CN111036203B - Niobium-containing catalyst, preparation method and application thereof, and glycerol hydrogenolysis method - Google Patents
Niobium-containing catalyst, preparation method and application thereof, and glycerol hydrogenolysis method Download PDFInfo
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Abstract
The invention relates to the field of glycerol hydrogenolysis, and discloses a niobium-containing catalyst, a preparation method and application thereof, and a glycerol hydrogenolysis method, wherein the catalyst comprises an alumina-containing carrier, a first active metal component and a second active metal component which are loaded on the alumina-containing carrier, and a niobium element, the first active metal component is at least one selected from Pt, ir, rh and Pd, the second active metal component is at least one selected from Zr, ta, mn, W and Re, and the catalyst meets the requirement of (Nb/Al) XPS /(Nb/Al) XRF =2-20, wherein (Nb/Al) XPS The weight ratio of niobium to aluminum in the catalyst is characterized by X-ray photoelectron spectroscopy, (Nb/Al) XRF The weight ratio of niobium element to aluminum element in the catalyst is characterized by X-ray fluorescence spectrum. The niobium-containing catalyst provided by the invention has higher activity and selectivity in the glycerin hydrogenolysis reaction process, and is particularly suitable for higher reaction temperature.
Description
Technical Field
The invention relates to the field of glycerol hydrogenolysis, in particular to a niobium-containing catalyst, a preparation method and application thereof, and a glycerol hydrogenolysis method.
Background
1,3-propylene glycol (1,3-PDO) is an important organic chemical raw material, and the most important purpose is to be used as a raw material of a novel polyester material, namely 1,3-propylene glycol terephthalate (PTT). The PTT fiber is generally considered to gradually replace terylene and chinlon to become large-scale fiber in the 21 st century, and has wide application prospect. In addition, the byproduct glycerol in the production process of the biodiesel is seriously excessive, and the research on the deep processing technology of the glycerol has important significance. Therefore, the preparation of 1,3-propanediol by using glycerol as a raw material is widely considered as a conversion way with important application prospect.
At present, the main methods for producing 1,3-propylene glycol from glycerol include a biological fermentation method, an ethylene oxide carbonylation method, an acrolein hydration and hydrogenation method, a one-step hydrogenation method and the like. The feedstocks for both the ethylene oxide carbonylation process and the acrolein hydrohydrogenation process are derived from petroleum and their development is limited by the petroleum feedstock. The one-step hydrogenation method has the advantages of wide raw material adaptability, short process flow, low hydrogen consumption, little environmental pollution, low toxicity and the like, and has important application prospect.
The literature (Green Chemistry,2011, 2004) uses Pt-coated/ZrO 2 The catalyst takes DMI as a solvent, and the conversion rate and the selectivity of glycerol are both high (83.5%) at the temperature of 170 ℃ and the pressure of 7.3MPa, but the disclosed method has the problems of high reaction pressure, environmental pollution of organic solvents and the like.
CN106588570A discloses a catalyst for preparing 1,3-propylene glycol by glycerol hydrogenation, which is characterized in that: it is ZrO 2 As a carrier, sequentially loading W, nb and Pt salt solution on ZrO by an impregnation method 2 In the catalyst, WO 3 、Nb 2 O 5 And Pt exists in a form, and the percentage contents of the Pt and the Pt in the catalyst are respectively as follows: WO 3 ：2.5-4.5％；Nb 2 O 5 ：0.3-2％；Pt：0.5-2%, the rest is carrier ZrO 2 Pt-Nb of (3) 2 O 5 /WO 3 /ZrO 2 A catalyst. But the selectivity of the catalyst is still low.
CN104582839A discloses a Pt-WOx catalyst using boehmite as a carrier, but the overall activity of the disclosed catalyst is low.
At present, 1,3-propylene glycol prepared by a glycerol one-step hydrogenation method generally has the problems of low catalyst activity, low 1,3-propylene glycol selectivity, low space-time yield, high catalyst cost and the like. Therefore, how to improve the utilization rate of active metals (such as Pt, ir, etc.), the selectivity of the catalyst, and reduce the cost of the catalyst has been a difficult point and a direction for the development of the glycerol hydrogenolysis catalyst.
Disclosure of Invention
The invention aims to overcome the defects of low activity and poor selectivity of a glycerol hydrogenolysis catalyst in the prior art, and provides a niobium-containing catalyst, a preparation method and application thereof and a glycerol hydrogenolysis method. The niobium-containing catalyst provided by the invention has higher activity and selectivity in the glycerin hydrogenolysis reaction process, and is particularly suitable for higher reaction temperature.
In order to achieve the above object, the present invention provides, in one aspect, a niobium-containing catalyst comprising an alumina-containing support, and a first active metal component and a second active metal component, which are supported on the alumina-containing support, the first active metal component being selected from at least one of Pt, ir, rh and Pd, and the second active metal component being selected from at least one of Zr, ta, mn, W and Re, and niobium, the catalyst satisfying (Nb/Al) XPS /(Nb/Al) XRF =2-20, wherein (Nb/Al) XPS The weight ratio of niobium to aluminum in the catalyst is characterized by X-ray photoelectron spectroscopy, (Nb/Al) XRF The weight ratio of niobium element to aluminum element in the catalyst is characterized by X-ray fluorescence spectrum.
Preferably, the molar ratio of niobium to the second active metal component is from 0.2 to 4:1, preferably 1 to 1.5:1.
in a second aspect, the present invention provides a method for preparing a niobium-containing catalyst, the method comprising:
(1) Impregnating an alumina-containing carrier with a solution containing a niobium-containing compound, and then drying and roasting the obtained solid material to obtain a niobium-modified carrier;
(2) Introducing a first active metal component selected from at least one of Pt, ir, rh and Pd and a second active metal component selected from at least one of Zr, ta, mn, W and Re onto the niobium-modified support by an impregnation process.
The preparation method of the catalyst provided by the invention is more beneficial to the dispersion of the first active metal component and the second active metal component and the interaction with the niobium modified carrier.
Preferably, in step (2), the second active metal component and the first active metal component are introduced sequentially onto the niobium modified support by an impregnation method.
In a third aspect, the present invention provides a niobium-containing catalyst obtained by the above-mentioned production method.
In a fourth aspect, the present invention provides the use of a niobium containing catalyst of the present invention in a hydrogenolysis reaction of glycerol.
In a fifth aspect, the present invention provides a glycerol hydrogenolysis method, including contacting a glycerol-containing raw material and hydrogen with a catalyst under a catalytic glycerol hydrogenolysis condition, wherein the catalyst is the niobium-containing catalyst provided by the present invention.
Compared with the catalyst with the same metal content prepared by the prior art, the catalyst containing niobium provided by the invention has obviously higher catalytic activity and selectivity for hydrogenolysis of glycerol.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides, in a first aspect, a niobium-containing catalyst comprising an alumina-containing support, and a first active metal component and a second active metal component both supported on the alumina-containing support, the first active metal component being selected from at least one of Pt, ir, rh and Pd, and the second active metal component being selected from at least one of Zr, ta, mn, W and Re, and niobium, the catalyst satisfying (Nb/Al) XPS /(Nb/Al) XRF =2-20, wherein (Nb/Al) XPS The weight ratio of niobium to aluminum in the catalyst is characterized by X-ray photoelectron spectroscopy, (Nb/Al) XRF The weight ratio of niobium element to aluminum element in the catalyst is characterized by X-ray fluorescence spectrum.
In the present invention, (Nb/Al) XPS The weight ratio of niobium element to aluminum element in the catalyst characterized by X-ray photoelectron spectroscopy is obtained by conversion of the peak area of the characteristic peak of the corresponding element. The measuring instrument for the X-ray photoelectron spectroscopy is an ESCALB 250 type instrument of Thermo Scientific company, and the measuring conditions are as follows: the excitation source was a 150kW monochromator Al K.alpha.X-ray, and the binding energy was corrected for the C1 s peak (284.8 eV).
In the present invention, (Nb/Al) XRF The weight ratio of niobium element to aluminum element in the catalyst characterized by X-ray fluorescence spectrum is shown, wherein a measuring instrument of the X-ray fluorescence spectrum is a 3271 instrument of Nippon science and electronics industry Co., ltd, and the measuring conditions are as follows: and tabletting and molding the powder sample, wherein the rhodium target is subjected to laser voltage of 50kV and laser current of 50mA.
According to a preferred embodiment of the present invention, the catalyst satisfies (Nb/Al) XPS /(Nb/Al) XRF =3-15, preferably the catalyst satisfies (NbAl) XPS /(Nb/Al) XRF =4-12, further preferably, the catalyst satisfies (NbAl) XPS /(Nb/Al) XRF ＝7-11.5。
According to the niobium-containing catalyst provided by the invention, preferably, the content of the niobium element is 0.1-15 wt%, the content of the first active metal component is 0.05-10 wt%, and the content of the second active metal component is 0.1-20 wt% based on the total amount of the catalyst.
More preferably, the content of the niobium element is 0.5 to 10% by weight, the content of the first active metal component is 0.1 to 8% by weight, and the content of the second active metal component is 0.5 to 15% by weight, based on the total amount of the catalyst.
Further preferably, the content of the niobium element is 1 to 8% by weight, the content of the first active metal component is 0.5 to 5% by weight, and the content of the second active metal component is 2 to 12% by weight, based on the total amount of the catalyst.
The content of each component in the niobium-containing catalyst can be measured by X-ray fluorescence spectrum analysis.
According to a preferred embodiment of the present invention, the molar ratio of niobium to the second active metal component is 0.2 to 4:1, preferably 1 to 1.5:1. with this preferred embodiment, it is more advantageous to increase the activity and selectivity of the catalyst.
According to the niobium-containing catalyst provided by the invention, preferably, the first active metal component is Pt and/or Ir, and further preferably Pt.
According to the niobium-containing catalyst provided by the present invention, preferably, the second active metal component is W and/or Re, and more preferably W.
According to one embodiment of the invention, the first active metal component is Pt and the second active metal component is W; alternatively, the first active metal component is Ir and the second active metal component is Re.
According to a preferred embodiment of the present invention, the alumina-containing support is selected from at least one of alumina, alumina-magnesia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia, more preferably, the alumina is present in an amount of more than 60% by weight, based on the total amount of alumina-containing support.
In a second aspect, the present invention provides a method for preparing a niobium-containing catalyst, the method comprising:
(1) Impregnating an alumina-containing carrier with a solution containing a niobium-containing compound, and then drying and roasting the obtained solid material to obtain a niobium-modified carrier;
(2) Introducing a first active metal component selected from at least one of Pt, ir, rh and Pd and a second active metal component selected from at least one of Zr, ta, mn, W and Re onto the niobium-modified support by an impregnation process.
According to the present invention, the niobium-containing compound may be dissolved in water or an organic solvent (ethanol), and the niobium-containing compound may be at least one selected from niobium oxalate, niobium chloride, niobium oxychloride and niobium fluoride, and is preferably niobium oxalate.
The selection of the alumina-containing carrier is as described above and will not be described herein.
The impregnation in step (1) can be carried out by conventional impregnation means in the art, and preferably, the specific embodiment of the impregnation in step (1) comprises: the alumina-containing support is mixed with the solution containing the niobium-containing compound (the temperature may be room temperature, preferably for not less than 5min, for example, may be 5 to 15min, preferably under stirring), and then subjected to rotary evaporation.
In the solution containing the niobium-containing compound in the step (1), the concentration of the niobium-containing compound in terms of niobium element is preferably 0.2 to 200 g/l, and more preferably 1 to 100 g/l.
In the present invention, the drying conditions in step (1) are not particularly limited, and preferably, the drying conditions include: the temperature is 80-350 deg.C, and the time is 0.01-24 hr, preferably 100-250 deg.C, and the time is 1-12 hr.
According to a preferred embodiment of the present invention, the firing conditions in step (1) include: the temperature is 300-1200 ℃, the temperature is preferably 350-1000 ℃, and the temperature is preferably 600-800 ℃; the time is 0.5 to 12 hours, more preferably 1 to 10 hours, and still more preferably 2 to 6 hours.
In the present invention, in the step (2), as long as the first active metal component and the second active metal component are introduced onto the niobium-modified support by an impregnation method, a specific introduction manner is not particularly limited, and the first active metal component and the second active metal component may be introduced together by a co-impregnation method, or the first active metal component may be introduced first and then the second active metal component may be introduced, or the second active metal component may be introduced first and then the first active metal component may be introduced.
According to a preferred embodiment of the present invention, in step (2), the second active metal component and the first active metal component are sequentially introduced onto the niobium modified support by an impregnation method. Preferably, step (2) comprises:
a) Impregnating the niobium-modified support with a solution containing a compound of a second active metal component, drying and optionally calcining the resulting solid material to obtain a catalyst precursor containing the second active metal component;
b) The catalyst precursor containing the second active metal component is impregnated with a solution containing a compound of the first active metal component and the resulting solid mass is dried and optionally calcined.
The inventors of the present invention found in the research that, when the niobium-modified alumina is used as the support, the method of sequentially introducing the second active metal component and the first active metal component has higher activity and selectivity than the method of introducing the first active metal component first and then introducing the second active metal component, and the method of introducing the first active metal component and the second active metal component together.
According to the preparation method provided by the present invention, the step a) and the step b) may or may not be performed with calcination, and the present invention is not particularly limited thereto.
According to a specific embodiment of the present invention, the compound of the first active metal component is selected from at least one of nitrate, acetate, hydroxycarbonate, chloride of one or more of Pt, ir, rh and Pd-containing elements. For example, the compound of the first active metal component may be chloroplatinic acid and/or iridium chloride.
According to one embodiment of the invention, the compound of the second active metal component is selected from at least one of nitrate, acetate, hydroxycarbonate, chloride of one or more of the elements Zr, ta, mn, W, re. For example, the compound of the second active metal component may be ammonium metatungstate and/or perrhenic acid.
The selection of the first active metal component and the second active metal component is as described above and will not be described herein again.
The concentration of the solution containing the compound of the second active metal component in step a) is preferably 0.2 to 200 g/l, more preferably 1 to 100 g/l, in terms of the second active metal component (i.e., in terms of the metal element).
In step a), the impregnation may be performed by means of impregnation conventional in the art, and preferably, the specific embodiment of the impregnation in step a) comprises: the niobium-modified support is mixed with a solution of a compound containing the second active metal component (the temperature may be room temperature, preferably for not less than 5min, for example, may be 5 to 15min, preferably under stirring), and then subjected to rotary evaporation.
In the present invention, the drying conditions in step a) are not particularly limited, and preferably, the drying conditions include: the temperature is 80-350 deg.C, and the time is 0.01-24 hr, preferably 100-250 deg.C, and the time is 1-12 hr.
According to a preferred embodiment of the present invention, the firing conditions of step a) include: the temperature is 300-900 deg.C, and the time is 0.5-12h, preferably 350-850 deg.C, and the time is 1-10h, preferably 400-800 deg.C, and the time is 2-8h.
The concentration of the compound containing the first active metal component in step b) is preferably 0.2 to 200 g/l, more preferably 1 to 100 g/l, in terms of the first active metal component (i.e., in terms of the metal element).
In step b), the impregnation may be carried out by conventional impregnation means in the art, and preferably, the specific embodiment of the impregnation in step b) comprises: the catalyst precursor containing the second active metal component is mixed with a solution of the compound containing the first active metal component (temperature may be room temperature, preferably for not less than 5min, for example, may be 5 to 15min, preferably under stirring), and then subjected to rotary evaporation.
The conditions for the rotary evaporation in steps (1), a) and (b) are not particularly limited in the present invention, and can be carried out according to the conventional conditions in the art. The conditions for rotary evaporation in steps (1), a) and b) may be the same or different. The conditions for rotary evaporation, such as described in steps (1), a), b), each independently include: the temperature is 20-90 ℃, preferably 30-75 ℃; the pressure is 0.001-0.05MPa, preferably 0.002-0.04MPa.
In the present invention, the drying conditions in step b) are not particularly limited, and preferably, the drying conditions include: the temperature is 80-350 deg.C, and the time is 0.01-24 hr, preferably 100-250 deg.C, and the time is 1-12 hr.
According to a preferred embodiment of the present invention, the firing conditions of step b) include: the temperature is 300-500 deg.C, and the time is 0.5-12h, preferably 300-450 deg.C, and the time is 1-10h, preferably 300-350 deg.C, and the time is 2-8h.
According to a preferred embodiment of the present invention, the niobium-containing compound, the alumina-containing support, the first active metal component and the second active metal component are used in such amounts that the resultant catalyst contains the niobium element in an amount of 0.1 to 15% by weight, the first active metal component in an amount of 0.05 to 10% by weight and the second active metal component in an amount of 0.1 to 20% by weight, based on the total amount of the catalyst.
More preferably, the niobium-containing compound, the alumina-containing support, the first active metal component and the second active metal component are used in amounts such that the resulting catalyst has a niobium element content of 0.5 to 10% by weight, a first active metal component content of 0.1 to 8% by weight and a second active metal component content of 0.5 to 15% by weight, based on the total amount of the catalyst.
Further preferably, the niobium-containing compound, the alumina-containing support, the first active metal component and the second active metal component are used in such amounts that the resultant catalyst contains the niobium element in an amount of 1 to 8% by weight, the first active metal component in an amount of 0.5 to 5% by weight and the second active metal component in an amount of 2 to 12% by weight, based on the total amount of the catalyst.
According to a preferred embodiment of the present invention, the molar ratio of the niobium-containing compound to the second active metal component, calculated as niobium element, is 0.2 to 4:1, preferably 1 to 1.5:1. the niobium-containing catalyst prepared by the preferred embodiment has higher catalyst activity and selectivity.
In a third aspect, the present invention provides a niobium-containing catalyst obtained by the above-mentioned preparation method.
In a fourth aspect, the present invention provides the use of a niobium containing catalyst of the present invention in a hydrogenolysis reaction of glycerol. The niobium-containing catalyst provided by the invention is applied to the hydrogenolysis reaction of glycerol, so that the catalyst has higher activity and selectivity, and in addition, the niobium-containing catalyst provided by the invention is suitable for higher reaction temperature (190-210 ℃).
According to the present invention, before the niobium-containing catalyst provided by the present invention is applied to the glycerol hydrogenolysis reaction, the niobium-containing catalyst is preferably used after being subjected to conventional reduction activation under a hydrogen-containing atmosphere. The conditions for reductive activation may include: the temperature is 100-800 ℃, preferably 120-600 ℃, and more preferably 150-400 ℃; the time is 0.5-72h, preferably 1-24h, more preferably 2-8h, and the hydrogen volume space velocity is 200-20000h -1 Preferably 300-15000h -1 More preferably 500 to 12000h -1 . The reduction activation may be performed in a pure hydrogen atmosphere, or may be performed in a mixed gas containing hydrogen and an inert gas, for example, in a mixed gas of hydrogen and nitrogen and/or argon. The hydrogen pressure may be from 0.01 to 4MPa, preferably from 0.1 to 2MPa.
In a fifth aspect, the invention provides a glycerol hydrogenolysis method, comprising contacting a glycerol-containing feedstock, hydrogen, and a catalyst under catalytic glycerol hydrogenolysis conditions, wherein the catalyst is the niobium-containing catalyst provided by the invention.
The apparatus for the hydrogenolysis of glycerol provided in accordance with the present invention can be carried out in any reactor sufficient to contact react the glycerol-containing feedstock with the niobium-containing catalyst under hydrogenation reaction conditions, such as a fixed bed reactor or an autoclave reactor.
The reaction conditions can be carried out by referring to the prior art, taking the evaluation of a fixed bed reactor as an example, in the raw material containing glycerol, the glycerol mass concentration is 5-95%, the solvent can be at least one of water, methanol, ethanol and propanol, the pressure is 0.1-8MPa, preferably 1-5MPa, more preferably 2-5MPa, the reaction temperature is 100-300 ℃, preferably 140-260 ℃, more preferably 190-210 ℃, the molar ratio of hydrogen to glycerol is 1-200, preferably 2-100, the volume space velocity of hydrogen is 200-20000h -1 Preferably 300-15000h -1 。
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. In the following examples, the percentages are by weight unless otherwise specified. In the following examples, the measuring instrument for X-ray photoelectron spectroscopy is an ESCALab250 type instrument from Thermo Scientific, under the following measurement conditions: an excitation light source is a monochromator Al K alpha X ray of 150kW, and the combination energy is corrected by adopting a C1 s peak (284.8 eV); the measuring instrument for X-ray fluorescence spectrum is 3271 type instrument of Japan science and electric machinery industry Co., ltd, and the measuring conditions are as follows: and tabletting and molding the powder sample, wherein the rhodium target is subjected to laser voltage of 50kV and laser current of 50mA.
In the following examples and comparative examples, the temperature of rotary evaporation was 50 ℃ and the pressure was 0.03MPa.
In the following examples, the catalyst composition is based on the total weight of the catalyst, and the mass percentages of the elements in the catalyst are determined by X-ray fluorescence spectroscopy.
Example 1
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
(1) 3.508g niobium oxalate is dissolved in 50mL deionized water to obtain an impregnation solution, 17.325g alumina microspheres (product of Sasol company, specific surface area 175 m) 2 /g) dispersing in the above maceration extract, stirring at room temperature (25 deg.C) for 10min, rotary evaporating to obtain sample,drying the sample at 120 ℃ for 2h, and then roasting at 700 ℃ for 2h to obtain a niobium modified carrier;
(2) The niobium modified carrier is dispersed into 1.662g ammonium metatungstate (W mass fraction is 72.17%) and dissolved in 40mL deionized immersion liquid, stirring is carried out for 10min at room temperature (25 ℃), rotary evaporation is carried out to obtain a sample, the sample is dried for 2h at 150 ℃, and then roasting is carried out for 2h at 600 ℃ to obtain a tungsten-containing catalyst precursor;
(3) The tungsten-containing catalyst precursor is dispersed into an impregnation solution formed by mixing 2.85wt% platinum-containing chloroplatinic acid solution (14.035 g) and 10mL of deionized water; stirring the mixture for 10min at room temperature (25 ℃), performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting the sample at 300 ℃ for 2h to obtain the niobium-containing catalyst C-1. The composition, XPS and XRF characterization results are shown in Table 1.
Comparative example 1
18.087g of alumina microspheres (product of Sasol, specific surface area 175 m) 2 /g) dispersing 1.663g ammonium metatungstate (W mass fraction 72.17%) in 40mL deionized impregnation solution, stirring at room temperature (25 ℃) for 10min, performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 600 ℃ for 2h; the obtained sample is dispersed into an impregnation solution formed by mixing chloroplatinic acid solution (14.035 g) containing 2.85wt% of platinum and 10mL deionized water; stirring at room temperature (25 ℃) for 10min, carrying out rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 300 ℃ for 2h to obtain the catalyst DC-1. The composition, XPS and XRF characterization results are shown in Table 1.
Comparative example 2
(1) 3.508g niobium oxalate was dissolved in 50mL deionized water to obtain a solution, 18.838g alumina microspheres (product of Sasol Corp., specific surface area 175 m) 2 /g) dispersing the niobium oxide in the impregnation liquid, stirring for 10min at room temperature (25 ℃), performing rotary evaporation to obtain a sample, drying the sample at 120 ℃ for 2h, and roasting at 700 ℃ for 2h to obtain a niobium modified carrier;
(2) Dispersing the niobium modified carrier into an impregnation solution formed by mixing a chloroplatinic acid solution (14.035 g) containing 2.85wt% of platinum and 10mL of deionized water; stirring at room temperature (25 ℃) for 10min, carrying out rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 300 ℃ for 2h to obtain the catalyst DC-2. The composition, XPS and XRF characterization results are shown in Table 1.
Comparative example 3
According to the preparation method disclosed in CN106588570A, a catalyst with the same composition as that of the catalyst in the embodiment 1 of the invention is prepared by using alumina as a carrier. Specifically, the method comprises the following steps:
(1) 17.325g of alumina microspheres (product of Sasol company, specific surface area 175 m) 2 /g) dispersing 1.662g ammonium metatungstate (W mass fraction 72.17%) in 40mL deionized impregnation liquid, stirring at room temperature (25 ℃) for 10min, performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 600 ℃ for 2h to obtain a tungsten-containing catalyst precursor;
(2) Dissolving 3.508g niobium oxalate in 50mL of deionized water to obtain an impregnation solution, dispersing the tungsten-containing catalyst precursor into the impregnation solution, stirring at room temperature (25 ℃) for 10min, performing rotary evaporation to obtain a sample, drying the sample at 120 ℃ for 2h, and roasting at 700 ℃ for 2h to obtain the tungsten-containing niobium-containing catalyst precursor;
(3) The tungsten-containing and niobium-containing catalyst precursor is dispersed into an impregnation solution formed by mixing 2.85wt% platinum-containing chloroplatinic acid solution (14.035 g) and 10mL of deionized water; stirring the mixture for 10min at room temperature (25 ℃), performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting the sample at 300 ℃ for 2h to obtain the niobium-containing catalyst DC-3. The composition, XPS and XRF characterization results are shown in Table 1.
Comparative example 4
Preparation of TiO by sol-gel method 2 -SiO 2 Support, i.e. TiO in a mass fraction of 10% by weight of the support composition 2 And 90% by mass of SiO 2 Preparing corresponding ethanol solution containing tetrabutyl titanate and ethanol solution containing tetraethyl silicate, uniformly mixing the two solutions, adding hydrochloric acid to form gel, aging and drying to obtain TiO 2 -SiO 2 And (3) a carrier.
The procedure is as in example 1, except that the alumina microspheres are replaced by TiO of equal mass 2 -SiO 2 And (3) a carrier. Thus obtaining the niobium-containing catalyst DC-4. The composition, XPS and XRF characterization results are shown in Table 1.
Example 2
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
(1) 1.17g of niobium oxalate was dissolved in 50mL of deionized water to obtain a solution, and 19.082g of alumina microspheres (product of Sasol company, specific surface area 175 m) 2 /g) dispersing the niobium oxide in the impregnation liquid, stirring for 10min at room temperature (25 ℃), performing rotary evaporation to obtain a sample, drying the sample at 120 ℃ for 2h, and roasting at 800 ℃ for 3h to obtain a niobium modified carrier;
(2) Dispersing the niobium-modified carrier into 0.554g of ammonium metatungstate (W mass fraction is 72.17%) to be dissolved in 40mL of deionized impregnation liquid, stirring at room temperature (25 ℃) for 10min, performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 600 ℃ for 2h to obtain a tungsten-containing catalyst precursor;
(3) The tungsten-containing catalyst precursor is dispersed into an impregnation solution formed by mixing 2.85wt% platinum-containing chloroplatinic acid solution (5.614 g) and 10mL of deionized water; stirring the mixture for 10min at room temperature (25 ℃), performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting the sample at 300 ℃ for 2h to obtain the niobium-containing catalyst C-2. The composition, XPS and XRF characterization results are shown in Table 1.
Example 3
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
(1) 9.356g niobium oxalate was dissolved in 100mL deionized water to obtain a solution, 13.941g alumina microspheres (product of Sasol Corp., specific surface area 175 m) 2 /g) dispersing the niobium oxide in the impregnation liquid, stirring for 10min at room temperature (25 ℃), performing rotary evaporation to obtain a sample, drying the sample at 120 ℃ for 2h, and roasting at 600 ℃ for 6h to obtain a niobium modified carrier;
(2) Dispersing the niobium-modified carrier into 3.325g of ammonium metatungstate (W mass fraction is 72.17%) to be dissolved in 40mL of deionized impregnation liquid, stirring at room temperature (25 ℃) for 10min, performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 600 ℃ for 2h to obtain a tungsten-containing catalyst precursor;
(3) The tungsten-containing catalyst precursor is dispersed into 35.088g of a platinum-containing 2.85wt% chloroplatinic acid solution; stirring at room temperature (25 ℃) for 10min, carrying out rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 300 ℃ for 2h to obtain the niobium-containing catalyst C-3. The composition, XPS and XRF characterization results are shown in Table 1.
Example 4
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
The procedure was followed as in example 1, except that in step (1), 0.62g of niobium oxalate was used. Thus obtaining the niobium-containing catalyst C-4. The composition, XPS and XRF characterization results are shown in Table 1.
Example 5
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
The procedure was followed as in example 1, except that, in the step (1), niobium oxalate was used in an amount of 10.3g. Thus obtaining the niobium-containing catalyst C-5. The composition, XPS and XRF characterization results are shown in Table 1.
Example 6
(1) The procedure of example 1, step (1), was followed to obtain a niobium-modified support;
(2) Dispersing the niobium-modified carrier into 84mL of perrhenic acid aqueous solution containing 13.1 g/L of rhenium, stirring at room temperature (25 ℃) for 10min, performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 600 ℃ for 2h to obtain a rhenium-containing catalyst precursor;
(3) The rhenium-containing catalyst precursor was dispersed in an impregnation solution of an iridium chloride solution containing 2.5% by weight of iridium (16.0 g) and 15mL of deionized water; stirring at room temperature (25 ℃) for 10min, carrying out rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 300 ℃ for 2h to obtain the niobium-containing catalyst C-6.
In the niobium-containing catalyst C-6, the Ir content was 2% by weight, the Re content was 6% by weight, and the Nb content was 3% by weight. (Nb/Al) XPS /(Nb/Al) XRF ＝9.1。
Example 7
(1) A niobium-modified support was obtained in the same manner as in step (1) of example 1;
(2) The niobium modified carrier is dispersed into an impregnation solution formed by mixing a chloroplatinic acid solution (14.035 g) containing 2.85wt% of platinum and 10mL of deionized water; stirring for 10min at room temperature (25 ℃), performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and roasting at 300 ℃ for 2h to obtain a platinum-containing catalyst precursor;
(3) And dispersing the platinum-containing catalyst precursor into 1.662g ammonium metatungstate (W mass fraction is 72.17%) and dissolving the ammonium metatungstate in 40mL deionized immersion liquid, stirring the mixture for 10min at room temperature (25 ℃), performing rotary evaporation to obtain a sample, drying the sample at 150 ℃ for 2h, and calcining the sample at 600 ℃ for 2h to obtain the niobium-containing catalyst C-7. The composition, XPS and XRF characterization results are shown in Table 1.
TABLE 1
Test example 1
This experimental example was used to determine the performance of the niobium-containing catalyst of the present invention on the hydrogenolysis reaction of glycerol.
The catalysts prepared in the above examples and comparative examples were evaluated according to the following procedures, respectively.
Weighing 1.5g of catalyst, loading the catalyst into a fixed bed reactor, reducing and activating the catalyst for 2h at 240 ℃ under the atmosphere of normal-pressure pure hydrogen, wherein the volume space velocity of the hydrogen is 8000h -1 . Cooling to 200 ℃ for reaction, and controlling the reaction pressure to be 3MPa, the hydrogen flow to be 15L/h and the flow of the 20 wt% glycerol aqueous solution to be 12mL/h. After the reaction was stabilized for 3 hours, the liquid after the reaction was collected and subjected to composition analysis by gas chromatography.
The mole percent of glycerol converted to 1,3-propanediol to converted glycerol was defined as 1,3-propanediol selectivity, and the mass (grams) of 1,3-propanediol formed per gram of Pt/Ir per unit time (h) was the catalyst space time yield, and the results are shown in table 2.
TABLE 2
As can be seen from the data in Table 2, the catalyst containing niobium provided by the invention has higher selectivity and activity of 1,3-propanediol when being applied to the glycerol hydrogenolysis reaction process compared with the glycerol hydrogenolysis catalyst provided by the prior art.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (26)
1. A niobium-containing catalyst comprising an alumina-containing support, and a first active metal component and a second active metal component both supported on the alumina-containing support, the first active metal component being at least one selected from the group consisting of Pt, ir, rh and Pd, and the second active metal component being at least one selected from the group consisting of Zr, ta, mn, W and Re, and niobium, which satisfies (Nb/Al) XPS /(Nb/Al) XRF =2-20, wherein (Nb/Al) XPS The weight ratio of niobium to aluminum in the catalyst is characterized by X-ray photoelectron spectroscopy, (Nb/Al) XRF The weight ratio of niobium element to aluminum element in the catalyst is characterized by X-ray fluorescence spectrum; based on the total amount of the catalyst, the content of the niobium element is 0.1-15 wt%, the content of the first active metal component is 0.05-10 wt%, and the content of the second active metal component is 0.1-20 wt%;
the preparation method of the catalyst comprises the following steps:
(1) Impregnating an alumina-containing carrier with a solution containing a niobium-containing compound, and then drying and roasting the obtained solid material to obtain a niobium-modified carrier;
(2) Introducing a first active metal component and a second active metal component onto the niobium modified support by an impregnation process.
2. The niobium-containing catalyst of claim 1, wherein the catalyst satisfies (Nb/Al) XPS /(Nb/Al) XRF =3-15。
3. The niobium-containing catalyst of claim 1, wherein the catalyst satisfies (Nb/Al) XPS /(Nb/Al) XRF =4-12。
4. The niobium-containing catalyst according to any one of claims 1 to 3,
based on the total amount of the catalyst, the content of the niobium element is 0.5 to 10 wt%, the content of the first active metal component is 0.1 to 8 wt%, and the content of the second active metal component is 0.5 to 15 wt%.
5. The niobium-containing catalyst according to claim 4,
based on the total amount of the catalyst, the content of the niobium element is 1 to 8 weight percent, the content of the first active metal component is 0.5 to 5 weight percent, and the content of the second active metal component is 2 to 12 weight percent.
6. The niobium-containing catalyst as claimed in any one of claims 1 to 3, wherein the molar ratio of niobium to the second active metal component is from 0.2 to 4:1.
7. the niobium-containing catalyst as claimed in claim 6, wherein the molar ratio of niobium to the second active metal component is 1 to 1.5:1.
8. the niobium-containing catalyst of any one of claims 1-3, wherein the first active metal component is Pt and/or Ir; the second active metal component is W and/or Re;
the alumina-containing support is at least one selected from the group consisting of alumina, alumina-magnesia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
9. The niobium-containing catalyst of claim 8, wherein the first active metal component is Pt; the second active metal component is W.
10. A method of preparing a niobium-containing catalyst, the method comprising:
(1) Impregnating an alumina-containing carrier with a solution containing a niobium-containing compound, and then drying and roasting the obtained solid material to obtain a niobium-modified carrier;
(2) Introducing a first active metal component selected from at least one of Pt, ir, rh and Pd and a second active metal component selected from at least one of Zr, ta, mn, W and Re onto the niobium modified support by an impregnation process;
the niobium-containing compound, the alumina-containing carrier, the first active metal component and the second active metal component are used in amounts such that the catalyst is obtained in which the content of the niobium element is 0.1 to 15% by weight, the content of the first active metal component is 0.05 to 10% by weight and the content of the second active metal component is 0.1 to 20% by weight, based on the total amount of the catalyst, and which satisfies (Nb/Al) XPS /(Nb/Al) XRF =2-20, wherein (Nb/Al) XPS The weight ratio of niobium to aluminum in the catalyst is characterized by X-ray photoelectron spectroscopy, (Nb/Al) XRF The weight ratio of niobium element to aluminum element in the catalyst is characterized by X-ray fluorescence spectrum.
11. The production method according to claim 10, wherein the niobium-containing compound is at least one selected from the group consisting of niobium oxalate, niobium chloride, niobium oxychloride and niobium fluoride;
and/or, the alumina-containing support is selected from at least one of alumina, alumina-magnesia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia;
and/or, the roasting condition of the step (1) comprises the following steps: the temperature is 300-1200 ℃; the time is 0.5-12h.
12. The production method according to claim 11, wherein the niobium-containing compound is niobium oxalate;
and/or, the roasting condition of the step (1) comprises the following steps: the temperature is 350-1000 ℃; the time is 1-10h.
13. The production method according to claim 10, wherein in the step (2), the second active metal component and the first active metal component are introduced onto the niobium-modified support in this order by an impregnation method.
14. The production method according to claim 13, wherein the step (2) includes:
a) Impregnating the niobium-modified support with a solution containing a compound of a second active metal component, drying and optionally calcining the resulting solid material to obtain a catalyst precursor containing the second active metal component;
b) The catalyst precursor containing the second active metal component is impregnated with a solution containing a compound of the first active metal component and the resulting solid mass is dried and optionally calcined.
15. The production method according to claim 10,
the compound of the first active metal component is selected from at least one of nitrate, acetate, basic carbonate and chloride containing one or more of Pt, ir, rh and Pd elements;
the compound of the second active metal component is selected from at least one of nitrate, acetate, basic carbonate and chloride containing one or more of Zr, ta, mn, W and Re.
16. The production method according to claim 10,
the first active metal component is Pt and/or Ir; the second active metal component is W and/or Re.
17. The production method according to claim 16, wherein the first active metal component is Pt; the second active metal component is W.
18. The production method according to any one of claims 10 to 17, wherein the niobium-containing compound, the alumina-containing support, the first active metal component and the second active metal component are used in amounts such that the catalyst is produced in which the content of the niobium element is 0.5 to 10% by weight, the content of the first active metal component is 0.1 to 8% by weight and the content of the second active metal component is 0.5 to 15% by weight, based on the total amount of the catalyst.
19. The production method according to claim 18, wherein the niobium-containing compound, the alumina-containing support, the first active metal component and the second active metal component are used in amounts such that the resultant catalyst contains the niobium element in an amount of 1 to 8% by weight, the first active metal component in an amount of 0.5 to 5% by weight and the second active metal component in an amount of 2 to 12% by weight, based on the total amount of the catalyst.
20. The production method according to any one of claims 10 to 17, wherein the molar ratio of the niobium-containing compound to the second active metal component in terms of niobium element is from 0.2 to 4:1.
21. the production method as claimed in claim 20, wherein the molar ratio of the niobium-containing compound to the second active metal component in terms of niobium element is 1 to 1.5:1.
22. a niobium-containing catalyst obtained by the production method as claimed in any one of claims 10 to 21.
23. Use of a niobium containing catalyst as claimed in any one of claims 1 to 9, 22 in the hydrogenolysis of glycerol.
24. A process for the hydrogenolysis of glycerol comprising contacting a feed comprising glycerol, hydrogen and a catalyst under catalytic hydrogenolysis conditions wherein the catalyst is the niobium-containing catalyst of any one of claims 1-9 and 22.
25. The method of claim 24, wherein the catalytic glycerol hydrogenolysis conditions comprise: the pressure is 0.1-8MPa, the reaction temperature is 100-300 ℃, the molar ratio of hydrogen to glycerin is 1-200, and the volume space velocity of hydrogen is 200-20000h -1 。
26. The method of claim 24, wherein the catalytic glycerol hydrogenolysis conditions comprise: the pressure is 1-5MPa, the reaction temperature is 140-260 ℃, the molar ratio of hydrogen to glycerol is 2-100, and the volume space velocity of hydrogen is 300-15000h -1 。
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