CN115414931A - Preparation method of Pd/ZnO catalyst for hydrogen production by methanol steam reforming - Google Patents
Preparation method of Pd/ZnO catalyst for hydrogen production by methanol steam reforming Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B01J35/23—
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- 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
A preparation method of Pd/ZnO catalyst for hydrogen production by methanol steam reforming belongs to the field of hydrogen production by methanol. The method comprises the following steps: firstly, dispersing zinc oxide into ethylene glycol to form suspension, then adding a sodium tetrachloropalladate precursor, soaking for a period of time, centrifuging, washing and drying to obtain a Pd/ZnO catalyst, reducing fresh Pd/ZnO by hydrogen to form part of PdZn alloy, and realizing high-selectivity hydrogen production by a double reduction means. The synthesis method is simpler than the industrial method, the synthesized material is high temperature resistant, the CO content in the by-product after the reaction at 400 ℃ is integrally lower, and the CH 4 Almost zero. The hydrogen production method has the advantages of high hydrogen production amount, few byproducts, simple and uncomplicated operation, capability of realizing portable hydrogen production and the like, and has good industrial prospect.
Description
Technical Field
The invention belongs to the field of hydrogen production by methanol, and designs a preparation method of a Pd/ZnO catalyst for hydrogen production by methanol steam reforming.
Background
With the increasing exhaustion of fossil energy and the demand for clean new energy, the development of hydrogen has become a common consensus among all parties. Hydrogen energy is rapidly developed and widely used due to its high energy and no pollution, especially in the fields of transportation vehicles, proton exchange membrane fuel cells, solid oxide fuel cells, etc.
But starting material H 2 The storage and supply problems of (2) still remain, and are becoming important to research. The traditional hydrogen production modes of electrolyzing water, natural gas, coal, hydride and the like have the defects of high energy consumption, environmental pollution, high cost, low hydrogen production amount and the like, and have the defects of difficult hydrogen storage, high danger, high price and the like in the links of storage, transportation, hydrogenation and the like due to the properties of low hydrogen density, flammability, explosiveness and the like. Methanol is undoubtedly the best choice for hydrogen production because of its advantages of high hydrogen-carbon ratio, easily available source, easy transportation, excess productivity, low price, etc.
Regarding methanol reforming technology, there are currently four hydrogen production modes: methanol steam reforming, methanol partial oxidation, methanol autothermal and methanol decomposition to produce hydrogen. The last three hydrogen production modes have the defects of oxygen gas introduction, low hydrogen production amount, difficult control of reaction, easy sintering of the catalyst, high CO content and the like, and the methanol steam reforming hydrogen production has no need of oxygen gas introduction, high hydrogen production amount and can react at a lower temperature (250-400 ℃), so the hydrogen production method is most widely applied. The methanol steam reforming is mainly divided into the following reaction steps:
CH 3 OH+H 2 O→3H 2 +CO 2 
CH 3 OH→2H 2 +CO
CO+H 2 O→CO 2 +H 2 
the methanol steam reforming catalytic system is mainly divided into two main types of Cu-based catalysts and noble metal-based (such as Pd and Pt) catalysts, the Cu content in copper is about 50%, the activity of the copper-based catalysts is high, but the high reaction temperature can cause the sintering deactivation of the catalysts, spontaneous combustion is easy to occur when the catalysts are exposed to air, the high sensitivity to extremely small amount of sulfur is realized, and hydrogen is introduced for obtaining full activityAnd carrying out in-situ pretreatment. Some add Zr, ce and other metals to Cu-based catalyst to enhance its anti-sintering ability, but CO 2 The selectivity is greatly affected. In contrast, the Pd group precursor activity is not as good as that of the Cu group, but as the reaction proceeds, has the advantages of high temperature resistance, difficult oxidation, long-term stability and the like.
Researchers find that the Pd/ZnO catalyst has excellent performance in the aspect of methanol steam reforming, and previous researches show that metal-carrier interaction between Pd and ZnO is strong, and partial PdZn alloy formed after reduction can enable the conversion rate of methanol and CO 2 The selectivity of (a) is enhanced. Because the Pd/ZnO has better reaction activity under a high-temperature system, but CO and CH are easily generated at high temperature 4 High conversion and high selectivity are difficult to achieve. Most of the Pd/ZnO studied by the predecessors have better performance but the preparation process is more complicated. Therefore, designing a simpler synthesis method and achieving both high activity and high selectivity of the Pd/ZnO catalyst is still important.
Disclosure of Invention
The invention aims to solve the problem of H of the existing catalyst 2 Low yield and CO 2 The Pd/ZnO catalyst with high catalytic efficiency is developed and the preparation method of the catalyst is provided. The method adopts wet impregnation, and prepares a series of Pd/ZnO catalysts loaded with different Pd by changing the dosage of the added sodium tetrachloropalladate precursor solution.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of Pd/ZnO catalyst for methanol steam reforming hydrogen production is characterized in that,
the method comprises the following steps:
step 1. 1.0g of zinc oxide was added to a flask containing 100mL of ethylene glycol and uniformly dispersed.
And 2, placing the white zinc oxide suspension obtained in the step 1 in a water bath, heating to 100 ℃, and adding circulating cooling water for protection.
And 3, adding a sodium tetrachloropalladate solution and stirring. The concentration of the sodium tetrachloropalladate solution used was 10mg/ml. The dosage of the sodium tetrachloropalladate is 2.765ml-11.06ml.
And 4, stirring the mixed solution obtained in the step 3 for 3 hours, stopping heating, adding 100mL of ethanol, stirring at room temperature for 30min, and carrying out centrifugation, ethanol washing and water washing to obtain solid powder.
And 5, freezing and vacuum drying the solid powder obtained in the step 4, and then grinding.
Step 6, calcining and reducing the powder ground in the step 5 in a tubular furnace, wherein the calcining atmosphere is H with the volume fraction of 5% 2 The balance of Ar, the reduction temperature is 300 ℃, and the reduction time is 2h. And naturally cooling to room temperature to obtain the Pd/ZnO catalyst.
Further, in step 4, the centrifugation rotation speed was 10000rpm, the number of ethanol washes was 2 times, and the number of water washes was 1 time.
Further, in step 5, freezing and vacuum drying are both carried out in a freeze dryer; the freezing time is 2h, and the vacuum drying time is 12h.
The invention has the following advantages:
1. the method adopts commercial nano zinc oxide as a carrier, synthesizes precursor suspension through wet impregnation, and obtains the Pd/ZnO catalyst through the steps of washing, drying, calcining and the like. Reduces the complex flow of preparing the carrier and solves the problem of complex conventional synthetic route of the catalyst.
2. The method adopts a wet method in the synthesis process. The reaction conditions are milder, the complexity is lower, and the large-scale industrial production is easier to realize.
3. The material synthesized by the method has high temperature resistance, the activity keeps rising with the rising of the temperature, and by-products of CO and CH are generated at higher reaction temperature 4 Less.
4. The Pd/ZnO catalyst synthesized by the method shows the optimal hydrogen yield (after 5h of reaction) in methanol steam reforming (1628 mmol/g) cat H), and CO 2 The selectivity is up to 97.7 percent, the conversion rate of methanol is 94 percent, the content of CO is lower than 1 percent, and is 0.5 percent, and the content of CH 4 Almost is zero, and has good industrial application prospect.
Drawings
FIG. 1 is a flow chart of Pd/ZnO catalyst preparation
FIG. 2 is an XRD pattern of Pd/ZnO catalyst (four different amounts of sodium tetrachloropalladate)
FIG. 3 is a graph showing the hydrogen yield variation of Pd/ZnO catalyst (four different amounts of sodium tetrachloropalladate) in methanol steam reforming hydrogen production
FIG. 4 is a graph showing the change of conversion rate of Pd/ZnO catalyst (four different amounts of sodium tetrachloropalladate) in methanol steam reforming hydrogen production
FIG. 5 shows CO generated by the Pd/ZnO catalyst (four different amounts of sodium tetrachloropalladate) in the methanol steam reforming for hydrogen production 2 Graph of selectivity variation
ABCD in FIGS. 2-5 correspond to examples 1-4, respectively.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
After the suspension containing 1.0g of zinc oxide is heated to 100 ℃, 2.765ml of sodium tetrachloropalladate solution with the concentration of 10mg/ml is added for hydrothermal reaction for 3 hours. The solution was then transferred to a beaker, 100mL of ethanol was added and stirred at room temperature for 30min, after which it was centrifuged in a centrifuge and after the supernatant was removed, ethanol was added to redisperse the precipitate and washed. The washing step was repeated 2 times and then 1 time with water, after which the precipitate was freeze-dried with a freeze-dryer and ground into a solid powder P. Calcining and reducing the solid powder P in a tubular furnace in a reducing atmosphere of 5%H 2 and/Ar (volume fraction), the reduction temperature is 300 ℃, the reduction time is 2 hours, and the Pd/ZnO catalyst A is obtained by grinding and screening after the calcining is finished and the natural cooling is carried out. The palladium content in A was 1wt%.
When the material A is subjected to XRD phase analysis, as shown in figure 1, the prepared sample has almost no signal of PdZn alloy. Grinding, tabletting and granulating (40-60 meshes) the synthesized catalyst, loading 100mg of the catalyst into a sample tube, wherein the ratio of quartz sand to the sample is 1:3, and fixing the sample tube in a reactor. The test conditions were pipeline carrier gas: 0.3MpaAr, ar flow: 15mL/min, liquid inlet amount: 0.05mL/min, S/C:1.2, vaporization temperature: 120 ℃ transThe reaction temperature is as follows: at 400 deg.c. After 5h of reaction, the hydrogen yield of the catalyst was 501.4mmol/g as shown in FIG. 2 cat H is used as the reference value. As shown in fig. 3, the methanol conversion of the catalyst was 26.1%, less than 30%. As shown in FIG. 4, CO of the catalyst 2 The selectivity was 93.0%, less than 95%.
Example 2
After the suspension containing 1.0g of zinc oxide is heated to 100 ℃, 5.530ml of sodium tetrachloropalladate solution with the concentration of 10mg/ml is added for hydrothermal reaction for 3 hours. The solution was then transferred to a beaker, 100mL of ethanol was added and stirred at room temperature for 30min, after which it was centrifuged in a centrifuge and after the supernatant was removed, ethanol was added to redisperse the precipitate and washed. The washing step was repeated 2 times and then 1 time with water, after which the precipitate was freeze-dried with a freeze-dryer and ground into a solid powder P. Calcining and reducing the solid powder P in a tubular furnace in a reducing atmosphere of 5%H 2 and/Ar (volume fraction), the reduction temperature is 300 ℃, the reduction time is 2 hours, and the Pd/ZnO catalyst B is obtained by grinding and screening after the calcining is finished and the natural cooling is carried out. The palladium content in B was 2wt%.
When the B material is subjected to XRD phase analysis, as shown in figure 1, the prepared sample has a less obvious signal of PdZn alloy. Grinding, tabletting and granulating (40-60 meshes) the synthesized catalyst, loading 100mg of the catalyst into a sample tube, wherein the ratio of quartz sand to the sample is 1:3, and fixing the sample tube in a reactor. The test conditions were pipeline carrier gas: 0.3MpaAr, ar flow: 15mL/min, liquid inlet amount: 0.05mL/min, S/C:1.2, vaporization temperature: 120 ℃, reaction temperature: at 400 deg.c. After 5h of reaction, the hydrogen yield of the catalyst was 1398.5mmol/g as shown in FIG. 2 cat H is used as the reference value. As shown in fig. 3, the methanol conversion of this catalyst was 83.6%. As shown in FIG. 4, CO of the catalyst 2 The selectivity was 97.8%, greater than 95%.
Example 3
After the suspension containing 1.0g of zinc oxide is heated to 100 ℃, 8.294ml of sodium tetrachloropalladate solution with the concentration of 10mg/ml is added for hydrothermal reaction for 3 hours. Then the solution was transferred to a beaker, added with 100mL of ethanol and stirred at room temperature for 30min, and then centrifuged with a centrifuge to remove the supernatant to obtainAfter that, ethanol was added to redisperse the precipitate for washing. The washing step was repeated 2 times and then 1 time with water, after which the precipitate was freeze-dried with a freeze-dryer and ground into a solid powder P. Calcining and reducing the solid powder P in a tubular furnace in a reducing atmosphere of 5%H 2 and/Ar (volume fraction), the reduction temperature is 300 ℃, the reduction time is 2 hours, and the Pd/ZnO catalyst C is obtained by grinding and screening after the calcining is finished and the natural cooling is carried out. The palladium content in C was 3wt%.
XRD phase analysis is carried out on the material C, and as shown in figure 1, pdZn alloy signals in the prepared sample are obvious. Grinding, tabletting and granulating (40-60 meshes) the synthesized catalyst, loading 100mg of the catalyst into a sample tube, wherein the ratio of quartz sand to the sample is 1:3, and fixing the sample tube in a reactor. The test conditions were pipeline carrier gas: 0.3MpaAr, ar flow: 15mL/min, liquid inlet amount: 0.05mL/min, S/C:1.2, vaporization temperature: 120 ℃, reaction temperature: at 400 ℃. After 5h of reaction, the hydrogen yield of the catalyst was 1628mmol/g, as shown in FIG. 2 cat H is used as the reference value. As shown in fig. 3, the methanol conversion of this catalyst was 94%. As shown in FIG. 4, CO of the catalyst 2 The selectivity was 97.7%, greater than 95%.
Example 4
After the suspension containing 1.0g of zinc oxide was heated to 100 ℃, 11.06ml of a 10mg/ml sodium tetrachloropalladate solution was added to conduct hydrothermal reaction for 3 hours. The solution was then transferred to a beaker, 100mL of ethanol was added and stirred at room temperature for 30min, after which it was centrifuged in a centrifuge and after the supernatant was removed, ethanol was added to redisperse the precipitate and washed. The washing step was repeated 2 times and then 1 time with water, after which the precipitate was freeze-dried with a freeze-dryer and ground into a solid powder P. Calcining and reducing the solid powder P in a tubular furnace in a reducing atmosphere of 5%H 2 and/Ar (volume fraction), the reduction temperature is 300 ℃, the reduction time is 2 hours, and the Pd/ZnO catalyst D is obtained by grinding and screening after the calcining is finished and the natural cooling is carried out. The palladium content in D was 4% by weight.
XRD phase analysis is carried out on the D material, as shown in figure 1, the PdZn alloy particles in the prepared sample are large, and the prepared sample has obvious PdZn alloy signal and Pd signal. Grinding, tabletting and granulating (40-60 meshes) the synthesized catalyst, loading 100mg of the catalyst into a sample tube, wherein the ratio of quartz sand to the sample is 1:3, and fixing the sample tube in a reactor. The test conditions were pipeline carrier gas: 0.3MpaAr, ar flow: 15mL/min, liquid inlet amount: 0.05mL/min, S/C:1.2, vaporization temperature: 120 ℃, reaction temperature: at 400 ℃. After 5h of reaction, the hydrogen yield of the catalyst was 1272.7mmol/g as shown in FIG. 2 cat H is used as the reference value. As shown in fig. 3, the methanol conversion of this catalyst was 68.4%. As shown in FIG. 4, CO of the catalyst 2 The selectivity was 97.6%, greater than 95%.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (3)
1. A preparation method of a Pd/ZnO catalyst for hydrogen production by methanol steam reforming is characterized by comprising the following steps:
step 1, adding 1.0g of zinc oxide into a flask containing 100mL of ethylene glycol for uniform dispersion;
step 2, putting the white zinc oxide suspension obtained in the step 1 into a water bath, heating to 100 ℃, and adding circulating cooling water for protection;
step 3, adding a sodium tetrachloropalladate solution and stirring; the concentration of the adopted sodium tetrachloropalladate solution is 10mg/ml; the dosage of the sodium tetrachloropalladate is 2.765ml-11.06ml;
step 4, stirring the mixed solution obtained in the step 3 for 3 hours, stopping heating, adding 100mL of ethanol, stirring for 30min at room temperature, and obtaining solid powder after centrifugation, ethanol washing and water washing;
step 5, freezing and vacuum drying the solid powder obtained in the step 4, and then grinding;
step 6, calcining and reducing the powder ground in the step 5 in a tubular furnace in a calcining atmosphere with volume fraction of 5 percentH 2 The balance of Ar, the reduction temperature is 300 ℃, and the reduction time is 2h; and naturally cooling to room temperature to obtain the Pd/ZnO catalyst.
2. The method for preparing the Pd/ZnO catalyst used for the hydrogen production by the steam reforming of the methanol as claimed in claim 1, wherein in the step 4, the centrifugal speed is 10000rpm, the number of times of ethanol washing is 2 times, and the number of times of water washing is 1 time.
3. The method for preparing the Pd/ZnO catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein in the step 5, freezing and vacuum drying are both carried out in a freeze dryer; the freezing time is 2h, and the vacuum drying time is 12h.
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