CN112316985A - Catalytic material for preparing methanol by carbon dioxide hydrogenation and preparation method thereof - Google Patents

Catalytic material for preparing methanol by carbon dioxide hydrogenation and preparation method thereof Download PDF

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CN112316985A
CN112316985A CN201910718004.6A CN201910718004A CN112316985A CN 112316985 A CN112316985 A CN 112316985A CN 201910718004 A CN201910718004 A CN 201910718004A CN 112316985 A CN112316985 A CN 112316985A
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uio
carbon dioxide
methanol
catalytic material
reaction
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洪昕林
刘国亮
刘唐康
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Wuhan Kelikai Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B01J35/23—
    • B01J35/393—
    • B01J35/615—
    • B01J35/617—
    • B01J35/647—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to the field of catalytic materials for preparing methanol by carbon dioxide hydrogenation, and discloses a catalytic material for preparing methanol by carbon dioxide hydrogenation and a preparation method thereof, wherein the method comprises the following steps: (1) in the presence of a solvent, carrying out a first contact reaction on UiO-66 and copper acetate to obtain a solution I; (2) and carrying out a second contact reaction on the solution I and sodium borohydride to obtain the catalytic material. The catalytic material for preparing methanol by carbon dioxide hydrogenation is a nano-scale copper nanocrystalline species, can increase the stability of the copper species and the catalytic capability of the catalyst for dissociating hydrogen and activating carbon dioxide, and is beneficial to the implementation of the carbon dioxide reduction reaction.

Description

Catalytic material for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
Technical Field
The invention relates to the field of catalytic materials for preparing methanol by hydrogenating carbon dioxide, in particular to a method for preparing a catalytic material for preparing methanol by hydrogenating carbon dioxide and the catalytic material for preparing methanol by hydrogenating carbon dioxide.
Background
The MOF material with a porous structure and high heat-resistant stability is a good carrier in the field of catalysis in recent years, and the copper-based material is widely used for catalytic reactions of preparing methanol by catalyzing carbon dioxide hydrogenation, catalytic conversion of water gas, photocatalytic degradation of organic matters, elimination of automobile tail gas (NO, CO and the like) and the like due to unique redox performance and high catalytic activity of the copper-based material.
The outer electronic structure of the transition element Cu is 3d104s1The ion source has three chemical valence states of +2, +1 and 0, and the standard reduction potential is lower, so that the ion source is easy to realize the interconversion among ions in the chemical valence states and has stronger redox capability. The catalytic reaction is mainly carried out on the copper surface, but pure CuOxThe oxide is extremely unstable in microstructure in a reducing atmosphere, is easy to be transformed into metal copper and is easy to be sintered at high temperature to cause the rapid reduction of the specific surface area, so that the catalytic activity is reduced extremely rapidly and even is inactivated.
Disclosure of Invention
The invention aims to obtain a catalytic material for preparing methanol by hydrogenating carbon dioxide, which has better catalytic performance, in particular to obtain the catalytic material for preparing methanol by hydrogenating carbon dioxide, which has excellent carbon dioxide conversion rate and methanol selectivity.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a catalytic material for preparing methanol by hydrogenating carbon dioxide, the method comprising:
(1) in the presence of a solvent, carrying out a first contact reaction on UiO-66 and copper acetate to obtain a solution I;
(2) and carrying out a second contact reaction on the solution I and sodium borohydride to obtain the catalytic material.
The second aspect of the invention provides a catalytic material for preparing methanol by hydrogenation of carbon dioxide prepared by the method.
The method for preparing the catalytic material for preparing the methanol by the hydrogenation of the carbon dioxide has the advantages of low cost, simple, convenient and safe operation, short reaction period and good product repeatability.
The catalytic material for preparing methanol by carbon dioxide hydrogenation is a nano-scale copper nanocrystalline species, can increase the stability of the copper species and the catalytic capability of the catalyst for dissociating hydrogen and activating carbon dioxide, and is beneficial to the implementation of the carbon dioxide reduction reaction.
Specifically, the catalytic material of the invention has low cost, high catalytic activity and high thermal stability, and can prepare hydrogen storage substances by catalytic reduction of carbon dioxide at a lower temperature: the methanol has good application in material research and reaction for preparing methanol by catalytic hydrogenation of carbon dioxide.
Drawings
FIG. 1 is an XRD spectrum of the products obtained in examples 1-4 of the present invention.
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.
As previously mentioned, a first aspect of the present invention provides a process for preparing a catalytic material for the hydrogenation of carbon dioxide to methanol, the process comprising:
(1) in the presence of a solvent, carrying out a first contact reaction on UiO-66 and copper acetate to obtain a solution I;
(2) and carrying out a second contact reaction on the solution I and sodium borohydride to obtain the catalytic material.
Said UiO-66 of the invention is also referred to as Zr-MOF material.
Preferably, the conditions of the first contact reaction include: the temperature is 10-40 ℃ and the time is 0.1-10 h.
Preferably, the first contact reaction is carried out under stirring at a rate of 50 to 500 rpm.
Preferably, in the step (1), the molar ratio of the copper acetate calculated by Cu element to the UiO-66 calculated by Zr element is (0.3-0.6): 1.
preferably, in step (1), the solvent is selected from at least one of methanol and ethanol. Also, the solvent is preferably used in the step (1) in an amount such that the concentration of UiO-66 is 1 to 30g/L, more preferably 5 to 20g/L, still more preferably 7.5 to 15g/L, for example, 10.6 g/L.
In step (1), a solvent and the UiO-66 are preferably mixed under ultrasonic conditions to form a solution, and the ultrasonic conditions in this step may be, for example: the ultrasonic frequency is 20KHz-60KHz, and the ultrasonic time is 0.1-4 h.
Preferably, in step (2), the conditions of the second contact reaction include: the temperature is 10-40 ℃ and the time is 0.1-10 h.
Preferably, in the step (2), the molar ratio of the sodium borohydride to the copper acetate calculated by Cu element is (4-5): 1.
the sodium borohydride can be subjected to a second contact reaction with the solution I, for example, in the form of a solution in methanol.
According to a particularly preferred embodiment, the method of this aspect further comprises preparing said UiO-66 by:
(a) mixing a zirconium source, water, formic acid, and terephthalic acid in the presence of a solvent to perform a hydrothermal reaction;
(b) and drying the solid product obtained after the hydrothermal reaction.
The inventor of the present invention found that the UiO-66 prepared by the aforementioned method of the present invention has better catalytic performance when used for preparing a catalytic material for preparing methanol by hydrogenating carbon dioxide, and the reason of the analysis of the inventor of the present invention may be: the UO-66 obtained by the preparation method provided by the preferred embodiment of the invention is MOFs material with cluster defects, and the MOFs material with cluster defects can be just used for confining nano-metal copper, so that the particle size of the MOFs material can be controlled in a range of 5-6nm most preferably, and the MOFs material has higher catalytic activity and stability.
In step (a), it is preferable that the zirconium source, water, formic acid and terephthalic acid are first mixed to form a mixed solution, and then the mixed solution is mixed with a solvent and subjected to hydrothermal reaction. More preferably, the mixing of the zirconium source, water, formic acid and terephthalic acid with the solvent is carried out under ultrasonic conditions, the frequency of the ultrasonic treatment may be, for example, 20KHz to 60KHz, and the time of the ultrasonic treatment may be, for example, 0.1 to 2 hours.
Preferably, in step (a), the hydrothermal reaction conditions include: the temperature is 100-140 ℃, and the time is 2-24 h.
Preferably, in step (a), the molar ratio of the zirconium source to the water, the formic acid and the terephthalic acid, calculated as Zr element, is 1 (3-3.5): (100) 110: 0.9-1.1.
Preferably, in step (a), the solvent is N, N' -dimethylformamide. It is particularly preferred that the molar ratio of the amount of N, N' -dimethylformamide used in step (a) to the amount of zirconium source used is (200-300): 1, more preferably (255-275): 1, more preferably (259) 269): 1.
the zirconium source of the present invention is a soluble salt capable of providing the element zirconium, and may be, for example, zirconium chloride.
In the present invention, the solid product is preferably separated from the product mixture obtained after the hydrothermal reaction by means of, for example, centrifugation.
Preferably, in step (b), the drying conditions include: the temperature is 30-80 ℃ and the time is 2-24 h.
Particularly preferably, in the step (b), the solid obtained by drying is subjected to a pulverization treatment to obtain a powder having an average particle diameter of 100-150 nm.
Preferably, the method of the present invention further comprises: in the step (2), the solid obtained after the second contact reaction is sequentially dried and calcined to obtain the catalytic material.
Preferably, in step (2), the drying conditions include: the temperature is 40-80 ℃ and the time is 2-24 h.
Preferably, in the step (2), the roasting conditions include: the temperature is 150 ℃ and 500 ℃, and the time is 0.5-8 h. Preferably, the calcination is carried out in a solution containing 10 vol% of H2Under an Ar atmosphere of (1).
According to a particularly preferred embodiment, the method of the invention comprises:
1) mixing and dissolving zirconium chloride, water, formic acid, terephthalic acid and N, N' -dimethylformamide;
2) carrying out hydrothermal reaction on the mixture obtained in the step 1);
3) carrying out centrifugal separation on a product mixture I obtained after the hydrothermal reaction to obtain a solid product I, and sequentially drying and crushing the solid product I to obtain UiO-66;
4) contacting the UiO-66 with methanol to form a mixture solution, and carrying out a first contact reaction on the mixture solution and copper acetate to obtain a solution I;
5) and carrying out a second contact reaction on the solution I and a methanol solution of sodium borohydride, carrying out centrifugal separation on a product mixture II obtained after the reaction to obtain a solid product II, and sequentially drying and roasting the solid product II.
As previously mentioned, the second aspect of the present invention provides a catalytic material for the hydrogenation of carbon dioxide to methanol, prepared by the aforementioned method.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available ones unless otherwise specified.
Wherein, the zirconium chloride is anhydrous zirconium chloride, and the copper acetate is monohydrate copper acetate.
Example 1
At 25 ℃, 0.233g of zirconium chloride, 0.054mL of water, 3.8mL of formic acid and 0.1662g of terephthalic acid are sequentially dissolved in 20mL of N, N '-dimethylformamide (zirconium chloride: water: formic acid: terephthalic acid: N, N' -dimethylformamide ═ 1:3:100:1:259) to obtain a mixture, after ultrasonic dispersion (frequency of 50KHz and time of 30min), hydrothermal reaction is carried out for 12h at 120 ℃, centrifugal washing is carried out after the reaction is finished, the precipitate obtained after the centrifugation is dried for 12h at 60 ℃ and then crushed, and the MOF material UiO-66 solid with the average particle size of 105 is obtained.
0.53g of solid UiO-66 (frequency 50KHz, time 15min) is dispersed in 50mL of methanol at 25 ℃ to obtain a dispersion of UiO-66 methanol with a mass concentration of 10.6g/L for later use.
0.1088g of sodium borohydride is dissolved in methanol at 25 ℃ to form a methanol solution of sodium borohydride with the mass concentration of 4.5g/L for later use.
Adding 0.1145g of copper acetate monohydrate into the UiO-66 methanol dispersion, stirring at 25 ℃ (the stirring speed is 400rpm) for 1h, then adding the sodium borohydride methanol solution, and stirring at 25 ℃ for reacting for 2.5 h; the molar ratio of the added sodium borohydride to the added copper acetate is n (NaBH)4) N (Cu) 5: 1. After the reaction is finished, centrifuging the obtained substance, drying the precipitate obtained after centrifugation at 60 ℃ for 12H, crushing the dried precipitate, and performing reaction in a tubular furnace at 300 ℃ until the volume of the precipitate is 10 percent H2Calcining for 2h in a/Ar atmosphere to obtain a blue [ Cu ] product]@ UiO-66 catalyst.
Example 2
At 25 ℃, 0.233g of zirconium chloride, water, formic acid and terephthalic acid are sequentially dissolved in N, N '-dimethylformamide (zirconium chloride: water: formic acid: terephthalic acid: N, N' -dimethylformamide: 1:3.5:110:1:269) to obtain a mixture, after ultrasonic dispersion (frequency of 40KHz and time of 30min), hydrothermal reaction is carried out for 15h at 110 ℃, centrifugal washing is carried out after the reaction is finished, precipitates obtained after the centrifugation are dried at 60 ℃ for 14h and then crushed, and then the MOF material UiO-66 solid with the average particle size of 105nm is obtained.
And dispersing solid UiO-66 in 50mL of methanol at 25 ℃ by ultrasonic waves (the frequency is 45KHz and the time is 10min) to obtain a UiO-66 methanol dispersion liquid with the mass concentration of 10.8g/L for later use.
At 25 ℃, dissolving sodium borohydride in methanol to form a sodium borohydride methanol solution with the mass concentration of 4.8g/L for later use.
Adding 0.1526g of copper acetate monohydrate into the UiO-66 methanol dispersion, stirring at 30 ℃ (the stirring speed is 350rpm) for 1.5h, and then adding the sodium borohydride AAlcohol solution is stirred and reacted for 4 hours at the temperature of 30 ℃; the molar ratio of the added sodium borohydride to the added copper acetate is n (NaBH)4) N (Cu) is 4: 1. After the reaction is finished, centrifuging the obtained substance, drying the precipitate obtained after centrifugation at 60 ℃ for 12H, crushing the dried precipitate, and performing reaction in a tubular furnace at 300 ℃ until the volume of the precipitate is 10 percent H2Calcining for 2h in a/Ar atmosphere to obtain a blue [ Cu ] product]@ UiO-66 catalyst.
Example 3
At 25 ℃, 0.233g of zirconium chloride, water, formic acid and terephthalic acid are sequentially dissolved in N, N '-dimethylformamide (zirconium chloride: water: formic acid: terephthalic acid: N, N' -dimethylformamide: 1:3:105:1:265) to obtain a mixture, after ultrasonic dispersion (frequency of 30KHz and time of 45min), hydrothermal reaction is carried out for 10h at 115 ℃, centrifugal washing is carried out after the reaction is finished, precipitates obtained after the centrifugation are dried for 12h at 60 ℃ and then crushed, and the MOF material UiO-66 solid with the average particle size of 105nm is obtained.
And dispersing solid UiO-66 in 50mL of methanol at 25 ℃ by ultrasonic (the frequency is 50KHz, and the time is 15min) to obtain a UiO-66 methanol dispersion liquid with the mass concentration of 10.6g/L for later use.
At 25 ℃, dissolving sodium borohydride in methanol to form a sodium borohydride methanol solution with the mass concentration of 4.5g/L for later use.
Adding 0.1908g of copper acetate monohydrate into the UiO-66 methanol dispersion, stirring at 35 ℃ (the stirring speed is 400rpm) for 1h, then adding the sodium borohydride methanol solution, and stirring at 35 ℃ for reacting for 2 h; the molar ratio of the added sodium borohydride to the added copper acetate is n (NaBH)4) N (Cu) is 4.5: 1. After the reaction is finished, centrifuging the obtained substance, drying the precipitate obtained after centrifugation at 60 ℃ for 12H, crushing the dried precipitate, and performing reaction in a tubular furnace at 300 ℃ until the volume of the precipitate is 10 percent H2Calcining for 2h in a/Ar atmosphere to obtain a blue [ Cu ] product]@ UiO-66 catalyst.
Example 4
A solid MOF material, UiO-66, was prepared using the same procedure as in example 1.
0.53g of the solid UiO-66 of this example was dispersed ultrasonically (at the same frequency and time as in example 1) in 50mL of methanol at 25 ℃ to give a dispersion of UiO-66 in methanol having a mass concentration of 10.6g/L for use.
At 25 ℃, 0.2175g of sodium borohydride is dissolved in methanol to form a methanol solution of sodium borohydride with the mass concentration of 4.5g/L for later use.
Adding 0.2289g of copper acetate monohydrate into the UiO-66 methanol dispersion, stirring at 25 ℃ (the stirring speed is the same as that in example 1) for 1h, then adding the sodium borohydride methanol solution, and stirring at 25 ℃ for reacting for 2.5 h; the molar ratio of the added sodium borohydride to the added copper acetate is n (NaBH)4) N (Cu) 5: 1. After the reaction is finished, centrifuging the obtained substance, drying the precipitate obtained after centrifugation at 60 ℃ for 12H, crushing the dried precipitate, and performing reaction in a tubular furnace at 300 ℃ until the volume of the precipitate is 10 percent H2Calcining for 2h in a/Ar atmosphere to obtain a blue [ Cu ] product]@ UiO-66 catalyst.
Example 5
This example was carried out in a similar manner to example 1, except that the MOF material Zr-UiO-66 solid in this example was prepared according to the method disclosed in Kobayashi et al, chem.Sci.,2019,10, 3289-3294.
The preparation process comprises the following steps: 881.2mg of ZrCl4Placed in 67.5mL of DMF and dissolved by ultrasound (frequency: 50KHz) to form a slightly turbid colorless solution. Next, 687.3mg of terephthalic acid was added to the solution, again dissolved by ultrasonic wave (frequency: 50KHz), 200uL of water was added, and the solution was sealed in a glass pressure vessel and then placed in an oven to be heated at 120 ℃ for 24 hours. The synthesized powdery white product is recovered by vacuum filtration and washed by DMF, ethanol and acetone. Subsequently, the sample was soaked in acetone (3X 20mL), and then ultra-pure water (3X 20mL) was added to the centrifuge tube for 1 day each, and recovered by centrifugation. Finally, the sample was dried in an oven at about 60 ℃ for 24 hours to obtain 150-200nm white Zr-UiO-66 powder.
The rest is the same as in example 1.
Comparative example 1
A solid MOF material, UiO-66, was prepared using the same procedure as in example 1.
A UiO-66 methanol dispersion having a mass concentration of 10.6g/L and a sodium borohydride methanol solution having a mass concentration of 4.5g/L were obtained in the same manner as in example 1 and were used.
Stirring the UiO-66 methanol dispersion, 0.1145g of copper acetate monohydrate and sodium borohydride methanol solution at 25 ℃ for 3.5h (the stirring speed is the same as that in example 1), wherein the molar ratio of the added sodium borohydride to the added copper acetate is n (NaBH)4) N (Cu) 5: 1. After the reaction is finished, centrifuging the obtained substance, drying the precipitate obtained after centrifugation at 60 ℃ for 12H, crushing the dried precipitate, and performing reaction in a tubular furnace at 300 ℃ until the volume of the precipitate is 10 percent H2Calcining for 2h in a/Ar atmosphere to obtain a blue [ Cu ] product]@ UiO-66 catalyst.
Test example 1
The catalysts of the above examples were tested to obtain specific surface area and pore size.
The specific surface area is obtained by testing Micromeritics ASAP-2010; the aperture was measured by Micromeritics ASAP-2010.
The results are shown in Table 1.
TABLE 1
Figure BDA0002156130260000091
Test example 2
The catalysts of the above examples were separately directed to CO2The gas is subjected to a performance test experiment for preparing methanol by catalytic hydrogenation, wherein CO is used2+H2The flow rate of the mixed gas was 36.0mL/min (25 vol% CO)275% by volume H2) The space velocity is 21600 mL/(g)catH) set up a mini fixed bed simulated reaction system, giving the data in tables 2, 3 and 4.
Table 2: the temperature is 220 DEG C
Serial number Sample name Conversion of carbon dioxide/%) Methanol space-time yield/mg.gcat -1h-1
1 30[Cu]@UiO-66 5.23 399.0
2 40[Cu]@UiO-66 4.75 367.0
3 50[Cu]@UiO-66 5.76 445.0
4 60[Cu]@UiO-66 4.87 376.0
5 5-[Cu]@UiO-66 2.2 102.4
6 D-30[Cu]@UiO-66 0.96 ～0.0
Table 3: the temperature is 240 DEG C
Serial number Sample name Conversion of carbon dioxide/%) Methanol space-time yield/mg.gcat -1h-1
1 30[Cu]@UiO-66 9.06 564.0
2 40[Cu]@UiO-66 8.47 575.0
3 50[Cu]@UiO-66 9.08 637.0
4 60[Cu]@UiO-66 7.39 568.0
5 5-[Cu]@UiO-66 4.3 225.2
6 D-30[Cu]@UiO-66 1.62 77.4
Table 4: the temperature is 260 DEG C
Serial number Sample name Conversion of carbon dioxide/%) Methanol space-time yield/mg.gcat -1h-1
1 30[Cu]@UiO-66 14.14 716.0
2 40[Cu]@UiO-66 12.54 721.0
3 50[Cu]@UiO-66 13.08 796.0
4 60[Cu]@UiO-66 11.2 739.0
5 5-[Cu]@UiO-66 7.7 339.0
6 D-30[Cu]@UiO-66 3.3 94.2
From the above results, it is clear that the catalytic material of the present invention has excellent carbon dioxide conversion rate and methanol selectivity, and exhibits excellent catalytic performance for carbon dioxide hydrogenation preparation.
Test example 3
The products obtained in examples 1 to 4 were subjected to X-ray powder diffraction (XRD) experiments using a Miniflex600 model XRD diffractometer manufactured by Rigaku corporation, and the results are shown in FIG. 1.
As can be seen from FIG. 1, copper and H are doped2After the/Ar reduction, the main structure of the catalyst carrier is basically destroyed, and a weak crystal phase peak of metallic copper appears, which indicates that the doping of the copper obviously changes the microstructure of the MOF material UiO-66 and forms a certain amount of copper nano crystals with micro-size, and the CO of the material2The performance of preparing methanol by catalytic hydrogenation is obviously improved.
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 (10)

1. A method for preparing a catalytic material for preparing methanol by hydrogenating carbon dioxide, which is characterized by comprising the following steps:
(1) in the presence of a solvent, carrying out a first contact reaction on UiO-66 and copper acetate to obtain a solution I;
(2) and carrying out a second contact reaction on the solution I and sodium borohydride to obtain the catalytic material.
2. The method of claim 1, wherein the conditions of the first contact reaction comprise: the temperature is 10-40 ℃, and the time is 0.1-10 h;
preferably, the first contact reaction is carried out under stirring at a rate of 50 to 500 rpm.
3. The process according to claim 1 or 2, wherein, in step (1), the molar ratio of the amount of copper acetate, calculated as Cu element, to the amount of UiO-66, calculated as Zr element, is (0.3-0.6): 1.
4. the method according to any one of claims 1 to 3, wherein in step (2), the conditions of the second contact reaction comprise: the temperature is 10-40 ℃, and the time is 0.1-10 h;
preferably, in the step (2), the molar ratio of the sodium borohydride to the copper acetate calculated by Cu element is (4-5): 1.
5. the method of any one of claims 1-4, further comprising preparing the UiO-66 by:
(a) mixing a zirconium source, water, formic acid, and terephthalic acid in the presence of a solvent to perform a hydrothermal reaction;
(b) and drying the solid product obtained after the hydrothermal reaction.
6. The method of claim 5, wherein in step (a), the conditions of the hydrothermal reaction comprise: the temperature is 100-140 ℃, and the time is 2-24 h;
preferably, in step (a), the molar ratio of the zirconium source to the water, the formic acid and the terephthalic acid, calculated as Zr element, is 1 (3-3.5): (100) 110: 0.9-1.1.
7. The process according to claim 5 or 6, wherein in step (a), the solvent is N, N' -dimethylformamide.
8. The method of any one of claims 5-7, wherein in step (b), the drying conditions comprise: the temperature is 30-80 ℃ and the time is 2-24 h.
9. The method of claim 1, wherein the method further comprises: in the step (2), drying and roasting the solid obtained after the second contact reaction to obtain the catalytic material;
preferably, in step (2), the drying conditions include: the temperature is 40-80 ℃, and the time is 2-24 h;
preferably, in the step (2), the roasting conditions include: the temperature is 150 ℃ and 500 ℃, and the time is 0.5-8 h.
10. A catalytic material for the hydrogenation of carbon dioxide to methanol, prepared by the process of any one of claims 1 to 9.
CN201910718004.6A 2019-08-05 2019-08-05 Catalytic material for preparing methanol by carbon dioxide hydrogenation and preparation method thereof Pending CN112316985A (en)

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