CN113145127A - Cu catalyst for hydrogen production by methanol steam reforming and preparation method and application thereof - Google Patents
Cu catalyst for hydrogen production by methanol steam reforming and preparation method and application thereof Download PDFInfo
- Publication number
- CN113145127A CN113145127A CN202110467291.5A CN202110467291A CN113145127A CN 113145127 A CN113145127 A CN 113145127A CN 202110467291 A CN202110467291 A CN 202110467291A CN 113145127 A CN113145127 A CN 113145127A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogen production
- steam reforming
- methanol steam
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous 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
- C01B2203/02—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
- C01B2203/1076—Copper or zinc-based 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
Abstract
The invention relates to a Cu catalyst for hydrogen production by methanol steam reforming, a preparation method and application thereof, wherein the catalyst comprises the following components in percentage by mass: 25 to 35 percent of CuO and Al2O3 60％‑75％，MOx0.1-15%, wherein M is one or more of Co, Mn and Zr, and the catalyst has a face-centered cubic spinel structure and can be used for methanol steam reforming hydrogen production reaction. Compared with the prior art, the catalyst has the advantages of high catalytic performance, good stability and the like.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and the catalyst is composed of mixed oxides which mainly comprise Cu and Al and are added with one or more of Co, Mn and Zr as auxiliaries.
Background
Under the background of the current social energy problem and the environmental pollution problem becoming more severe, hydrogen is considered as one of the most promising energy sources to replace fossil fuels as a new green and environment-friendly energy source, and has been widely studied in recent years.
Hydrogen is a secondary energy source and cannot be directly exploited from the natural environment. The preparation method of the hydrogen comprises the steps of hydrogen production by water electrolysis, hydrogen production by fossil fuel, hydrogen production by ammonia decomposition, hydrogen production by biomass and the like. In recent years, the hydrogen production by methanol conversion is widely applied due to the advantages of low cost, convenient storage and transportation, mild reaction conditions, few byproducts and the like. The methanol hydrogen production technology mainly comprises partial oxidation hydrogen production by methanol, hydrogen production by methanol steam reforming and hydrogen production by methanol autothermal reforming.
The catalyst is a core content of the methanol hydrogen production technology. For the development and application of the catalyst, two systems of a non-noble metal catalyst and a noble metal catalyst are mainly included. Among them, noble metal catalysts show high catalytic activity and excellent stability in the reaction of producing hydrogen from methanol, but the development of noble metal catalysts is limited due to their high price. In a non-noble metal catalyst system, the copper-based catalyst has the most research and the most application, shows better catalytic activity and selectivity in application and has low price. It has been reported that, among the copper-based catalysts, a catalyst having a spinel structure passes through H2Shows good catalytic performance in the reaction [ appl.Catal.B: environ, 2011,106,650-]。
Although the catalyst with the spinel structure shows better catalytic performance in the reaction of preparing hydrogen from methanol, the stability of the catalyst does not meet the requirement of industrialization. Because the Taman temperature of copper is lower, the copper-based catalyst can be gradually agglomerated in the reaction process, so that crystal grains are gradually grown, and finally the catalyst is inactivated. Therefore, a catalyst which has high activity, good stability, low cost and easy industrialization is needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a Cu catalyst for methanol steam reforming hydrogen production, which has high activity, good stability and low cost, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: a Cu catalyst for hydrogen production by methanol steam reforming comprises the following components in percentage by mass: 25 to 35 percent of CuO and Al2O360 to 75 percent of catalyst and 0.1 to 15 percent of MOxM, wherein M is one or more of Co, Mn and Zr, x is 1 to 3, and the catalyst has a face-centered cubic spinel structure.
A preparation method of a Cu catalyst for hydrogen production by methanol steam reforming comprises the following steps:
step 1: dissolving soluble precursors of Cu, Al and M in ethanol water solution to prepare 0.1-1.0 mol.L-1The solution of (1);
step 2: weighing a precipitant with the mole number of (1-1.3) sigma niXi, wherein ni is the mole number of metal ions, and Xi is the valence of the metal ions, dissolving the precipitant in an ethanol aqueous solution to prepare a solution with the same volume as that of the step 1;
and step 3: and (3) putting the solution obtained in the steps (1) and (2) into a reactor at a constant speed, stirring vigorously, aging at a constant temperature of 50-80 ℃ for 2-4h, filtering, drying a filter cake at a temperature of 100-120 ℃, tabletting, grinding and sieving, sieving with a 40-60-mesh sieve, putting the powder in a muffle furnace at a temperature of 600-1000 ℃ and roasting for 0-6h, preferably for 1-3h to obtain the catalyst.
The coprecipitation synthesis method of the catalyst can be replaced by other synthesis methods. The other synthesis method is selected from a urea method, a hydrothermal synthesis method, a mechanochemical method and a solution combustion synthesis method.
The precursor of Al is aluminum chloride, aluminum nitrate, pseudo-boehmite, gamma-Al2O3One or more of them.
The precursor of Al is pseudo-boehmite or gamma-Al2O3In this case, the precursor is previously put into an ethanol aqueous solution.
The precursor of Cu is one or more of copper chloride, copper nitrate and copper acetate.
The precursor of Co is one or more of cobalt chloride, cobalt nitrate and cobalt acetate;
the precursor of Mn is one or more of manganese chloride, manganese nitrate and manganese acetate;
the precursor of Zr is one or more of zirconium chloride, zirconium nitrate and zirconium oxynitrate.
The mass fraction of the ethanol water solution is 0-50%, preferably 20-40%.
The precipitator in the step 2 is one or more selected from sodium carbonate, ammonium carbonate and potassium carbonate.
In the step 1, one or more soluble precursors of Si, Fe, Ce, La, Mg and Mo can be added into the ethanol water solution to be used as a composite carrier.
The application of the Cu catalyst for preparing hydrogen by reforming methanol steam is characterized in that the catalyst is applied to a methanol steam reforming hydrogen preparation process, and the using conditions are as follows: the reaction temperature is 200 ℃ and 350 ℃, the reaction pressure is normal pressure and 2MPa, and the mass space velocity is 0.1-3.5h-1、H2O/CH3OH molar ratio of 0.5-3.5: 1.
compared with the prior art, the invention has the following beneficial effects:
1. the catalyst of the invention is composed of mixed oxides which mainly comprise Cu and Al and are added with one or more of Co, Mn and Zr as auxiliary agents, and is of a copper-aluminum spinel oxide structure, and the chemical formula of the composite oxides is AB2O4Wherein A and B are typically a divalent cation and a trivalent cation, respectively. In the spinel structure, unit cells are piled up by oxygen anions and divalent ions to form 64 tetrahedral vacancies and 32 octahedral vacancies, divalent copper ions and trivalent metal cations are separated from each other, and copper is confined in the spinel lattice and is separated by oxygen atoms or voids. Compared with a non-spinel structure supported catalyst, the spinel structure has good stability, and active Cu generated by reduction under the spinel structure has relatively high dispersity and anti-sintering performance. By gradually reducing the spinel in the reaction process by the reaction raw materials, the method is simple to operate, low in cost, smaller in copper particles obtained by reduction, and better in activity and stability.
2. The invention adopts an improved coprecipitation method to prepare the catalyst, firstly, metal precursors are dissolved and mixed in ethanol water solution, and then precipitator which is 1 to 1.3 times of the sum of the mole number of the metal ions and the valence of the metal ions is added to dissolve in the ethanol water solution, so that the soluble precursors are dispersed more uniformly in the ethanol water solution; excess precipitant completes the precipitation of the metal cation. The obtained catalyst precursor is roasted at high temperature in a muffle furnace to form a stable copper-aluminum spinel oxide structure.
3. The catalyst of the invention has good catalytic activity, and the initial conversion rate of methanol can reach 99% under the condition that the catalyst is not subjected to pre-reduction treatmentIn the invention, due to the unique spinel structure of the catalyst, active components are slowly released on line and new active centers are formed in the hydrogen production reaction by methanol steam reforming, so that the deactivation speed of the catalyst is slowed down. In the environment of raw material gas, active metal Cu is slowly released from spinel skeleton structure of spinel structure catalyst, so that the catalyst has active center supplement in a long period of reaction time, and at the same time, Cu not separated out from spinel structure2+Ions are kept in a spinel-structured framework to form defect spinel, and the defect spinel has a stabilizing effect on newly generated active Cu particles to a certain extent. Therefore, the conversion rate of the methanol of the catalyst can be maintained to be more than 85 percent after the catalyst is used for 200 hours.
4. The cost is low, and the raw materials are mainly cheap non-noble metal catalysts which are easy to obtain.
5. The preparation method is simple, easy to industrialize, low in pollution, free of pre-reduction treatment of the catalyst before use, and suitable for large-scale industrialized use.
Drawings
FIG. 1 is an XRD spectrum of a catalyst of example 1 of the present invention;
FIG. 2 is H for catalyst of example 1 of the present invention2-TPR spectrum;
FIG. 3 is a graph of methanol conversion over time for Cu-Mn-Al spinel catalyst synthesized in inventive example 3 and a Cu-Zn-Al catalyst used commercially.
FIG. 4 is a plot of CO selectivity as a function of time.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
The phase structure of the catalyst was analyzed by means of a D/max-2200/PC X-ray diffractometer from Japan chemical company. The test conditions were: cu target (λ ═ 0.154056nm), scan range 10 to 90 °, scan step 0.005 °, scan speed 5 ° · min-1Tube voltage 40kV and tube current40mA。
H-adsorptivity of catalyst by PCA-1200 model of Beijing Piaode electronics GmbH2-TPR test.
The catalyst performance test is carried out by adopting a fixed bed reactor, and the gas phase product is analyzed by adopting a gas chromatograph of Nanjing Kejie analytical instrument, Inc. and provided with a 5A molecular sieve column, a TDX-01 column, a PEG-20M column, a TCD detector and an FID detector, so that the conversion rate and the selectivity are obtained.
Example 1
Accurately weigh 5.95 grams of CuCl2·2H2O, 51.10 g Al (NO)3)3·9H2O and 1.25 g Mn (NO) with a mass fraction of 50%3)2Adding deionized water into the solution to prepare 200ml of mixed solution; accurately weigh 25.73 grams of Na2CO3Deionized water was added to prepare 200ml of a mixed solution. Pumping the two parts of the obtained aqueous solution into a reactor at a constant speed through a sample injection pump, violently stirring, aging at a constant temperature of 70 ℃ for 3 hours, filtering, drying a filter cake at 100 ℃, tabletting, grinding and sieving by a 40-mesh sieve, and roasting sieved powder in a muffle furnace at 850 ℃ for 0 hour (namely, the muffle furnace is heated to 850 ℃ from the normal temperature by a program at a speed of 3 ℃/min, and then the temperature is directly and naturally reduced to the normal temperature state without the constant temperature maintaining operation (0 hour). The catalyst is obtained, and the mass fraction of each component is as follows: 27.94% of CuO and Al2O369.47% and 2.76% of Mn oxide.
XRD characterization of the catalyst was performed by X-ray diffraction technique, and the results are shown in FIG. 1. All diffraction peaks in the spectra were assigned to spinel, indicating that the synthesized catalyst has a face-centered cubic spinel structure.
H is carried out on the catalyst by adopting a chemical adsorption instrument2TPR characterization, the results are shown in FIG. 2.
1.0g of catalyst of 40-60 meshes was filled in the reactor, the temperature was raised to 270 ℃ to start the reaction of the feed, and the reaction conditions and results are shown in Table 1.
Example 2
Accurately weigh 8.36 grams of Cu (NO)3)2·3H2O, 24.21 g Al (NO)3)3·9H2O, 2.48 g Mn (NO) with mass fraction of 50%3)2Solution and 0.48 g Zr (NO)3)45H2O, adding 50% by weight of ethanol aqueous solution to prepare 200ml of mixed solution, and accurately weighing 6.63 g of gamma-Al2O3Putting into a reactor; accurately weigh 13.42 g (NH)4)2CO3Ethanol water solution with the mass fraction of 50 percent is added to prepare 200ml of mixed solution. Pumping the obtained two solutions into a reactor at a constant speed through a sample injection pump, violently stirring, aging at a constant temperature of 60 ℃ for 6 hours, filtering, drying a filter cake at 120 ℃, tabletting, grinding and screening through a 40-mesh sieve, and roasting screened powder in a muffle furnace at 900 ℃ for 3 hours to obtain the catalyst, wherein the mass fraction of each component is as follows: 27.52% of CuO and Al2O369.73%, Mn oxide 1.38%, ZrO21.37%. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 3
Accurately weigh 8.32 grams of Cu (NO)3)2·3H2O, 48.42 g Al (NO)3)3·9H2O and 3.08 g Mn (NO) with a mass fraction of 50%3)2Adding deionized water into the solution to prepare 200ml of mixed solution; accurately weighing 25.08 g of Na2CO3Deionized water was added to prepare 200ml of a mixed solution. Pumping the two parts of the obtained aqueous solution into a reactor at a constant speed through a sample injection pump, violently stirring, aging at a constant temperature of 65 ℃ for 3 hours, filtering, drying a filter cake at 120 ℃, tabletting, grinding and sieving by a 40-mesh sieve, and roasting sieved powder in a muffle furnace at 800 ℃ for 3 hours to obtain the catalyst, wherein the mass fraction of each component is as follows: 27.54% of CuO and Al2O365.83% and Mn oxide 6.80%. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
The above synthesized catalyst was compared with a Cu-Zn-Al catalyst used industrially by reaction tests, and the change of conversion of methanol with time was shown in FIG. 3. Therefore, the synthesized catalyst shows higher catalytic activity and stability in the reaction.
Example 4
Accurately weigh 8.28 grams of Cu (NO)3)2·3H2O, 47.55 g Al (NO)3)3·9H2O and 2.52 g Mn (CH3COO)2Adding 25% by mass of ethanol aqueous solution to prepare 200ml of mixed solution; accurately weighing 25.08 g of Na2CO3And adding 25% by mass of ethanol water solution to prepare 200ml of mixed solution. Pumping the two obtained water solutions into a reactor at a constant speed through a sample injection pump, violently stirring, aging at a constant temperature of 75 ℃ for 4 hours, filtering, drying a filter cake at 130 ℃, tabletting, grinding and sieving by a 40-mesh sieve, and roasting sieved powder in a muffle furnace at 750 ℃ for 6 hours to obtain the catalyst, wherein the mass fraction of each component is as follows: 27.41% of CuO and Al2O364.65%, and 8.12% of Mn oxide. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 5
Accurately weigh 4.09 grams of Cu (CH)3COO)248.31 g Al (NO)3)3·9H2O, 0.59 g MnCl2And 0.78 g ZrCl4Adding 50% by mass of ethanol aqueous solution to prepare 250ml of mixed solution; 44.96 g K are accurately weighed2CO3Ethanol water solution with the mass fraction of 50 percent is added to prepare 250ml of mixed solution. Pumping the two parts of the obtained water solution into a reactor at a constant speed through a sample injection pump, violently stirring, aging at a constant temperature of 55 ℃ for 5 hours, filtering, drying a filter cake at 115 ℃, tabletting, grinding and sieving by a 40-mesh sieve, and roasting the sieved powder in a muffle furnace at 1000 ℃ for 1 hour to obtain the catalyst, wherein the mass fraction of each component is as follows: 26.52% of CuO and Al2O365.68%, Mn oxide 4.11%, ZrO23.69%. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 6
Accurately weigh 4.10 grams of Cu (NO)3)2·3H2O, 3.08 g Cu (CH)3COO)229.49 g AlCl3·6H2O and 4.86 g Mn (NO) with a mass fraction of 50%3)2Adding 25% of solutionPreparing 250ml of mixed solution by using ethanol water solution; accurately weighing 24.46 g of Na2CO3And adding 25% by mass of ethanol water solution to prepare 250ml of mixed solution. Pumping the two parts of the obtained water solution into a reactor at a constant speed through a sample injection pump, violently stirring, aging at a constant temperature of 60 ℃ for 2 hours, filtering, drying a filter cake at 125 ℃, tabletting, grinding and sieving by a 40-mesh sieve, and roasting sieved powder in a muffle furnace at 950 ℃ for 1 hour to obtain the catalyst, wherein the mass fraction of each component is as follows: 27.15% of CuO and Al2O362.30% and Mn oxide 10.72%. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 7
Accurately weigh 4.10 grams of Cu (NO)3)2·3H2O, 3.08 g Cu (CH)3COO)244.13 g Al (NO)3)3·9H2O and 4.86 g Mn (NO) with a mass fraction of 50%3)2Adding deionized water to prepare 200ml of mixed solution, and accurately weighing 6.38 g of AlOOH.0.5H2Putting O into a reactor; accurately weigh 11.25 g of Na2CO3And 16.89 g K2CO3Deionized water was added to prepare 200ml of a mixed solution. Pumping the two parts of the obtained water solution into a reactor at a constant speed through a sample injection pump, violently stirring, aging at a constant temperature of 60 ℃ for 2 hours, filtering, drying a filter cake at 125 ℃, tabletting, grinding and sieving by a 40-mesh sieve, and roasting sieved powder in a muffle furnace at 950 ℃ for 1 hour to obtain the catalyst, wherein the mass fraction of each component is as follows: 28.08% of CuO and Al2O370.71% and 1.39% of Mn oxide. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 8
2.96 g of CuCl was accurately weighed2·2H2O, 3.15 g Cu (CH)3COO)250.20 g of Al (NO)3)3·9H2O and 0.93 g Mn (NO) with a mass fraction of 50%3)2Solution and 0.33 g MnCl2Adding deionized water to prepare 250ml of mixed solution; accurately weigh 25.51 grams of Na2CO3Adding deionized water250ml of mixed solution is prepared. Pumping the two parts of the obtained aqueous solution into a reactor at a constant speed through a sample injection pump, violently stirring, aging at a constant temperature of 65 ℃ for 3 hours, filtering, drying a filter cake at 100 ℃, tabletting, grinding and sieving by a 40-mesh sieve, and roasting the sieved powder in a muffle furnace at 850 ℃ for 0 hour to obtain the catalyst, wherein the mass fraction of each component is as follows: 27.81% of CuO and Al2O368.25% and 4.12% of Mn oxide. The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
Example 9
Accurately weigh 8.43 grams of Cu (NO)3)2·3H2O, 51.03 g Al (NO)3)3·9H2O and 3.04 g Co (NO) with a mass fraction of 33.4%3)2Adding deionized water into the solution to prepare 200ml of mixed solution; accurately weighing 25.80 g of Na2CO3Deionized water was added to prepare 200ml of a mixed solution. Pumping the two parts of the obtained water solution into a reactor at a constant speed through a sample injection pump, violently stirring, aging at a constant temperature of 70 ℃ for 3 hours, filtering, drying a filter cake at 100 ℃, tabletting, grinding and sieving by a 40-mesh sieve, and roasting sieved powder in a muffle furnace at 850 ℃ for 0 hour to obtain the catalyst, wherein the mass fraction of each component is as follows: 27.73% of CuO and Al2O369.38% and 2.90% of Co oxide. . The catalyst was evaluated in the same manner as in example 1, and the reaction conditions and results are shown in Table 1.
TABLE 1 reaction conditions and results of the examples
As can be seen from Table 1, the catalyst of the present invention has good catalytic activity, and the initial conversion rate of methanol can reach more than 99% without pre-reduction treatment.
The stability of the catalyst obtained in example 3 was examined, and as shown in FIG. 3, the Cu-Mn-Al catalyst obtained in example 3 and a commercial Cu-Zn-Al catalyst were subjected to a methanol steam reforming hydrogen production reaction, and the results are shown in Table 2 below:
TABLE 2 methanol conversion over time
It can be seen that the conversion rate of methanol of the catalyst of the invention can still be kept above 85% after reaction for about 200h, while the conventional commercial catalyst is basically deactivated after reaction for 85 h.
The selectivity of the product hydrogen in the reaction of the catalyst prepared in each example is about 74%, wherein the hydrogen yield of Cu-Mn-Al in example 3 after 50h reaction is 883.6ml/kgcat./s, and the hydrogen yield of industrial Cu-Zn-Al after 50h reaction is 674.1 ml/kgcat./s.
The CO selectivity of Cu-Mn-Al in example 3 was about 0.82-0.91%, and the CO selectivity of commercial Cu-Zn-Al was about 1.24-1.37%, as shown in FIG. 4. CO generated after the hydrogen production from the methanol can be removed through subsequent reaction, and no influence on the environment is caused. The difference is that the load of the subsequent treatment of the catalyst with good selectivity is small, and the cost is low.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are merely illustrative and not restrictive, and it should be understood that other embodiments may be easily implemented by those skilled in the art by means of replacement or modification according to the technical contents disclosed in the specification, and therefore, all changes and modifications that come within the spirit and technical conditions of the present invention should be included in the claims of the present invention.
Claims (10)
1. A Cu catalyst for preparing hydrogen by reforming methanol with steam is characterized by thatThe catalyst comprises the following components in percentage by mass: 25 to 35 percent of CuO and Al2O3 60％-75％，MOx0.1-15%, wherein M is one or more of Co, Mn and Zr, x is 1-3, and the catalyst has a face-centered cubic spinel structure.
2. A method of producing a Cu catalyst for hydrogen production by methanol steam reforming according to claim 1, comprising the steps of:
step 1: dissolving soluble precursors of Cu, Al and M in ethanol water solution to prepare 0.1-1.0 mol.L-1The solution of (1);
step 2: weighing a precipitant with the mole number of (1-1.3) sigma niXi, wherein ni is the mole number of metal ions, and Xi is the valence of the metal ions, dissolving the precipitant in an ethanol aqueous solution to prepare a solution with the same volume as that of the step 1;
and step 3: and (3) putting the solution obtained in the steps (1) and (2) into a reactor at a constant speed, stirring vigorously, aging at a constant temperature of 50-80 ℃ for 2-4h, filtering, drying a filter cake at the temperature of 100-120 ℃, tabletting, grinding and sieving, and roasting the sieved powder in a muffle furnace at the temperature of 600-1000 ℃ for 0-6h to obtain the catalyst.
3. The method for preparing the Cu catalyst for hydrogen production by methanol steam reforming as claimed in claim 2, wherein the precursor of Al is aluminum chloride, aluminum nitrate, pseudo-boehmite, gamma-Al2O3One or more of the above;
when the precursor of Al is pseudo-boehmite or gamma-Al2O3When in use, the solution is put into ethanol water solution in advance, and stirred vigorously to form suspension, and then soluble precursors of Cu and M are added.
4. The preparation method of the Cu catalyst for hydrogen production by methanol steam reforming as claimed in claim 2, wherein the precursor of Cu is one or more of cupric chloride, cupric nitrate and cupric acetate.
5. The preparation method of the Cu catalyst for hydrogen production by methanol steam reforming as claimed in claim 2, wherein the precursor of Co is one or more of cobalt chloride, cobalt nitrate and cobalt acetate;
the precursor of Mn is one or more of manganese chloride, manganese nitrate and manganese acetate;
the precursor of Zr is one or more of zirconium chloride, zirconium nitrate and zirconium oxynitrate.
6. The method for preparing a Cu catalyst for hydrogen production by methanol steam reforming according to claim 2, wherein the mass fraction of the ethanol aqueous solution is 0 to 50%.
7. The method for preparing a Cu catalyst for hydrogen production by methanol steam reforming as claimed in claim 2, wherein the precipitant in step 2 is one or more selected from sodium carbonate, ammonium carbonate and potassium carbonate.
8. The preparation method of the Cu catalyst for hydrogen production by methanol steam reforming as claimed in claim 2, wherein in step 1, one or more oxide precursors of Si, Fe, Ce, La, Mg and Mo can be added to the ethanol aqueous solution as a composite carrier.
9. Use of a Cu catalyst according to claim 1 for hydrogen production by methanol steam reforming, wherein the catalyst is used in a process for hydrogen production by methanol steam reforming.
10. Use of a Cu catalyst for hydrogen production by methanol steam reforming according to claim 9, characterized in that the conditions for hydrogen production by methanol steam reforming are: the reaction temperature is 200 ℃ and 350 ℃, the pressure is normal pressure and 2MPa, and the mass space velocity is 0.1-3.5h-1、H2O/CH3OH molar ratio of 0.5-3.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110467291.5A CN113145127B (en) | 2021-04-28 | 2021-04-28 | Cu catalyst for preparing hydrogen by reforming methanol and steam, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110467291.5A CN113145127B (en) | 2021-04-28 | 2021-04-28 | Cu catalyst for preparing hydrogen by reforming methanol and steam, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113145127A true CN113145127A (en) | 2021-07-23 |
| CN113145127B CN113145127B (en) | 2023-10-17 |
Family
ID=76872109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110467291.5A Active CN113145127B (en) | 2021-04-28 | 2021-04-28 | Cu catalyst for preparing hydrogen by reforming methanol and steam, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113145127B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155582A (en) * | 2022-08-22 | 2022-10-11 | 上海交通大学绍兴新能源与分子工程研究院 | Active carbon-loaded methanol reforming hydrogen production catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO841453L (en) * | 1984-04-12 | 1985-10-14 | Norsk Hydro As | CATALYST AND USE OF THE CATALYST IN CONVERSION OF METHANOL. |
| EP1161992A1 (en) * | 2000-06-07 | 2001-12-12 | Japan ,represented by Secretary of Agency of Industrial Science and Technology | New catalysts for oxidative steam reforming of methanol as a new and efficient method for the selective production of hydrogen for fuel cells and their synthesis method |
| CN1586718A (en) * | 2004-07-29 | 2005-03-02 | 复旦大学 | Nano carbon material modified copper base catalyst and its preparing method |
| CN1850331A (en) * | 2006-05-30 | 2006-10-25 | 华东师范大学 | CuZnAl composite oxide catalyst, its preparing and use |
-
2021
- 2021-04-28 CN CN202110467291.5A patent/CN113145127B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO841453L (en) * | 1984-04-12 | 1985-10-14 | Norsk Hydro As | CATALYST AND USE OF THE CATALYST IN CONVERSION OF METHANOL. |
| EP1161992A1 (en) * | 2000-06-07 | 2001-12-12 | Japan ,represented by Secretary of Agency of Industrial Science and Technology | New catalysts for oxidative steam reforming of methanol as a new and efficient method for the selective production of hydrogen for fuel cells and their synthesis method |
| CN1586718A (en) * | 2004-07-29 | 2005-03-02 | 复旦大学 | Nano carbon material modified copper base catalyst and its preparing method |
| CN1850331A (en) * | 2006-05-30 | 2006-10-25 | 华东师范大学 | CuZnAl composite oxide catalyst, its preparing and use |
Non-Patent Citations (3)
| Title |
|---|
| RAPHAEL 0. IDEM AND NARENDRA N. BAKHSHI: ""Production of Hydrogen from Methanol over Promoted Coprecipitated Cu-AI Catalysts: The Effects of Various Promoters and Catalyst Activation Methods"", 《ZND. ENG. CHEM. RES》 * |
| 李玉敏: "《工业催化原理》", 31 December 1995, 天津大学出版社 * |
| 沈建跃, 科学技术文献出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155582A (en) * | 2022-08-22 | 2022-10-11 | 上海交通大学绍兴新能源与分子工程研究院 | Active carbon-loaded methanol reforming hydrogen production catalyst and preparation method and application thereof |
| CN115155582B (en) * | 2022-08-22 | 2024-04-09 | 上海交通大学绍兴新能源与分子工程研究院 | Activated carbon-loaded catalyst for preparing hydrogen by reforming methanol and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113145127B (en) | 2023-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111229215B (en) | Metal high-dispersion supported catalyst based on carbon quantum dot induction and preparation method and application thereof | |
| CN110327933B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN110102294B (en) | Composite oxide loaded Pd-based catalyst, and preparation method and application thereof | |
| EP2318131B1 (en) | Catalyst for direct production of light olefins and preparation method thereof | |
| CN114405505B (en) | Platinum modified indium-based oxide catalyst and preparation method and application thereof | |
| JP4211900B2 (en) | Metal fine particle supported hydrocarbon reforming catalyst and method for producing the same | |
| JP2020505227A (en) | Manganese doped nickel methanation catalyst | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN113145127A (en) | Cu catalyst for hydrogen production by methanol steam reforming and preparation method and application thereof | |
| CN113058613B (en) | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof | |
| CN111992213B (en) | Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol | |
| WO2005030391A1 (en) | Catalyst and method for the generation of co-free hydrogen from methane | |
| CN115837275A (en) | Perovskite type high-entropy oxide and preparation method and application thereof | |
| CN113634251B (en) | Praseodymium-based carrier supported nano gold catalyst, and preparation method and application thereof | |
| CN111495375B (en) | Vermicular CuNi/Al 2 O 3 Catalyst, preparation method and application thereof | |
| WO2018141648A1 (en) | Iron-doped nickel methanation catalysts | |
| KR101594901B1 (en) | Cokes oven gas reforming catalyst for manufacturing synthesis gas, method for preparing the same and method for manufacturing synthesis gas from cokes oven gas using the same | |
| CN113083325A (en) | Catalyst Ru for ammonia borane hydrolysis hydrogen production1-xCox/P25 and preparation method thereof | |
| CN114308061A (en) | NiAu bimetallic alloy nano catalyst and synthesis and application thereof | |
| CN107224980B (en) | Preparation method of carbon dioxide methanation catalyst without reduction activation | |
| CN115212885B (en) | Cobalt silicate derived cobalt-based catalyst for directly preparing low-carbon alcohol from synthesis gas, preparation method and pretreatment method | |
| CN112973775B (en) | Catalyst containing MCM-22 molecular sieve and application thereof in liquid fuel preparation by synthesis gas one-step method | |
| CN111495374B (en) | Coated CoNi/Al 2 O 3 Catalyst, preparation method and application thereof | |
| KR102438144B1 (en) | Alkaline earth metals-based catalyst for water gas shift reaction and preparation method thereof | |
| CN113522303A (en) | CoMnOx nano-catalyst for directly preparing low-carbon alcohol from synthesis gas, and preparation method and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |