CN108328574B - Method for preparing hydrogen by phenol adsorption enhanced reforming - Google Patents
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Abstract
The invention discloses a method for preparing hydrogen by phenol adsorption enhanced reforming. The method is to fill a fixed bed reactor with the functions of catalyzing and absorbing CO2The functional Ni-Ca-Al-O bifunctional catalyst takes weight hourly space velocity of 0.432-2.592h under the condition that inert gas is taken as carrier gas‑1Introducing a phenol solution with the concentration of 0.0399-0.1594g/ml, and controlling the reaction temperature at 400-700 ℃; when CO is present2After the adsorption saturation, the catalyst is regenerated for 0.1-3h at 500-1000 ℃ in an inert atmosphere. The purity of the hydrogen obtained by the method can reach more than 98 percent, the conversion rate of the phenol reaches more than 99 percent, and the stability of catalysis and adsorption is good.
Description
Technical Field
The invention belongs to the technical field of energy, and particularly relates to a method for producing hydrogen by phenol adsorption enhanced reforming.
Background
In recent years, with the rapid increase in global energy demand, fossil energy is rapidly consumed, and at the same time, serious environmental and climate problems are caused. Therefore, the research of biomass resource conversion into energy and chemical raw materials with the main purpose of finding alternatives to fossil raw materials has attracted attention in many countries of the world. Hydrogen energy is regarded as the most promising clean energy source in the 21 st century, and hydrogen energy research has been widely conducted in many countries and regions in the world since the 70 th century. Although most of the raw materials for hydrogen production at present adopt fossil fuels such as methane and the like, the hydrogen production technology is continuously developed to gradually convert the hydrogen production raw materials into sustainable energy sources such as biomass and the like in consideration of the problem of environmental protection.
At present, the method for producing hydrogen by biomass is mainly divided into two methods, namely biomass pyrolysis hydrogen production and biomass gasification hydrogen production, but the two hydrogen production methods have the problems of serious coking and the like in the actual operation process, so that the hydrogen concentration and the hydrogen yield are greatly reduced, the main substance for forming coke is an aromatic compound with high carbon content, and phenols are the most common one. Therefore, how to remove the coke in the actual production to improve the stability of biomass conversion is very important. Many researches focus on focusing for catalytic steam reforming, so that not only can coke with complex composition be removed, but also hydrogen with higher heat value can be generated, and therefore, the method has good application prospect.
Maite Artetxe et Al (Fuel,2016,184:629-636) uses Ni/Al2O3The catalyst carries out steam reforming on the phenol, and the conversion rate of the phenol reaches 81 percent; qingqing Peng et al (ACS Sustainable Chemistry)&Engineering 2017,5:2098-2108) adopts Ni/Fe nano-catalyst to carry out steam reforming on phenol, so that the conversion rate of phenol can reach 87%, and the yield of hydrogen can reach 81%. Although steam reforming of phenol can yield relatively high conversion, the hydrogen produced is relatively low in purity and contains a significant amount of CO2CO and CH4And the by-products need to be further separated and purified to obtain the hydrogen with higher purity. Compared with the steam reforming process, the adsorption enhanced steam reforming process introduces the adsorbent, and can remove CO in situ2The byproduct can promote the water vapor change reaction so as to move the reaction equilibrium to the direction of generating hydrogen, thereby obtaining high-purity hydrogen. At present, the research on the adsorption enhanced steam reforming hydrogen production basically utilizes some compounds with lower carbon content (such as methane, ethanol, acetic acid, glycerol, etc.) as raw materials. The CN102070125A patent performs adsorption enhanced reforming on methane to produce hydrogen, and the concentration of the obtained hydrogen can reach 90%. The patent CN107098311A adopts a Ca-Co-O catalyst to adsorb and enhance glycerol to reform and produce hydrogen, so that the concentration of the hydrogen can reach 95 percent. However, the research of using substances with high carbon content in coke, such as phenol, for adsorption-enhanced reforming hydrogen production has been reported only rarely.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing hydrogen by phenol adsorption enhanced reforming.
A method for preparing hydrogen by phenol adsorption enhanced reforming comprises the following steps:
(1) filling the fixed bed reactor with the functions of catalyzing and absorbing CO2A functional Ni-Ca-Al-O catalyst;
(2) injecting a phenol aqueous solution into the fixed bed reactor to react under the condition of taking inert gas as a carrier gas; the concentration of the phenol aqueous solution is 0.0399-0.1594g/ml, and the weight hourly space velocity of the phenol aqueous solution is 0.432-2.592h-1The reaction temperature is 400-700 ℃.
Preferably, the Ni-Ca-Al-O catalyst in the step (1) contains nickel oxide (NiO), mayenite (Ca)12Al14O33,Ca3Al2(OH)12) The preparation method of the Ni-Ca-Al-O composite comprises the following steps: dissolving nickel salt, calcium salt and aluminum salt in water, drying, and calcining at 500-1000 ℃ for 1-10h to obtain the Ni-Ca-Al-O catalyst.
Further preferably, the nickel salt is nickel nitrate.
More preferably, the calcium salt is one or more of calcium nitrate, calcium chloride and calcium phosphate.
More preferably, the aluminum salt is one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
Further preferably, the molar ratio of calcium to aluminum in the calcium salt and the aluminum salt is (0.8-3.8): 1; the Ni content in the Ni-Ca-Al-O catalyst is 5 wt% -20 wt%.
Further preferably, the calcining temperature is 800-900 ℃, and the calcining time is 4-6 h.
Preferably, the concentration of the phenol aqueous solution in the step (2) is 0.0598g/ml-0.0797 g/ml.
Preferably, the weight hourly space velocity of the aqueous phenol solution in the step (2) is 1.296h-1-1.944h-1。
Preferably, the temperature of the reaction in step (2) is 500-650 ℃.
Preferably, in step (2), when the Ni-Ca-Al-O catalyst adsorbs CO2After saturation, the catalyst is regenerated in argon atmosphere at the regeneration temperature of 500-1000 ℃ for 0.1-3 h.
Further preferably, the regeneration temperature is 800-850 ℃, and the regeneration time is 0.5-1 h.
Compared with the prior art, the invention has the following advantages:
the invention adopts phenol to adsorb and enhance steam reforming, and compared with the steam reforming process, the purity of hydrogen is greatly improved and can reach 98 percent; the Ni-Ca-Al-O catalyst has high activity and good stability.
Drawings
FIG. 1 is an X-ray diffraction chart of the Ni-Ca-Al-O catalyst obtained in example 1.
FIG. 2 is a TEM image of the Ni-Ca-Al-O catalyst obtained in example 1.
Detailed Description
The following examples and drawings further illustrate the embodiments of the present invention, but the scope of the present invention is not limited to the following embodiments.
The hydrogen concentration in the following examples was determined by Gas Chromatography (GC) analysis, and GC detection was calculated using an internal standard method.
Examples 1 to 5:
weighing 0.0043mol of nickel nitrate, 0.064mol of calcium salt in table 1 and 0.023mol of aluminum salt in table 1, dissolving in 50ml of water, drying at 120 ℃, roasting the obtained product in a muffle furnace at 800 ℃ for 4h to obtain a Ni-Ca-Al-O catalyst, filling the Ni-Ca-Al-O catalyst in a fixed bed, using argon as a carrier gas, and using 1.296h-1The weight hourly space velocity of (2) is that phenol aqueous solution with the concentration of 0.0797g/ml is introduced, the reaction temperature is 550 ℃, and the purity of hydrogen in the product after 15min of reaction is shown in the following table 1. The X-ray diffraction pattern and TEM pattern of the Ni-Ca-Al-O catalyst obtained in example 1 are shown in FIGS. 1 and 2.
TABLE 1
Examples | 1 | 2 | 3 | 4 | 5 |
Calcium salt | Calcium nitrate | Calcium nitrate | Calcium nitrate | Calcium phosphate | Calcium chloride |
Aluminium salts | Aluminium nitrate | Aluminium sulphate | Aluminium chloride | Cobalt chloride | Cobalt sulfate |
Purity of hydrogen (%) | 98.66 | 93.24 | 92.56 | 91.26 | 90.25 |
Examples 6 to 11:
weighing 0.0043mol of nickel nitrate, 0.064mol of calcium nitrate and 0.023mol of aluminum nitrate, dissolving in 50ml of water, drying at 120 ℃, roasting the obtained product under the condition shown in Table 2 to obtain a Ni-Ca-Al-O catalyst, filling the Ni-Ca-Al-O catalyst in a fixed bed, using argon as a carrier gas, and carrying out reaction for 1.296h-1The weight hourly space velocity of (2) was determined by introducing 0.0797g/ml aqueous phenol solution at a reaction temperature of 550 deg.C and the purity of hydrogen in the product after 15min of reaction is shown in Table 2 below.
TABLE 2
Examples | 1 | 6 | 7 | 8 | 9 | 10 | 11 |
Calcination temperature (. degree.C.) | 800 | 800 | 800 | 800 | 500 | 900 | 1000 |
Calcination time (h) | 4 | 1 | 6 | 10 | 4 | 4 | 4 |
Purity of hydrogen (%) | 98.66 | 94.10 | 95.32 | 94.2 | 92.12 | 95.42 | 94.10 |
Examples 12 to 15:
calcium nitrate, aluminum nitrate and nickel nitrate shown in Table 3 were weighed and dissolved in 50ml of water, dried at 120 ℃ and the resulting product was calcined in a muffle furnace at 800 ℃ for 4h to obtain Ni-Ca-Al-O catalysts of different Ni contents. In the reaction of phenol adsorption enhanced steam reforming, a fixed bed reactor is filled with Ni-Ca-Al-O catalyst, argon is used as carrier gas, and the reaction time is 1.296h-1The weight hourly space velocity of (2) was that an aqueous solution of phenol was fed at a concentration of 0.0797g/ml, the reaction temperature was 550 ℃, and the purity of hydrogen and the conversion rate of phenol in the product after 15min of reaction were as shown in Table 3 below.
TABLE 3
Examples | 12 | 1 | 13 | 14 | 15 |
Nickel nitrate (mol) | - | 0.0043 | 0.0086 | 0.0129 | 0.0172 |
Calcium nitrate (mol) | 0.067 | 0.064 | 0.061 | 0.057 | 0.054 |
Aluminium nitrate (mol) | 0.024 | 0.023 | 0.022 | 0.020 | 0.019 |
Purity of hydrogen (%) | 77.95 | 98.66 | 98.65 | 98.6 | 98.47 |
Phenol conversion (%) | 51.52 | 100 | 100 | 100 | 100 |
Examples 16 to 18:
calcium nitrate, aluminum nitrate and nickel nitrate shown in Table 4 were weighed and dissolved in 50ml of water, dried at 120 ℃ and the resulting product was calcined in a muffle furnace at 800 ℃ for 4h to obtain Ni-Ca-Al-O catalysts of different calcium/aluminum ratios. In the reaction of phenol adsorption enhanced steam reforming, a fixed bed reactor is filled with Ni-Ca-Al-O catalyst, argon is used as carrier gas, and the reaction time is 1.296h-1The weight hourly space velocity of (2) was that an aqueous solution of phenol was fed at a concentration of 0.0797g/ml, the reaction temperature was 550 ℃, and the purity of hydrogen and the conversion of phenol in the product after 15min of reaction were as shown in Table 4 below.
TABLE 4
Examples | 1 | 16 | 17 | 18 |
Nickel nitrate (mol) | 0.0043 | 0.0043 | 0.0043 | 0.0043 |
Calcium nitrate (mol) | 0.064 | 0.040 | 0.056 | 0.068 |
Aluminium nitrate (mol) | 0.023 | 0.050 | 0.031 | 0.018 |
Purity of hydrogen (%) | 98.66 | 94.12 | 98.67 | 97.80 |
Phenol conversion (%) | 100 | 86.97 | 100 | 97.14 |
Examples 19 to 22
0.0043mol of nickel nitrate, 0.064mol of calcium nitrate and 0.023mol of aluminum nitrate are weighed and dissolved in 50ml of water, the mixture is dried at 120 ℃, the obtained product is roasted for 4 hours at 800 ℃ to obtain a Ni-Ca-Al-O catalyst, the Ni-Ca-Al-O catalyst is filled in a fixed bed, argon is used as carrier gas, phenol water solution with the concentration of 0.0797g/ml is introduced at the weight hourly space velocity shown in the table 6, and the purity of hydrogen and the conversion rate of phenol in the product after 15min of reaction are shown in the table 6 below.
TABLE 6
Examples | 19 | 20 | 1 | 21 | 22 |
Weight hourly space velocity (h)-1) | 0.432 | 0.648 | 1.296 | 1.944 | 2.592 |
Hydrogen gas concentration (%) | 98.31 | 98.27 | 98.66 | 97.42 | 95.27 |
Examples 23 to 26
Weighing 0.0043mol of nickel nitrate, 0.064mol of calcium nitrate and 0.023mol of aluminum nitrate, dissolving in 50ml of water, drying at 120 ℃, roasting the obtained product for 4h at 800 ℃ to obtain a Ni-Ca-Al-O catalyst, filling the Ni-Ca-Al-O catalyst in a fixed bed, using argon as a carrier gas,at 1.296h-1The concentration of the phenol solution fed at the weight hourly space velocity of (2) is shown in Table 7, and the purity of hydrogen and the conversion of phenol in the product after 15min of reaction are shown in Table 7 below.
TABLE 7
Examples | 23 | 24 | 1 | 25 | 26 |
Phenol concentration (g/ml) | 0.0399 | 0.0598 | 0.0797 | 0.1196 | 0.1594 |
Hydrogen gas concentration (%) | 98.64 | 98.45 | 98.66 | 97.96 | 96.51 |
Examples 27 to 31:
0.0043mol of nickel nitrate, 0.064mol of calcium nitrate and0.023mol of aluminum nitrate is dissolved in 50ml of water and dried at 120 ℃, the obtained product is roasted for 4 hours at 800 ℃ to obtain the Ni-Ca-Al-O catalyst, the Ni-Ca-Al-O catalyst is filled in a fixed bed, argon is used as carrier gas, and the reaction time is 1.296 hours-1The weight hourly space velocity of (2) was determined by introducing an aqueous solution of phenol at a concentration of 0.0797g/ml, the reaction temperature was as shown in Table 5, and the purity of hydrogen and the conversion of phenol in the product after 15min of reaction are as shown in Table 8 below.
TABLE 8
Examples | 27 | 28 | 1 | 29 | 30 | 31 |
Temperature of | 400 | 500 | 550 | 600 | 650 | 700 |
Purity of hydrogen (%) | 70.1 | 99.71 | 98.66 | 96.22 | 86.48 | 83.01 |
Phenol conversion (%) | 65.8 | 98.66 | 100 | 100 | 100 | 100 |
Examples 32 to 38
And (3) cycle experiment: weighing 0.0043mol of nickel nitrate, 0.064mol of calcium nitrate and 0.023mol of aluminum nitrate, dissolving in 50ml of water, drying at 120 ℃, roasting the obtained product at 800 ℃ for 4h to obtain a Ni-Ca-Al-O catalyst, filling the Ni-Ca-Al-O catalyst in a fixed bed, using argon as a carrier gas, and taking 1.296h as-1Introducing 0.0797g/ml of phenol aqueous solution at the weight hourly space velocity, wherein the reaction temperature is 550 ℃, the reaction time is 100min, and when the Ni-Ca-Al-O catalyst adsorbs CO2After saturation, regeneration was carried out under argon atmosphere according to the conditions of Table 6, and the cycle was repeated three times. The results of GC analysis of the purity of hydrogen and the conversion of phenol in the product after 15min of reaction are shown in Table 9.
TABLE 9
Examples | 32 | 33 | 34 | 35 | 36 | 37 | 38 |
Regeneration temperature (. degree.C.) | 800 | 800 | 800 | 800 | 500 | 700 | 1000 |
Regeneration time (h) | 0.1 | 0.5 | 1 | 3 | 1 | 1 | 1 |
Ring 1 hydrogen purity (%) | 95.64 | 96.76 | 98.34 | 97.68 | 95.35 | 97.99 | 96.87 |
Circle 2 hydrogen purity (%) | 95.46 | 96.54 | 98.72 | 97.65 | 95.56 | 97.86 | 96.54 |
Circle 3 hydrogen purity (%) | 95.42 | 96.37 | 98.95 | 97.63 | 95.01 | 97.57 | 96.31 |
Cycle 1 phenol conversion (%) | 95.20 | 96.34 | 99.99 | 98.67 | 94.02 | 98.89 | 95.46 |
2 nd-Ring conversion of phenol (%) | 95.24 | 96.45 | 99.99 | 98.65 | 94.01 | 98.56 | 95.62 |
Circle 3Phenol conversion (%) | 95.11 | 96.21 | 99.98 | 98.74 | 94.11 | 98.77 | 95.04 |
Example 39
Stability test: and (3) cycle experiment: weighing 0.0043mol of nickel nitrate, 0.064mol of calcium nitrate and 0.023mol of aluminum nitrate, dissolving in 50ml of water, drying at 120 ℃, roasting the obtained product at 800 ℃ for 4h to obtain a Ni-Ca-Al-O catalyst, filling the Ni-Ca-Al-O catalyst in a fixed bed, using argon as a carrier gas, and taking 1.296h as-1Introducing 0.0797g/ml of phenol aqueous solution at the weight hourly space velocity, wherein the reaction temperature is 550 ℃, the reaction time is 100min, and when the Ni-Ca-Al-O catalyst adsorbs CO2After saturation, regeneration is carried out for 1h at 800 ℃ in an argon atmosphere, and circulation is carried out for 30 times. The results of GC analysis of the purity of hydrogen and the conversion of phenol in the product after 15min of reaction are shown in Table 10.
Number of cycles | 1 | 5 | 10 | 20 | 30 |
Purity of hydrogen (%) | 98.75 | 98.82 | 98.69 | 98.69 | 98.97 |
Phenol conversion (%) | 100 | 100 | 99.10 | 99.73 | 99.63 |
From the results in table 10, it can be seen that under the above conditions, the use of Ni-Ca-Al-O catalyst shows very good stability to phenol adsorption-enhanced steam reforming, and during 30 cycles of cycle, the purity of hydrogen can reach more than 98%, and the conversion rate of phenol can also reach more than 99%.
It should be emphasized that the above-described embodiments are merely examples for clearly illustrating the present invention and are not to be considered as limiting the embodiments. Other variants will be apparent to those skilled in the art on the basis of the foregoing description, and it is not necessary to exemplify all the embodiments herein, but obvious variations are nevertheless within the scope of the invention.
Claims (9)
1. The method for preparing hydrogen by phenol adsorption enhanced reforming is characterized by comprising the following steps of:
(1) filling a Ni-Ca-Al-O catalyst in a fixed bed reactor;
(2) injecting an aqueous solution of phenol into the solid with an inert gas as a carrier gasReacting in a fixed bed reactor; the concentration of the phenol aqueous solution is 0.0399-0.1594g/ml, and the weight hourly space velocity of the phenol aqueous solution is 0.432-2.592h-1The reaction temperature is 400-700 ℃;
the preparation method of the Ni-Ca-Al-O catalyst in the step (1) comprises the following steps: dissolving nickel salt, calcium salt and aluminum salt in water, drying, and calcining at 500-1000 ℃ for 1-10h to obtain the Ni-Ca-Al-O catalyst.
2. The method of claim 1, wherein the nickel salt is nickel nitrate.
3. The method of claim 1, wherein the calcium salt is one or more of calcium nitrate, calcium chloride and calcium phosphate.
4. The method of claim 1, wherein the aluminum salt is one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
5. The process according to claim 1, characterized in that the molar ratio of calcium to aluminum in the calcium and aluminum salts is (0.8-3.8): 1; the Ni content in the Ni-Ca-Al-O catalyst is 5 wt% -20 wt%.
6. The method as claimed in claim 1, wherein the calcination temperature is 800-900 ℃ and the calcination time is 4-6 h.
7. The method as claimed in claim 1, wherein the temperature of the reaction in step (2) is 500-650 ℃.
8. The method according to claim 1, wherein in the step (2), the Ni-Ca-Al-O catalyst adsorbs CO2After saturation, the catalyst is regenerated in argon atmosphere at the regeneration temperature of 500-1000 ℃ for 0.1-3 h.
9. The method as claimed in claim 8, wherein the temperature of the regeneration is 800-850 ℃ and the time of the regeneration is 0.5-1 h.
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CN104973571A (en) * | 2015-06-24 | 2015-10-14 | 中国矿业大学 | Method for producing synthetic gas taking H2 as main part and carbon nano tube by water-containing tar |
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