min to carry out catalytic hydrogenation reaction for 24h;

[0234] 3) After the reaction is completed, the mixture is naturally cooled to room temperature, the catalyst is taken out and filtered out to obtain isopropanol, n-propanol, 1,2-propylene glycol, 1,3-propylene glycol and unreacted glycerol filtrate, and n-propanol is obtained after distillation and separation.

[0235] Figure 3 This is the liquid chromatogram of the solution after the reaction in step 2) of Application Example 4.

[0236] The same mass of 1,3-propylene glycol products synthesized by the catalysts prepared in Comparative Example 1 and Examples 1 to 14 (according to Application Example 3) were taken respectively, and the 1,3-propylene glycol in all the products was determined by high performance liquid chromatography, and the conversion rate, selectivity and yield of 1,3-propylene glycol were calculated. The evaluation parameters are shown in Table 1.

[0237] Table 1 Catalytic performance of the catalysts obtained in Examples 1 to 14 for hydrogenation of glycerol to produce 1,3-propylene glycol

[0238]

[0239] It can be seen from Table 1 that the catalytic performance and selectivity of the synthesized catalysts are relatively high under Examples 1 to 14. It can be seen from the data analysis of Examples 1 to 3 in Table 1 that in the preparation process of the catalyst, the catalyst carrier in Example 1 is the best to use Al2O3, and the catalyst prepared therefrom is used to synthesize 1,3-propylene glycol, and the selectivity of 1,3-propylene glycol is the highest.

[0240] Through the data analysis of Examples 4 to 6 in Table 1, it can be seen that in the preparation process of the catalyst, the ammonium metatungstate in Example 4 is the best precursor, and the yield of the catalyst 1,3-propylene glycol prepared therefrom is the highest.

[0241] Through the data analysis of Comparative Example 1, Examples 7 and 8 in Table 1, it can be seen that in the preparation process of the catalyst, the catalyst prepared by the UV-enhanced impregnation method in Example 8 is the best, and the catalyst prepared therefrom has the highest yield of 1,3-propylene glycol.

[0242] Through the data analysis of Examples 8, 9 and 10 in Table 1, it can be seen that in the preparation process of the catalyst, the treatment time of 0.5h in Example 8 is the best, the results caused by each treatment time are not much different, and the catalyst prepared therefrom has the highest yield of 1,3-propylene glycol.

[0243] Through the data analysis of Examples 8, 11 and 12 in Table 1, it can be seen that in the preparation process of the catalyst, the calcination temperature of 450° C. in Example 11 is optimal, and the yield of 1,3-propylene glycol prepared by the catalyst is the highest.

[0244] Through the data analysis of Examples 8, 13 and 14 in Table 1, it can be seen that in the preparation process of the catalyst, the reduction time of 5 h in Example 8 is optimal, and the yield of 1,3-propylene glycol prepared by the catalyst is the highest.

[0245] Table 2 Orthogonal experimental design factors and levels

[0246]

[0247] Table 3 Orthogonal experimental scheme and experimental results analysis

[0248]

[0249]

[0250] Through the analysis of the orthogonal experimental data in Table 2 and Table 3, it can be known that the experimental scheme of the type of tungsten precursor in step S1, the auxiliary impregnation means and the auxiliary impregnation time in step S2, the calcination temperature in step S3, and the reduction time in step S5 is as follows: the tungsten precursor in step S1 is ammonium metatungstate, the auxiliary impregnation means in step S2 is ultraviolet, the auxiliary impregnation time is 0.5h, the calcination temperature in step S3 is 450°C, and the reduction time in step S5 is 5h. The yield of the catalyst 1,3-propylene glycol prepared under these conditions is 43.7%.

[0251] The n-propanol products were synthesized using the catalysts prepared in Comparative Example 1 and Example 11 (according to Application Example 4). The n-propanol contents in all the products were determined by HPLC, and the conversion rate, selectivity and yield of n-propanol were calculated. The evaluation parameters are shown in Table 4.

[0252] Table 4 Catalytic performance of the catalysts obtained in Comparative Example 1 and Example 11 for hydrogenation of glycerol to produce n-propanol

[0253]

[0254] It can be seen from Table 4 that, compared with Comparative Example 1, the catalyst prepared in Example 11 can significantly improve the catalyst performance.

[0255] The description of the above embodiments is only used to help understand the method of the present invention and its core idea. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but will conform to the widest range consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a catalyst, comprising the following steps: S1) dropping a tungsten-containing precursor solution onto a metal oxide support and mixing them in equal volumes; The tungsten-containing precursor is selected from at least one of ammonium tungstate, ammonium metatungstate, tungstic acid, sodium tungstate and phosphotungstic acid; S2) after auxiliary impregnation by strengthening means, aging at room temperature, drying, and crushing to obtain powder A; the strengthening means is selected from at least one of microwave irradiation, ultraviolet irradiation and ultrasonic irradiation; S3) calcining the powder A in an air atmosphere to obtain powder B; S4) dropping the chloroplatinic acid precursor solution onto the powder B, mixing them in equal volumes, and using the strengthening means to assist in impregnation, aging at room temperature, and drying to obtain powder C; S5) calcining the powder C in an air atmosphere to obtain powder D; S6) subjecting the powder D to reduction treatment under a hydrogen atmosphere to obtain a catalyst.

2. The preparation method according to claim 1, characterized in that: In step S1), the metal oxide carrier is a nano-scale oxide powder, selected from at least one of nano-aluminum oxide, nano-silicon oxide and nano-zirconium oxide.

3. The preparation method according to claim 1, characterized in that: In step S1), the tungsten-containing precursor solution is obtained by dissolving a tungsten-containing precursor in deionized water; the concentration of the tungsten-containing precursor solution is 0.005-0.5 mol / L.

4. The preparation method according to claim 1, characterized in that: In step S2), the frequency of the microwave irradiation is 2000-3000 MHz; the wavelength of the ultraviolet irradiation is ≤400 nm, and the light intensity is 4-16 mW / cm 2 ; The frequency of the ultrasonic irradiation is 30 to 50 KHz, and the power is 70 to 150 W; The auxiliary impregnation time is 0.5 to 2 hours; the aging time is 2 to 10 hours.

5. The preparation method according to claim 1, characterized in that: In step S3), the calcination temperature is 300-600°C and the calcination time is 4-6 hours; After the calcination, the process further comprises cooling.

6. The preparation method according to claim 1, characterized in that: In step S4), the chloroplatinic acid precursor solution is obtained by dissolving chloroplatinic acid in deionized water; the concentration of the chloroplatinic acid precursor solution is 0.01 to 0.5 g / mL; The frequency of the microwave irradiation is 2000-3000 MHz; the wavelength of the ultraviolet irradiation is ≤400 nm, and the light intensity is 4-16 mW / cm 2 ; The frequency of the ultrasonic irradiation is 30 to 50 KHz, and the power is 70 to 150 W; The auxiliary impregnation time is 0.5 to 2 hours; the aging time is 2 to 10 hours.

7. The preparation method according to claim 1, characterized in that: In step S5), the calcination temperature is 400-600°C and the calcination time is 4-6 hours; After the calcination, the process further comprises cooling.

8. The preparation method according to claim 1, characterized in that: In step S6), the reduction treatment temperature is 300-500°C and the time is 1-5h; After the reduction treatment, the method further comprises cooling.

9. The catalyst obtained by the preparation method according to any one of claims 1 to 8.

10. Use of the catalyst according to claim 9 in catalytic hydrogenation synthesis reaction.

11. A method for preparing 1,3-propylene glycol and / or n-propanol, comprising the following steps: Carrying out a catalytic hydrogenation reaction of glycerol, water and a catalyst under a hydrogen atmosphere at 160 to 220° C. to obtain 1,3-propylene glycol and / or n-propanol; The catalyst is the catalyst according to claim 9.

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