CN113145127B - Cu catalyst for preparing hydrogen by reforming methanol and steam, and preparation method and application thereof - Google Patents
Cu catalyst for preparing hydrogen by reforming methanol and steam, and preparation method and application thereof Download PDFInfo
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- 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
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- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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Abstract
The invention relates to a Cu catalyst for preparing hydrogen by reforming methanol and steam, a preparation method and application thereof, wherein the catalyst comprises the following components in percentage by mass: 25% -35% of CuO and Al 2 O 3 60％‑75％，MO x 0.1-15%, 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 the hydrogen production reaction of methanol steam reforming. 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 auxiliary agents.
Background
In the background of the increasingly severe energy problems and environmental pollution problems in the current society, hydrogen is considered as one of the most promising energy sources for replacing fossil fuels as a green and environment-friendly new energy source, and has been widely studied in recent years.
Hydrogen is not directly developed and utilized from natural environment as a secondary energy source. The preparation method of hydrogen comprises water electrolysis hydrogen production, fossil fuel hydrogen production, ammonia decomposition hydrogen production, biomass hydrogen production and the like. In recent years, the methanol conversion hydrogen production is widely applied due to the advantages of low cost, convenient storage and transportation, mild reaction conditions, few byproducts and the like. The technology for producing the hydrogen by methanol mainly comprises the steps of producing the hydrogen by partial oxidation of the methanol, producing the hydrogen by reforming the methanol and the water vapor and producing the hydrogen by autothermal reforming the methanol.
The catalyst is a core content of the technology for producing hydrogen from methanol. For the development and application of the catalyst, two systems of a non-noble metal catalyst and a noble metal catalyst are mainly included. Wherein the noble metal catalyst shows high catalytic activity in the reaction of preparing hydrogen from methanolAnd excellent stability, but the development of noble metal catalysts is limited due to the high price. Among non-noble metal catalyst systems, copper-based catalysts are most studied and widely used, and have good catalytic activity and selectivity in application and low cost. It has been reported that, among copper-based catalysts, catalysts having a spinel structure undergo H 2 Exhibits good catalytic properties in the reaction [ appl. Catalyst. B: environ.,2011,106,650-656 ]]。
Although the spinel-structured catalyst shows better catalytic performance in the methanol hydrogen production reaction, the stability of the catalyst does not meet the industrial requirement yet. Because the Tasmann temperature of copper is lower, the copper-based catalyst can be gradually agglomerated in the reaction process, so that crystal grains are gradually grown up, and finally the catalyst is deactivated. Therefore, a catalyst which is high in activity, good in stability, low in cost and easy to industrialize is sought.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a Cu catalyst for preparing hydrogen by reforming methanol steam, which has high activity, good stability and low price, and a preparation method and application thereof.
The aim of the invention can be achieved by the following technical scheme: a Cu catalyst for the production of hydrogen from the steam reforming of methanol, the catalyst comprising the following components in mass fraction: 25% -35% of CuO and Al 2 O 3 60% -75% of 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.
A method for preparing a Cu catalyst for preparing hydrogen by reforming methanol and steam, which comprises the following steps:
step 1: the soluble precursors of Cu, al and M are dissolved in ethanol water solution to prepare 0.1-1.0mol.L -1 Is a solution of (a);
step 2: weighing a precipitator with the mole number of (1-1.3) sigma niXi, wherein ni is the mole number of metal ions, xi is the valence of the metal ions, and dissolving the precipitator in an ethanol water solution to prepare a solution with the same volume as that in the step 1;
step 3: and (3) uniformly pumping the solutions obtained in the steps (1) and (2) into a reactor, stirring vigorously, aging at a constant temperature of 50-80 ℃ for 2-4 hours, filtering, drying a filter cake at 100-120 ℃, tabletting, grinding and sieving, and placing the sieved powder in a muffle furnace for roasting at 600-1000 ℃ for 0-6 hours, preferably 1-3 hours to obtain the catalyst.
The co-precipitation synthesis method of the catalyst can be replaced by other synthesis methods. The other synthesis method is selected from urea method, hydrothermal synthesis method, mechanochemical method and solution combustion synthesis method.
The precursor of Al is aluminum chloride, aluminum nitrate, pseudo-boehmite, gamma-Al 2 O 3 One or more of them.
The precursor of Al is pseudo-boehmite or gamma-Al 2 O 3 In this case, the precursor is put into an aqueous ethanol solution in advance.
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 zirconyl nitrate.
The mass fraction of the ethanol aqueous solution is 0-50%, preferably 20-40%.
The precipitant 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, mo can be added into the ethanol water solution to serve as a composite carrier.
The application of the Cu catalyst for preparing hydrogen by reforming methanol and water vapor is that the catalyst is applied to the hydrogen preparation process by reforming methanol and water vapor, and the application conditions are as follows: the reaction temperature is 200-350 ℃, the reaction pressure is normal pressure-2 MPa, and the mass space velocity is 0.1-3.5h -1 、H 2 O/CH 3 OH molar ratio 0.5-3.5:1.
compared with the prior art, the invention has the following beneficial effects:
1. the catalyst is composed of mixed oxide mainly containing Cu and Al and 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 oxide is AB 2 O 4 Wherein a and B are typically divalent cations and trivalent cations, respectively. In the spinel structure, 64 tetrahedral vacancies and 32 octahedral vacancies are formed in the unit cell by packing of oxygen negative divalent ions, the divalent copper ions and trivalent metal cations are separated from each other, and copper is confined in the spinel lattice and separated by oxygen atoms or voids. Compared with a supported catalyst with a non-spinel structure, the stability of the spinel structure is good, and active Cu generated by reduction under the spinel structure has relatively high dispersity and sintering resistance. The spinel is gradually reduced in the reaction process by the reaction raw materials, so that the operation is simple, the cost is low, and the copper particles obtained by reduction are smaller and the activity and stability are better.
2. The invention adopts an improved coprecipitation method to prepare a catalyst, firstly, each metal precursor is dissolved and mixed in an ethanol water solution, then a precipitator which is 1 to 1.3 times of the sum of the mole number of metal ions and the valence of the metal ions is matched, and the metal precursor is dissolved in the ethanol water solution, so that the soluble precursor is dispersed more uniformly in the ethanol water solution; the excess precipitant causes the metal cations to precipitate completely. The obtained catalyst precursor is roasted in a muffle furnace at high temperature to form a stable copper aluminum spinel oxide structure.
3. The catalyst has good catalytic activity, and under the condition that the catalyst is not subjected to pre-reduction treatment, the initial conversion rate of methanol can reach more than 99 percent, and 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 of the methanol steam reforming, so that the deactivation speed of the catalyst is slowed down. The catalyst with spinel structure slowly releases active metal Cu from the spinel framework structure in the environment of the raw material gas, so that the catalyst has the supplement of active centers in a quite long period of reaction time, and Cu which is not precipitated from the spinel structure is also available 2+ The ions being held at the tipDefective spinels are formed in the framework of the spinel structure, and the novel active Cu particles are stabilized to a certain extent. Therefore, after the catalyst is used for 200 hours, the conversion rate of methanol can still be maintained to be more than 85 percent.
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, suitable for large-scale industrialized use, and the catalyst does not need pre-reduction treatment before use.
Drawings
FIG. 1 is an XRD spectrum of the catalyst of example 1 of the invention;
FIG. 2 is a schematic representation of H of the catalyst of example 1 of the present invention 2 -a TPR profile;
FIG. 3 is a graph showing the methanol conversion over time for the Cu-Mn-Al spinel catalyst synthesized in example 3 of the present invention and a Cu-Zn-Al catalyst used in industry.
Fig. 4 is a graph of CO selectivity over time.
Detailed Description
The following examples are illustrative of the present invention and are not intended to limit the scope of the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. The test methods in the following examples are conventional methods unless otherwise specified.
The phase structure of the catalyst was analyzed by using a D/max-2200/PC type X-ray diffractometer from Japanese physics Co. The test conditions were: cu target (lambda= 0.154056 nm), scanning range 10-90 DEG, scanning step length 0.005 DEG, scanning speed 5 DEG min -1 The tube voltage was 40kV and the tube current was 40mA.
H catalyst Using PCA-1200 chemisorber from Beijing Peaode electronics Inc 2 -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 which is provided with a 5A molecular sieve column, a TDX-01 column, a PEG-20M column, a TCD detector and a FID detector and is manufactured by Nanjing Kejie analytical instruments Co.
Example 1
Accurately weigh 5.95 g CuCl 2 ·2H 2 O, 51.10 g Al (NO) 3 ) 3 ·9H 2 O and 1.25 g of Mn (NO) with a mass fraction of 50% 3 ) 2 Adding deionized water into the solution to prepare 200ml of mixed solution; accurately weigh 25.73 g Na 2 CO 3 Deionized water was added to prepare 200ml of a mixed solution. And (3) pumping the obtained two parts of aqueous solution into a reactor at a constant speed through a sample injection pump, vigorously stirring, aging at a constant temperature of 70 ℃ for 3 hours, filtering, drying a filter cake at 100 ℃, tabletting, grinding, sieving with a 40-mesh sieve, placing the sieved powder into a muffle furnace, roasting for 0 hour at 850 ℃ (namely, the muffle furnace is started from normal temperature, the temperature is programmed to 850 ℃ at a speed of 3 ℃/min, then the operation (0 hour) of keeping the constant temperature is not performed, and directly and naturally cooling to the normal temperature state). The catalyst is obtained, and the mass fractions of the components are as follows: cuo=27.94%, al 2 O 3 69.47%, oxide of mn=2.76%.
The catalyst was XRD characterized using X-ray diffraction techniques and the results are shown in figure 1. All diffraction peaks in the spectra were assigned to spinels, indicating that the synthesized catalyst had a face-centered cubic spinel structure.
H for catalyst by chemical adsorption instrument 2 TPR characterization, results are shown in figure 2.
Filling 1.0g of catalyst with 40-60 meshes into a reactor, heating to 270 ℃, and starting a feeding reaction, wherein the reaction conditions and the results are shown in Table 1.
Example 2
Accurately weigh 8.36 g Cu (NO) 3 ) 2 ·3H 2 O, 24.21 g Al (NO) 3 ) 3 ·9H 2 O, 2.48 g of Mn (NO) with mass fraction of 50% 3 ) 2 Solution and 0.48 g Zr (NO) 3 ) 4 5H2O, adding 50% ethanol water solution to prepare 200ml mixed solution, accurately weighing 6.63 g gamma-Al 2 O 3 Putting the mixture into a reactor; 13.42 g (NH) 4 ) 2 CO 3 Adding 50% ethanol water solution to prepare 200ml mixed solution. The obtained mixture is pumped by a sample injection pumpThe two solutions are stirred at a constant speed and are fed into a reactor, the mixture is stirred vigorously, the mixture is aged for 6 hours at a constant temperature of 60 ℃, then is filtered, a filter cake is dried at 120 ℃, is pressed into tablets, is ground and passes through a 40-mesh sieve, and the sieved powder is placed into a muffle furnace for roasting for 3 hours at 900 ℃ to obtain the catalyst, wherein the mass fractions of the components are as follows: cuo=27.52%, al 2 O 3 69.73%, oxide of mn=1.38%, zrO 2 =1.37%. 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 g Cu (NO) 3 ) 2 ·3H 2 O, 48.42 g Al (NO) 3 ) 3 ·9H 2 O and 3.08 g of Mn (NO) with mass fraction of 50% 3 ) 2 Adding deionized water into the solution to prepare 200ml of mixed solution; accurately weigh 25.08 g Na 2 CO 3 Deionized water was added to prepare 200ml of a mixed solution. And (3) pumping the obtained two parts of aqueous solution into a reactor at a constant speed through a sample injection pump, vigorously stirring, aging at a constant temperature of 65 ℃ for 3 hours, filtering, drying a filter cake at 120 ℃, tabletting, grinding, sieving with a 40-mesh sieve, and roasting the sieved powder in a muffle furnace at 800 ℃ for 3 hours to obtain the catalyst, wherein the mass fractions of the components are as follows: cuo=27.54%, al 2 O 3 65.83%, oxide of mn=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 reaction test of the above synthesized catalyst was compared with that of an industrially used Cu-Zn-Al catalyst, and the methanol conversion was changed with time as shown in FIG. 3. The synthesized catalyst can be seen to have higher catalytic activity and stability in the reaction.
Example 4
Accurately weigh 8.28 g Cu (NO) 3 ) 2 ·3H 2 O, 47.55 g Al (NO) 3 ) 3 ·9H 2 O and 2.52 g Mn (CH 3 COO) 2 Adding an ethanol water solution with the mass fraction of 25% to prepare 200ml of mixed solution; accurately weigh 25.08 g Na 2 CO 3 Adding 25% ethanol water solution to prepare 200ml mixed solution. The two obtained aqueous solutions are pumped into a reactor at a constant speed through a sample injection pump,and (3) vigorously stirring, aging at a constant temperature of 75 ℃ for 4 hours, filtering, drying a filter cake at 130 ℃, tabletting, grinding, sieving with a 40-mesh sieve, and roasting the sieved powder in a muffle furnace at 750 ℃ for 6 hours to obtain the catalyst, wherein the mass fractions of the components are as follows: cuo=27.41%, al 2 O 3 64.65%, oxide of mn=8.12%. 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) 3 COO) 2 48.31 g of Al (NO) 3 ) 3 ·9H 2 O, 0.59 g MnCl 2 And 0.78 g ZrCl 4 Adding 50% ethanol water solution to prepare 250ml mixed solution; 44.96 g of K is accurately weighed 2 CO 3 Adding 50% ethanol water solution to prepare 250ml mixed solution. And (3) pumping the obtained two parts of aqueous solution into a reactor at a constant speed through a sample injection pump, vigorously stirring, aging at a constant temperature of 55 ℃ for 5 hours, filtering, drying a filter cake at 115 ℃, tabletting, grinding, sieving with 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 fractions of the components are as follows: cuo=26.52%, al 2 O 3 =65.68%, oxide of mn=4.11%, zrO 2 =3.69%. 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 g Cu (NO) 3 ) 2 ·3H 2 O, 3.08 g Cu (CH) 3 COO) 2 29.49 g AlCl 3 ·6H 2 O and 4.86 g of Mn (NO) with a mass fraction of 50% 3 ) 2 Adding an ethanol water solution with the mass fraction of 25% into the solution to prepare 250ml of mixed solution; accurately weigh 24.46 g Na 2 CO 3 An aqueous ethanol solution with a mass fraction of 25% was added to prepare 250ml of a mixed solution. And (3) pumping the obtained two parts of aqueous solution into a reactor at a constant speed through a sample injection pump, vigorously stirring, aging at a constant temperature of 60 ℃ for 2 hours, filtering, drying a filter cake at 125 ℃, tabletting, grinding, sieving with a 40-mesh sieve, and roasting the sieved powder in a muffle furnace at 950 ℃ for 1 hour to obtain the catalyst, wherein the mass fractions of the components are as follows: cuo= 27.15%, al 2 O 3 62.30%, oxide of mn=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 g Cu (NO) 3 ) 2 ·3H 2 O, 3.08 g Cu (CH) 3 COO) 2 44.13 g of Al (NO) 3 ) 3 ·9H 2 O and 4.86 g of Mn (NO) with a mass fraction of 50% 3 ) 2 Adding deionized water into the solution to prepare 200ml of mixed solution, accurately weighing 6.38 g AlOOH.0.5H 2 O is put into a reactor; accurately weigh 11.25 g Na 2 CO 3 And 16.89 g K 2 CO 3 Deionized water was added to prepare 200ml of a mixed solution. And (3) pumping the obtained two parts of aqueous solution into a reactor at a constant speed through a sample injection pump, vigorously stirring, aging at a constant temperature of 60 ℃ for 2 hours, filtering, drying a filter cake at 125 ℃, tabletting, grinding, sieving with a 40-mesh sieve, and roasting the sieved powder in a muffle furnace at 950 ℃ for 1 hour to obtain the catalyst, wherein the mass fractions of the components are as follows: cuo=28.08%, al 2 O 3 =70.71%, and Mn oxide=1.39%. 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
Accurately weigh 2.96 g CuCl 2 ·2H 2 O, 3.15 g Cu (CH) 3 COO) 2 50.20 g of Al (NO) 3 ) 3 ·9H 2 O and 0.93 g of Mn (NO) with mass fraction of 50% 3 ) 2 Solution and 0.33 g MnCl 2 Adding deionized water to prepare 250ml of mixed solution; accurately weigh 25.51 g Na 2 CO 3 Deionized water was added to prepare 250ml of a mixed solution. And (3) pumping the obtained two parts of aqueous solution into a reactor at a constant speed through a sample injection pump, vigorously stirring, aging at a constant temperature of 65 ℃ for 3 hours, filtering, drying a filter cake at 100 ℃, tabletting, grinding, sieving with 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 fractions of the components are as follows: cuo=27.81%, al 2 O 3 =68.25%, and Mn oxide=4.12%. 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 g Cu (NO) 3 ) 2 ·3H 2 O, 51.03 g Al (NO) 3 ) 3 ·9H 2 O and 3.04 g of Co (NO) with mass fraction of 33.4% 3 ) 2 Adding deionized water into the solution to prepare 200ml of mixed solution; accurately weigh 25.80 g Na 2 CO 3 Deionized water was added to prepare 200ml of a mixed solution. And (3) pumping the obtained two parts of aqueous solution into a reactor at a constant speed through a sample injection pump, vigorously stirring, aging at a constant temperature of 70 ℃ for 3 hours, filtering, drying a filter cake at 100 ℃, tabletting, grinding, sieving with 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 fractions of the components are as follows: cuo=27.73%, al 2 O 3 69.38%, co oxide=2.90%. . 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 for each example
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 of the catalyst.
Taking the catalyst prepared in example 3 as an example to examine the stability, as shown in fig. 3, the Cu-Mn-Al catalyst obtained in example 3 was subjected to a methanol steam reforming hydrogen production reaction with an industrial commercial Cu-Zn-Al catalyst, and the specific results are shown in the following table 2:
TABLE 2 methanol conversion over time
It can be seen that the catalyst of the present invention can maintain the methanol conversion rate at more than 85% after about 200 hours of reaction, whereas the conventional commercial catalyst has been substantially deactivated after 85 hours of reaction.
The catalyst prepared in each of the above examples had a hydrogen selectivity of about 74% in the reaction, wherein the hydrogen yield of Cu-Mn-Al in example 3 after 50 hours of reaction was 883.6ml/kgcat./ s, and the hydrogen yield of industrial Cu-Zn-Al after 50 hours of reaction was 674.1ml/kgcat./ s.
The CO selectivity of Cu-Mn-Al in example 3 was about 0.82 to 0.91%, and the CO selectivity of industrial Cu-Zn-Al was about 1.24 to 1.37%, as shown in FIG. 4. The CO generated after the hydrogen production of the methanol can be removed through subsequent reactions, and the environmental impact is avoided. 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 embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, but other embodiments can be easily made by those skilled in the art through substitution or modification according to the technical disclosure in the present specification, so that all changes and modifications made in the principle and process conditions of the present invention should be included in the scope of the present invention.
Claims (1)
1. The Cu catalyst for preparing hydrogen by reforming methanol and steam is characterized in that the preparation method of the catalyst comprises the following steps:
accurately weigh 5.95 g CuCl 2 ·2H 2 O, 51.10 g Al (NO) 3 ) 3 ·9H 2 O and 1.25 g of Mn (NO) with a mass fraction of 50% 3 ) 2 Adding deionized water into the solution to prepare 200mL of mixed solution; accurately weigh 25.73 g Na 2 CO 3 Adding deionized water to prepare 200ml of mixed solution; pumping the obtained two aqueous solutions into a reaction vessel at uniform speed by a sample injection pumpIn a device, violently stirring, aging at the constant temperature of 70 ℃ for 3 hours, filtering, drying a filter cake at the temperature of 100 ℃, tabletting, grinding, sieving with a 40-mesh sieve, placing the sieved powder into a muffle furnace for roasting, heating the muffle furnace to 850 ℃ at the speed of 3 ℃/min, then, not performing the operation of keeping the constant temperature, and directly and naturally cooling to the normal temperature state to obtain the catalyst, wherein the mass fractions of the components are as follows: cuo=27.94%, al 2 O 3 69.47%, oxide of mn=2.76%;
XRD characterization is carried out on the catalyst by adopting an X-ray diffraction technology, all diffraction peaks in the spectrogram are attributed to spinel, and the synthesized catalyst has a face-centered cubic spinel structure.
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| CN1586718A (en) * | 2004-07-29 | 2005-03-02 | 复旦大学 | Nano carbon material modified copper base catalyst and its preparing method |
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