CN109622010B - Method for catalyzing formaldehyde dehydrogenation by using Pd @ CNx mosaic catalyst - Google Patents

Method for catalyzing formaldehyde dehydrogenation by using Pd @ CNx mosaic catalyst Download PDF

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CN109622010B
CN109622010B CN201811488328.7A CN201811488328A CN109622010B CN 109622010 B CN109622010 B CN 109622010B CN 201811488328 A CN201811488328 A CN 201811488328A CN 109622010 B CN109622010 B CN 109622010B
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catalyst
cnx
mixed solution
mosaic
formaldehyde
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CN109622010A (en
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程党国
万超
陈丰秋
詹晓力
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Zhejiang University ZJU
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Zhejiang University ZJU
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds

Abstract

The invention discloses a method for catalyzing formaldehyde dehydrogenation by using a Pd @ CNx mosaic catalyst. The Pd @ CNx mosaic catalyst is placed in a reactor, the reactor is placed in a water bath, the temperature is raised, then a mixed solution of formaldehyde and sodium hydroxide is added for reaction, and the generated hydrogen is collected by adopting a drainage method. The Pd @ CNx mosaic catalyst was prepared as follows: a) dissolving and mixing palladium chloride and glucosamine hydrochloride to form a uniform solution, and adding melamine into the uniform solution; b) stirring the mixed solution to dryness, transferring the mixed solution to a tubular furnace, and roasting the mixed solution at a certain temperature to obtain Pd2+@ CNx; c) roasting the obtained Pd2+@ CNx was transferred to a tube atmosphere furnace with a gas containing H2Reducing the mixed gas to obtain the Pd @ CNx mosaic catalyst. The Pd @ CNx mosaic catalyst with high activity and high selectivity for preparing hydrogen by formaldehyde dehydrogenation can be prepared by adjusting the molar ratio of metal Pd, C and N in the catalyst.

Description

Method for catalyzing formaldehyde dehydrogenation by using Pd @ CNx mosaic catalyst
Technical Field
The invention belongs to the technical field of chemistry and chemical engineering, and particularly relates to a method for catalyzing formaldehyde dehydrogenation by using a Pd @ CNx mosaic catalyst.
Background
The search and exploration of novel clean energy are important ways for solving energy crisis and environmental problems and realizing sustainable development of human beings, at present, the product after conversion caused by hydrogen energy is only water and has high energy density, so that the method is known as the clean energy in the 21 st century, and particularly the utilization of a hydrogen fuel cell is most economical and efficient. The development of efficient hydrogen storage materials is key to the realization of large-scale applications of hydrogen fuel cells.
Formaldehyde (HCHO) is a novel chemical hydride at present, has chemical temperature, is liquid at normal temperature, can well utilize the existing energy devices, and is regarded as one of the most promising hydrogen energy supply materials for fuel cells. The formaldehyde decomposition has two ways, one is directly decomposed to generate hydrogen and carbon monoxide, and the carbon monoxide easily causes poisoning of a fuel cell catalyst; the other way of generating hydrogen and carbon dioxide through hydrolysis is an ideal hydrogen energy release way, and the key point for controlling the two ways is to develop a high-efficiency formaldehyde dehydrogenation catalyst. The palladium-based catalyst is more applied in dehydrogenation reaction and is also a main component of the formaldehyde dehydrogenation catalyst, the construction of the high-efficiency palladium catalyst with a novel structure is very important for the formaldehyde dehydrogenation reaction, and the mosaic catalyst is designed based on the self-assembly and other related principles and aims to improve the stability and selectivity of the catalyst.
Disclosure of Invention
The invention aims to provide a method for catalyzing formaldehyde dehydrogenation by using a Pd @ CNx mosaic catalyst aiming at the defects of the prior art, wherein the Pd @ CNx mosaic catalyst realizes the complete dehydrogenation of formaldehyde under a mild condition, and the catalyst has good catalytic activity and selectivity.
The technical scheme adopted by the invention for solving the technical problem is as follows.
The prepared Pd @ CNxPlacing the mosaic catalyst in a reactor, placing the reactor in a water bath, heating to 5-50 ℃, and adding a mixed solution of formaldehyde and sodium hydroxide with a molar ratio of 1 (0.6-2) into the reactor for reaction to obtain a product hydrogen;
the mass ratio of the catalyst to the mixed solution is 1 (100-200);
the Pd @ CNx mosaic catalyst comprises Pd and CNx, wherein the mass ratio of palladium chloride, glucosamine hydrochloride and melamine is 1 (2-4.5) to (6-8); pd is from palladium chloride, and CNx is from glucosamine hydrochloride and melamine;
the Pd @ CNx mosaic catalyst is prepared by the following steps:
dissolving palladium chloride and glucosamine hydrochloride according to a certain mass ratio to form a uniform mixed solution, and adding melamine into the mixed solution according to a certain mass ratio;
step (2) stirring the mixed solution at a certain temperature until the mixed solution is dried, transferring the mixed solution to a tubular furnace, and roasting the mixed solution at a certain temperature to obtain Pd2+@CNx；
Pd obtained by roasting in step (3)2+And transferring the @ CNx to a tubular atmosphere furnace, and reducing by using mixed gas at a certain temperature to obtain the Pd @ CNx mosaic catalyst.
Further, in the preparation step (1) of the Pd @ CNx mosaic catalyst: the mass ratio of the palladium chloride to the glucosamine hydrochloride to the melamine is 1 (2-4.5) to (6-8).
Further, in the step (2) for preparing the Pd @ CNx mosaic catalyst: stirring until the drying temperature is 75-110 ℃, the roasting temperature of the tubular furnace is 520-680 ℃, the roasting time is 4-7 h, and the mass ratio of Pd to CNx is 1: (20-32), x is 0.8-1.1.
Further, in the step (3) of preparing the Pd @ CNx mosaic catalyst: the reduction temperature of the tubular atmosphere furnace is 250-360 ℃, the reduction time is 2-5H, and the mixed gas for reduction is H2/N2In which H is2The volume ratio of (A) is 3-10%.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a self-assembly method, the catalyst preparation uses palladium chloride, glucosamine hydrochloride and melamine mixed solution to obtain Pd by roasting2+@ CNx, calcining a certain amount of the obtained Pd2+@ CNx was transferred to a tube atmosphere furnace with a gas containing H at a certain temperature2The Pd @ CNx mosaic catalyst is prepared by reducing the mixed gas, and the catalyst has high activity and selectivity. The catalyst is used for carrying out the formaldehyde dehydrogenation reaction, the dehydrogenation conversion rate and the selectivity are both 100 percent, and the TOF value of the reaction is more than 240h-1The reaction time is 2h after being recycled, and the TOF value of the reaction is still more than 230h-1。
Detailed description of the invention
The present invention will be described in further detail by way of examples. The examples are not to be construed as limiting the invention.
Example 1:
process for preparing catalyst
Dissolving 0.1g of palladium chloride, 0.2g of glucosamine hydrochloride and 0.6g of melamine in 200mL of deionized water, fully stirring the mixed solution in a water bath at 75 ℃ until the mixed solution is dried, transferring the mixed solution to a tubular furnace, roasting the mixed solution for 7 hours at 520 ℃, and obtaining Pd after roasting2+@ CNx, noted as Pd2+@20CN0.8. Pd is added2+@20CN0.8Placing in a tube type atmosphere furnace, and reducing in a reducing atmosphere to 3% H2/N2The reduction time is 2h at the reduction temperature of 250 ℃, and the catalyst is recorded as Pd @20CN0.8And (4) sealing and storing.
Dehydrogenation process
50mg of the catalyst is loaded into a tubular reactor, the tubular reactor is placed in a water bath, the reaction temperature is controlled to be 5 ℃, 5g of mixed solution of formaldehyde and sodium hydroxide with the molar ratio of 1:0.6 is dripped into the tubular reactor, reaction gas is collected, the selectivity of hydrogen after reaction is 100 percent, the conversion rate of formaldehyde is 100 percent, and the TOF value of the reaction is 245h-1The reaction time is 2h after recycling, and the TOF value of the reaction is still more than 239h-1。
Example 2
Process for preparing catalyst
Dissolving 0.1g of palladium chloride, 0.3g of glucosamine hydrochloride and 0.6g of melamine in 200mL of deionized water, fully stirring the mixed solution in a water bath at 90 ℃ until the mixed solution is dried, transferring the mixed solution to a tubular furnace, roasting the mixed solution for 5 hours at 560 ℃, and obtaining Pd after roasting2+@ CNx, noted as Pd2+@25CN0.95. Pd is added2+@25CN0.95Placing in a tube type atmosphere furnace with 8% H in reducing atmosphere2/N2The reduction time is 4h at the reduction temperature of 280 ℃, and the catalyst is recorded as Pd @25CN0.95And (4) sealing and storing.
Dehydrogenation process
50mg of the catalyst is loaded into a tubular reactor, the tubular reactor is placed in a water bath, the reaction temperature is controlled to be 40 ℃, 10g of mixed solution of formaldehyde and sodium hydroxide with the molar ratio of 1:1.3 is dripped into the tubular reactor, reaction gas is collected, the selectivity of hydrogen after reaction is 100 percent, the conversion rate of formaldehyde is 100 percent, and the TOF value of the reaction is 320h-1The reaction time is 2h after being recycled, and the TOF value of the reaction is still more than 310h-1。
Example 3
Process for preparing catalyst
Dissolving 0.1g of palladium chloride, 0.45g of glucosamine hydrochloride and 0.8g of melamine in 200mL of deionized water, fully stirring the mixed solution in a water bath at 110 ℃ until the mixed solution is dried, transferring the mixed solution to a tubular furnace, roasting the mixed solution for 4 hours at 680 ℃, and obtaining Pd after roasting2+@ CNx, noted as Pd2+@32CN1.1. Pd is added2+@32CN1.1Placing in a tube type atmosphere furnace with 10% H in reducing atmosphere2/N2When the reduction temperature is 360 DEG CM 5h, catalyst is marked as Pd @32CN1.1And (4) sealing and storing.
Dehydrogenation process
50mg of the catalyst is loaded into a tubular reactor, the tubular reactor is placed in a water bath, the reaction temperature is controlled to be 50 ℃, 9g of mixed solution of formaldehyde and sodium hydroxide with the molar ratio of 1:2 is dripped into the tubular reactor, reaction gas is collected, the selectivity of hydrogen after reaction is 100 percent, the conversion rate of formaldehyde is 100 percent, and the TOF value of the reaction is 480h-1The reaction time of the catalyst is 2h after being recycled, and the TOF value of the reaction is still larger than 465h-1。
Example 4
Process for preparing catalyst
Dissolving 0.1g of palladium chloride, 0.4g of glucosamine hydrochloride and 0.7g of melamine in 200mL of deionized water, fully stirring the mixed solution in a water bath at 100 ℃ until the mixed solution is dried, transferring the mixed solution to a tubular furnace, roasting the mixed solution for 5 hours at 630 ℃, and obtaining Pd after roasting2+@ CNx, noted as Pd2+@28CN1.03. Pd is added2+@28CN1.03Placing in a tube type atmosphere furnace with 6% H in reducing atmosphere2/N2The reduction time is 3h at the reduction temperature of 310 ℃, and the catalyst is recorded as Pd @28CN1.03And (4) sealing and storing.
Dehydrogenation process
50mg of the catalyst is loaded into a tubular reactor, the tubular reactor is placed in a water bath, the reaction temperature is controlled to be 35 ℃, 7g of mixed solution of formaldehyde and sodium hydroxide with the molar ratio of 1:0.8 is dripped into the tubular reactor, reaction gas is collected, the selectivity of hydrogen after reaction is 100 percent, the conversion rate of formaldehyde is 100 percent, and the TOF value of the reaction is 360 hours-1The reaction time is 2h after being recycled, and the TOF value of the reaction is still larger than 352h-1。
Example 5
Process for preparing catalyst
Dissolving 0.1g of palladium chloride, 0.35g of glucosamine hydrochloride and 0.75g of melamine in 200mL of deionized water, fully stirring the mixed solution in a water bath at 90 ℃ until the mixed solution is dried, transferring the mixed solution to a tubular furnace, roasting the mixed solution for 5.5 hours at 660 ℃, and obtaining Pd after roasting2+@ CNx, noted as Pd2+@30CN1.07. Will be provided withPd2+@30CN1.07Placing in a tube type atmosphere furnace, and reducing in 7% H atmosphere2/N2The reduction time is 3.5h at the reduction temperature of 310 ℃, and the catalyst is recorded as Pd @30CN1.07And (4) sealing and storing.
Dehydrogenation process
50mg of the catalyst is loaded into a tubular reactor, the tubular reactor is placed in a water bath, the reaction temperature is controlled to be 20 ℃, 8g of mixed solution of formaldehyde and sodium hydroxide with the molar ratio of 1:1.6 is dripped into the tubular reactor, reaction gas is collected, the selectivity of hydrogen after reaction is 100 percent, the conversion rate of formaldehyde is 100 percent, and the TOF value of the reaction is 320h-1The reaction time is 2h after being recycled, and the TOF value of the reaction is still more than 310h-1。
Example 6
Process for preparing catalyst
Dissolving 0.1g of palladium chloride, 0.4g of glucosamine hydrochloride and 0.65g of melamine in 200mL of deionized water, fully stirring the mixed solution in a water bath at 105 ℃ until the mixed solution is dried, transferring the mixed solution to a tubular furnace, roasting the mixed solution for 4.5 hours at 570 ℃, and obtaining Pd after roasting2+@ CNx, noted as Pd2+@26CN0.93. Pd is added2+@26CN0.93Placing in a tube type atmosphere furnace with 4% H in reducing atmosphere2/N2The reduction time is 3.5h at the reduction temperature of 330 ℃, and the catalyst is recorded as Pd @26CN0.93And (4) sealing and storing.
Dehydrogenation process
50mg of the catalyst is loaded into a tubular reactor, the tubular reactor is placed in a water bath, the reaction temperature is controlled to be 15 ℃, 6g of mixed solution of formaldehyde and sodium hydroxide with the molar ratio of 1:1.4 is dripped into the tubular reactor, reaction gas is collected, the selectivity of hydrogen after reaction is 100 percent, the conversion rate of formaldehyde is 100 percent, and the TOF value of the reaction is 290h-1The reaction time of TOF is still more than 281h after the reaction is recycled for 2h-1。
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (1)

1. The method for catalyzing formaldehyde dehydrogenation by using Pd @ CNx mosaic catalyst is characterized in that the prepared Pd @ CNxPlacing the mosaic catalyst in a reactor, placing the reactor in a water bath, heating to 5-50 ℃, and adding a mixed solution of formaldehyde and sodium hydroxide with a molar ratio of 1 (0.6-2) into the reactor for reaction to obtain a product hydrogen;
the Pd @ CNxThe mass ratio of the mosaic catalyst to the mixed liquid of formaldehyde and sodium hydroxide is 1 (100-200);
the Pd @ CNx mosaic catalyst is prepared by the following steps:
dissolving palladium chloride and glucosamine hydrochloride according to a certain mass ratio to form a uniform mixed solution, and adding melamine into the uniform mixed solution according to a certain mass ratio;
step (2) stirring the mixed solution obtained in the step (1) at a certain temperature until the mixed solution is dried, transferring the mixed solution to a tubular furnace, and roasting the mixed solution at a certain temperature to obtain Pd2+@CNx；
Step (3) roasting the obtained Pd2+The @ CNx is transferred to a tubular atmosphere furnace and reduced by mixed gas at a certain temperature to prepare the Pd @ CNx mosaic catalyst;
in the step (1): the mass ratio of the palladium chloride to the glucosamine hydrochloride to the melamine is 1 (2-4.5) to (6-8);
in the step (2): stirring until the drying temperature is 75-110 ℃, the roasting temperature of the tubular furnace is 520-680 ℃, the roasting time is 4-7 h, and the mass ratio of Pd to CNx is 1: (20-32), x is 0.8-1.1;
in the step (3): the reduction temperature of the tubular atmosphere furnace is 250-360 ℃, the reduction time is 2-5H, and the mixed gas for reduction is H2/N2In which H is2The volume ratio of (A) is 3-10%.
CN201811488328.7A 2018-12-06 2018-12-06 Method for catalyzing formaldehyde dehydrogenation by using Pd @ CNx mosaic catalyst Active CN109622010B (en)

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