CN115414931B - Preparation method of Pd/ZnO catalyst for preparing hydrogen by methanol steam reforming - Google Patents

Preparation method of Pd/ZnO catalyst for preparing hydrogen by methanol steam reforming Download PDF

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CN115414931B
CN115414931B CN202211063569.3A CN202211063569A CN115414931B CN 115414931 B CN115414931 B CN 115414931B CN 202211063569 A CN202211063569 A CN 202211063569A CN 115414931 B CN115414931 B CN 115414931B
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hydrogen
catalyst
methanol
steam reforming
zno
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CN115414931A (en
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孙少瑞
王慧敏
王亚鑫
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Beijing University of Technology
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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 preparing hydrogen by steam reforming of methanol, which belongs to the field of hydrogen preparation of methanol. The method comprises the following steps: firstly, zinc oxide is dispersed into ethylene glycol to form suspension, then sodium tetrachloropalladate precursor is added, after soaking for a period of time, centrifugal washing and drying are carried out, thus obtaining Pd/ZnO catalyst, fresh Pd/ZnO is reduced by hydrogen to form part of PdZn alloy, and the double reduction means realizes high-selectivity hydrogen production. Compared with the industrial simple synthesis method, the synthesized material has high temperature resistance, the CO content in the byproducts after the reaction at 400 ℃ is integrally lower, and CH 4 Almost zero. The hydrogen production method has the advantages of high hydrogen yield, less byproducts, simple and uncomplicated operation, capability of realizing portable hydrogen production, and the like, and has good industrial prospect.

Description

Preparation method of Pd/ZnO catalyst for preparing hydrogen by methanol steam reforming
Technical Field
The invention belongs to the field of hydrogen production from methanol, and designs a preparation method of a Pd/ZnO catalyst for hydrogen production from methanol steam reforming.
Background
With the increasing exhaustion of fossil energy and the need for clean new energy, the development of hydrogen has become a consensus among all parties. The hydrogen energy has been 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 raw material H 2 The storage and supply problems of (a) remain and become a serious issue in research. The traditional hydrogen production modes such as electrolysis of water, natural gas, coal, hydride and the like have the defects of high energy consumption, environmental pollution, high cost, low hydrogen yield and the like, and have the defects of difficult hydrogen storage, high risk, high price and the like in the links of storage, transportation, hydrogenation and the like due to the characteristics of low hydrogen density, inflammability, explosiveness and the like. Methanol is the best choice for producing hydrogen because of its high hydrogen-carbon ratio, easily available sources, easy transportation, surplus productivity and low price.
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 latter three hydrogen production modes have the defects of low hydrogen production amount, poor control of reaction, easy sintering of catalyst, high CO content and the like, and the methanol steam reforming hydrogen production can react at a lower temperature (250-400 ℃) without introducing oxygen, high hydrogen production amount and the like, so that the application is most widely used. The methanol steam reforming is mainly divided into the following 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
methanol steam reforming catalyst systems are mainly divided into two major classes, namely Cu-based catalysts and noble metal-based (such as Pd and Pt) catalysts, wherein the Cu content in the copper-based catalyst is about 50%, the activity of the copper-based catalyst is higher, but the catalyst is deactivated by sintering due to the excessive reaction temperature, and the catalyst is easy to generate spontaneous combustion when exposed to air, has higher sensitivity to extremely small amount of sulfur, and performs in-situ pretreatment on hydrogen to obtain complete activity. On the basis of Cu-based catalyst, zr, ce and other metals are added to enhance the sintering resistance, but CO 2 The selectivity is greatly affected. In comparison, pd-based early-stage activity is not as good as Cu-based, but has the advantages of high temperature resistance, difficult oxidation, long-term stability and the like along with the reaction.
The Pd/ZnO series catalyst has been found by researchers to have excellent performance in steam reforming of methanol, and the former has been studied to show that the metal-carrier interaction between Pd and ZnO is strong, and the formation of part of PdZn alloy after reduction can lead to the conversion rate of methanol and CO 2 Is enhanced. Because Pd/ZnO has better reactivity under a high-temperature system, CO and CH are usually easier to generate under high temperature 4 High conversion and high selectivity are difficult to achieve. Most of the former studies have better Pd/ZnO properties but the preparation process is more complicated. Therefore, it is still important to design a simpler synthesis method and to achieve both high activity and high selectivity Pd/ZnO catalysts.
Disclosure of Invention
The invention aims to solve the problem of H of the existing catalyst 2 Low yield and CO 2 The selectivity is lower, a Pd/ZnO catalyst with high catalytic efficiency is developed, and a preparation method of the catalyst is provided. The method adopts wet impregnation, and prepares a series of Pd/ZnO catalysts loaded by different Pd by changing the dosage of the added sodium tetrachloropalladate precursor solution.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of Pd/ZnO catalyst for preparing hydrogen by methanol steam reforming 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 dispersed uniformly.
And 2, placing the zinc oxide white suspension obtained in the step 1 into a water bath kettle, heating to 100 ℃, and adding circulating cooling water for protection.
And 3, adding the 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 in the step 3 for 3 hours, stopping heating, adding 100mL of ethanol, stirring for 30 minutes at room temperature, and obtaining solid powder after centrifugation, ethanol and water washing.
And 5, freezing the solid powder obtained in the step 4, drying in vacuum and grinding.
Step 6, calcining and reducing the powder ground in the step 5 in a tube furnace, wherein the calcining atmosphere is H with the volume fraction of 5 percent 2 The rest is 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 centrifugal speed was 10000rpm, the number of times of ethanol washing was 2 times, and the number of times of water washing was 1 time.
Further, in step 5, both freezing and vacuum drying are performed in a freeze dryer; the freezing time was 2h and the vacuum drying time was 12h.
The invention has the following advantages:
1. the method adopts commercial nano zinc oxide as a carrier, synthesizes precursor suspension by wet impregnation, and obtains Pd/ZnO catalyst by washing, drying, calcining and other steps. Reduces the complex flow for preparing the carrier and solves the problem of complex conventional synthetic route of the catalyst.
2. The method adopts a wet method for preparation in the synthesis process. The reaction condition is 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, keeps the trend of increasing the activity along with the increase of the temperature, and produces CO and CH as byproducts at higher reaction temperature 4 Less.
4. The Pd/ZnO catalyst synthesized by the method shows the optimal hydrogen yield (after 5 hours of reaction) in the steam reforming of methanol (1628 mmol/g) cat /h), and CO 2 The selectivity is up to 97.7%, the conversion rate of methanol is 94%, the CO content is lower than 1%, and the CH content is 0.5% 4 Almost zero, and has good industrial application prospect.
Drawings
FIG. 1 is a flow chart for preparing Pd/ZnO catalyst
FIG. 2 is an XRD pattern for Pd/ZnO catalysts (four different sodium tetrachloropalladates loadings)
FIG. 3 is a graph showing the variation of hydrogen yield of Pd/ZnO catalyst (four different amounts of sodium tetrachloropalladate) in the steam reforming of methanol to produce hydrogen
FIG. 4 is a graph showing the change in conversion of Pd/ZnO catalyst (four different amounts of sodium tetrachloropalladate) in the steam reforming of methanol to produce hydrogen
FIG. 5 is a graph of CO in the steam reforming of methanol with Pd/ZnO catalyst (four different sodium tetrachloropalladate levels) 2 Selective change pattern
ABCD in fig. 2-5 correspond to examples 1-4, respectively.
Detailed Description
The invention will be described in further detail with reference to the drawings and examples.
Example 1
After heating a suspension containing 1.0g of zinc oxide to 100 ℃, 2.765ml of a sodium tetrachloropalladate solution having a concentration of 10mg/ml was added, and the hydrothermal reaction was carried out for 3 hours. The solution was then transferred to a beaker, stirred at room temperature for 30min after adding 100mL of ethanol, and then centrifuged with a centrifuge, after which the supernatant was removed and the precipitate was redispersed with ethanol for washing. The washing step was repeated 2 times and 1 time with water, after which the precipitate was freeze-dried with a freeze dryer and ground to a solid powder P. Calcining and reducing the solid powder P in a tube furnace under 5%H reducing atmosphere 2 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 sieving after the calcination is naturally cooled. The palladium content in A was 1wt%.
XRD phase analysis was performed on the above A material, and as shown in FIG. 1, the prepared sample had almost no signal of PdZn alloy. Grinding, tabletting and granulating (40-60 mesh) the synthesized catalyst, taking 100mg of the catalyst, placing the catalyst in a sample tube, fixing the sample tube in a reactor, wherein the ratio of quartz sand to sample is 1:3. The test conditions were pipeline carrier gas: 0.3MpaAr, ar flow: 15mL/min, liquid inlet: 0.05mL/min, S/C:1.2, vaporization temperature: 120 ℃, reaction temperature: 400 ℃. After 5 hours of reaction, as shown in FIG. 2, the hydrogen yield of the catalyst was 501.4mmol/g cat And/h. As shown in fig. 3, the methanol conversion of the catalyst was 26.1%, less than 30%. As shown in FIG. 4, the CO of the catalyst 2 The selectivity was 93.0% and less than 95%.
Example 2
After heating a suspension containing 1.0g of zinc oxide to 100 ℃, 5.530ml of a sodium tetrachloropalladate solution having a concentration of 10mg/ml was added, and the hydrothermal reaction was carried out for 3 hours. The solution was then transferred to a beaker, stirred at room temperature for 30min after adding 100mL of ethanol, and then centrifuged with a centrifuge, after which the supernatant was removed and the precipitate was redispersed with ethanol for washing. The washing step was repeated 2 times and then washed with water 1The precipitate was then freeze-dried with a freeze dryer and ground to a solid powder P. Calcining and reducing the solid powder P in a tube furnace under 5%H reducing atmosphere 2 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 sieving after the calcination is naturally cooled. The palladium content in B was 2wt%.
XRD phase analysis was performed on the above B material, and as shown in FIG. 1, the prepared sample had a less pronounced signal of PdZn alloy. Grinding, tabletting and granulating (40-60 mesh) the synthesized catalyst, taking 100mg of the catalyst, placing the catalyst in a sample tube, fixing the sample tube in a reactor, wherein the ratio of quartz sand to sample is 1:3. The test conditions were pipeline carrier gas: 0.3MpaAr, ar flow: 15mL/min, liquid inlet: 0.05mL/min, S/C:1.2, vaporization temperature: 120 ℃, reaction temperature: 400 ℃. After 5 hours of reaction, as shown in FIG. 2, the hydrogen yield of the catalyst was 1398.5mmol/g cat And/h. As shown in fig. 3, the methanol conversion of the catalyst was 83.6%. As shown in FIG. 4, the CO of the catalyst 2 The selectivity is 97.8% and is more than 95%.
Example 3
After heating a suspension containing 1.0g of zinc oxide to 100 ℃, 8.294ml of a sodium tetrachloropalladate solution having a concentration of 10mg/ml was added, and the hydrothermal reaction was carried out for 3 hours. The solution was then transferred to a beaker, stirred at room temperature for 30min after adding 100mL of ethanol, and then centrifuged with a centrifuge, after which the supernatant was removed and the precipitate was redispersed with ethanol for washing. The washing step was repeated 2 times and 1 time with water, after which the precipitate was freeze-dried with a freeze dryer and ground to a solid powder P. Calcining and reducing the solid powder P in a tube furnace under 5%H reducing atmosphere 2 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 sieving after the calcination is naturally cooled. The palladium content in C was 3wt%.
XRD phase analysis is carried out on the C material, and as shown in figure 1, the PdZn alloy signal in the prepared sample is obvious. Grinding, tabletting and granulating (40-60 mesh) the synthesized catalyst, loading 100mg of catalyst into sample tube, mixing quartz sand and sample at a ratio of1:3, sample tubes were fixed in the reactor. The test conditions were pipeline carrier gas: 0.3MpaAr, ar flow: 15mL/min, liquid inlet: 0.05mL/min, S/C:1.2, vaporization temperature: 120 ℃, reaction temperature: 400 ℃. After 5h of reaction, the hydrogen yield of the catalyst was 1628mmol/g as shown in FIG. 2 cat And/h. As shown in fig. 3, the methanol conversion of the catalyst was 94%. As shown in FIG. 4, the CO of the catalyst 2 The selectivity is 97.7% and is more than 95%.
Example 4
After heating a suspension containing 1.0g of zinc oxide to 100 ℃, 11.06ml of a sodium tetrachloropalladate solution having a concentration of 10mg/ml was added, and the hydrothermal reaction was carried out for 3 hours. The solution was then transferred to a beaker, stirred at room temperature for 30min after adding 100mL of ethanol, and then centrifuged with a centrifuge, after which the supernatant was removed and the precipitate was redispersed with ethanol for washing. The washing step was repeated 2 times and 1 time with water, after which the precipitate was freeze-dried with a freeze dryer and ground to a solid powder P. Calcining and reducing the solid powder P in a tube furnace under 5%H reducing atmosphere 2 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 sieving after the calcination is naturally cooled. The palladium content in D was 4wt%.
XRD phase analysis was carried out on the D material, and as shown in FIG. 1, the prepared sample had larger particles of the PdZn alloy and had a significant signal of the PdZn alloy, in addition to the Pd signal. Grinding, tabletting and granulating (40-60 mesh) the synthesized catalyst, taking 100mg of the catalyst, placing the catalyst in a sample tube, fixing the sample tube in a reactor, wherein the ratio of quartz sand to sample is 1:3. The test conditions were pipeline carrier gas: 0.3MpaAr, ar flow: 15mL/min, liquid inlet: 0.05mL/min, S/C:1.2, vaporization temperature: 120 ℃, reaction temperature: 400 ℃. After 5 hours of reaction, as shown in FIG. 2, the hydrogen yield of the catalyst was 1272.7mmol/g cat And/h. As shown in fig. 3, the methanol conversion of the catalyst was 68.4%. As shown in FIG. 4, the CO of the catalyst 2 The selectivity is 97.6% and is more than 95%.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and 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 and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.

Claims (3)

1. A method for preparing a Pd/ZnO catalyst for preparing hydrogen by steam reforming of methanol, which 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, placing the zinc oxide white suspension obtained in the step 1 into a water bath kettle, heating to 100 ℃, and adding circulating cooling water for protection;
step 3, adding a sodium tetrachloropalladate solution to stir; the concentration of the sodium tetrachloropalladate solution is 10mg/ml; the dosage of the sodium tetrachloropalladate is 2.765ml-11.06ml;
step 4, stirring the mixed solution in the step 3 for 3 hours, stopping heating, adding 100mL of ethanol, stirring for 30 minutes at room temperature, and obtaining solid powder after centrifugation, ethanol and water washing;
step 5, freezing, vacuum drying and grinding the solid powder obtained in the step 4;
step 6, calcining and reducing the powder ground in the step 5 in a tube furnace, wherein the calcining atmosphere is H with the volume fraction of 5 percent 2 The rest is 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 a Pd/ZnO catalyst for steam reforming of methanol to produce hydrogen as defined in claim 1, wherein in step 4, the centrifugal speed is 10000rpm, the number of times of ethanol washing is 2, and the number of times of water washing is 1.
3. The method for preparing a Pd/ZnO catalyst for use in the steam reforming of methanol to produce hydrogen as defined in claim 1, wherein in step 5, both freezing and vacuum drying are performed in a freeze dryer; the freezing time was 2h and the vacuum drying time was 12h.
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