CN116020412A - Carbon material for adsorbing carbon monoxide, preparation method thereof and adsorption method of carbon monoxide - Google Patents
Carbon material for adsorbing carbon monoxide, preparation method thereof and adsorption method of carbon monoxide Download PDFInfo
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Abstract
The invention relates to the technical field of carbon material preparation, and discloses a carbon material for adsorbing carbon monoxide, a preparation method thereof and an adsorption method of carbon monoxide. According to the method, the cheap lignin is used as a carbon source, the characteristics of high carbon content are utilized, the cupric salt, the cupric carboxylate and the lignin are uniformly mixed, and are roasted and activated under the mixing of alkali metal salts, the carbon material with cuprous base load can be obtained through single roasting, the preparation process is simple, the raw materials are cheap, the preparation cost is low, the carbonization process of the lignin is fully activated due to the addition of the alkali metal salts, the dispersity of cuprous base active components in the carbon material is improved, the prepared carbon material has a very high specific surface area and a rich pore structure, the application in the fields of adsorption and the like is facilitated, the adsorption capacity of the carbon material to carbon monoxide can reach more than 45mL/g at normal temperature and normal pressure, and the carbon material has good carbon monoxide adsorption performance.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, in particular to a carbon material for adsorbing carbon monoxide, a preparation method thereof and an adsorption method of carbon monoxide.
Background
The hydrogen fuel cell vehicle is a new energy vehicle development direction with great potential, and has the advantages of zero emission, high energy conversion efficiency, wide fuel source and the like. A stable, reliable, low cost source of hydrogen is a fundamental condition for fuel cell automotive scale-up applications. The preparation, storage, transportation and other processes of hydrogen all have the problem of complex impurity gas pollution. Wherein, the content of carbon monoxide in the hydrogen gas is limited to below 200ppb because carbon monoxide can cause irreversible carbon corrosion and other permanent damage to electrodes in the fuel cell.
Activated carbon is a black powder or a block, granular, honeycomb amorphous carbon material. The activated carbon contains oxygen and hydrogen in addition to carbon elements, which remain in the carbon due to incomplete carbonization, or extraneous non-carbon elements are chemically bonded to the surface of the activated carbon during activation, such as oxidation of the surface of the activated carbon or oxidation of the surface of the activated carbon by steam when activated with steam; the main raw materials of the activated carbon can be almost all organic materials rich in carbon, such as coal, wood, fruit shells, coconut shells, walnut shells, apricot shells, jujube shells and the like. These carbonaceous materials are converted to activated carbon by pyrolysis at elevated temperature and pressure in an activation furnace; activated carbon is widely used in the fields of industrial adsorption, catalyst preparation and the like due to its good specific surface area and its readily available route.
CN1683249a discloses a carbon monoxide adsorbing material of copper (I) chloride, which is obtained by loading several copper precursors onto activated carbon and sintering at high temperature, wherein the loading amount of the active component copper chloride is more than 50%, and the carbon monoxide adsorption capacity is only 58mL/g at normal temperature and normal pressure.
Ma J, li L, jin R et al (CO adsorption on activated carbon-supported Cu-based adsorbent prepared by a facile route [ J ]. Separation & Purification Technology,2010,76 (1): 89-93.) utilize the principle of spontaneous monolayer dispersion to disperse CuCl on the surface of a support to prepare a highly effective CO adsorbent, and the adsorbent is obtained by mixing CuCl with activated carbon and calcining at 350℃for several hours. The adsorption capacity of the catalyst for carbon monoxide is only 56mL/g at the maximum at normal temperature and normal pressure.
The adsorption material for adsorbing carbon monoxide developed in the prior art mainly loads copper (I) chloride on carriers comprising active carbon, molecular sieve, alumina and the like, but the adsorption capacity of the adsorption material is limited, so that the removal depth of the adsorption material for carbon monoxide is influenced, the loading amount of active components is high, and the economic type of material development is also influenced. Therefore, there is a need to develop a carbon-based adsorbent material having a high adsorption capacity and a simple preparation process.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a carbon material for adsorbing carbon monoxide, a preparation method thereof and an adsorption method of carbon monoxide, wherein the carbon material has better carbon monoxide adsorption capacity, and the preparation process is simple, the raw materials are cheap, and the preparation cost is low.
In order to achieve the above object, a first aspect of the present invention provides a method for producing a carbon material for adsorbing carbon monoxide, the method comprising the steps of:
(1) Mixing cupric salt, cupric carboxylate, lignin and alkali metal salt in the presence of solvent to obtain suspension;
(2) Drying the suspension, and then roasting in an inert atmosphere;
(3) Washing the product obtained by roasting in the step (2), and then drying.
In a second aspect, the present invention provides a carbon material for adsorbing carbon monoxide produced by the production method of the first aspect.
In a third aspect, the present invention provides a method for adsorbing carbon monoxide, comprising:
contacting a gas containing carbon monoxide with a carbon material to adsorb carbon monoxide contained in the gas on the carbon material; wherein the carbon material is the carbon material of the second aspect.
According to the preparation method, the cheap lignin is used as a carbon source, the characteristics of high carbon content are utilized, the cupric salt, the copper carboxylate and the lignin are uniformly mixed, and are roasted and activated under the mixing of alkali metal salts, the preparation method can obtain the carbon material with cuprous base load through single roasting, the preparation process is simple, the raw materials are cheap, the preparation cost is low, the carbonization process of the lignin is fully activated due to the addition of the alkali metal salts, the dispersity of cuprous base active components in the carbon material is improved, the prepared carbon material has a very high specific surface area and a rich pore structure, the application in the fields of adsorption and the like is facilitated, and the carbon material has good carbon monoxide adsorption performance.
Drawings
FIG. 1 is N of the carbon material prepared in example 1 2 Adsorption-desorption isotherms;
FIG. 2 is a BJH pore size distribution curve of the carbon material prepared in example 1;
fig. 3 is an XPS diagram of the carbon material prepared in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a method for producing a carbon material for adsorbing carbon monoxide, the method comprising the steps of:
(1) Mixing cupric salt, cupric carboxylate, lignin and alkali metal salt in the presence of solvent to obtain suspension;
(2) Drying the suspension, and then roasting in an inert atmosphere;
(3) Washing the product obtained by roasting in the step (2), and then drying.
The inventor of the present invention found in the course of research that lignin, which is a cross-linked phenol polymer having a relatively high carbon content and a sufficient raw material and low cost, can be used as an excellent raw material for synthesizing an activated carbon-based adsorption material because lignin is a complex organic polymer which forms an important structural material in supporting tissues of vascular plants and some algae.
According to some embodiments of the invention, in step (1), a cupric salt, cupric carboxylate, lignin, and alkali metal salt are mixed in the presence of a solvent to obtain a suspension. The order of addition of the materials is not particularly limited as long as the object of the present invention can be achieved by obtaining a suspension, and in order to further improve the adsorption performance of the produced carbon material, the mixing preferably includes:
(1-1) first mixing a cupric salt, a copper carboxylate and a solvent to obtain a precursor solution;
(1-2) second mixing the precursor solution with lignin and an alkali metal salt to obtain the suspension. The above preferred embodiments are advantageous in promoting the dispersion of the active ingredient as well as in promoting the dispersion of the active ingredient during the subsequent calcination.
According to some embodiments of the invention, preferably, in step (1-1), the first mixing comprises heating and stirring; more preferably, the conditions for heating and stirring include: the temperature is 60-80deg.C, and the time is 10-20min.
According to some embodiments of the invention, preferably, in step (1-2), the conditions of the second mixing include: the process is carried out under the condition of stirring, the temperature is 60-80 ℃ and the time is 30-60min.
According to some embodiments of the invention, preferably, the molar ratio of the cupric salt to cupric carboxylate is 0.5-1.5:1, preferably 0.85-1.25:1. the molar ratio of the cupric salt to the cupric carboxylate is in the above-defined range to facilitate the formation of the cuprous component.
According to some embodiments of the invention, preferably, the divalent copper salt is selected from copper chloride and/or copper bromide.
According to some embodiments of the invention, preferably, the copper carboxylate is selected from at least one of copper formate, copper acetate and copper citrate.
According to some embodiments of the invention, the divalent copper salt and the copper carboxylate are preferably used in amounts such that the resulting carbon material has a content of the monovalent copper salt of 20-50 wt%, preferably 25-45 wt%, based on the total weight of the carbon material. Preferably, the monovalent copper salt is selected from CuCl and/or CuBr.
According to some embodiments of the present invention, the kind of the solvent is not particularly limited, so long as a suspension can be formed, preferably the solvent is water and/or ethanol, more preferably water; the amount of the solvent is not particularly limited, and the solvent may be used in the same manner as described above, so long as a suspension can be formed.
According to some embodiments of the present invention, the alkali metal salt may be selected from a wide range of alkali metal salts, as is conventional in the art. Preferably, the alkali metal salt is a potassium salt and/or a sodium salt, more preferably at least one of potassium chloride, potassium nitrate, potassium sulfate, sodium chloride, sodium nitrate, and sodium sulfate, and still more preferably potassium chloride. In the step (1), the addition of the alkali metal salt is helpful for activating the carbonization process of lignin to form a structured material with high specific surface area, and is also beneficial for improving the dispersity of the cuprous active component in the carbon material, so as to improve the adsorption effect of the carbon material on carbon monoxide.
According to some embodiments of the invention, the lignin is selected from a wide range of lignin, and lignin conventional in the art can be used. Preferably, the lignin is alkali washed lignin.
According to some embodiments of the invention, preferably, the mass ratio of the cupric salt to lignin is 0.2-1:1, preferably 0.25 to 0.5:1.
according to some embodiments of the invention, preferably, the mass ratio of alkali metal salt to lignin is 0.2-2:1, preferably 0.5-1:1. the mass ratio of the alkali metal salt to the lignin is within the above preferred range, so that the lignin can form a rich pore structure in the process of sintering the lignin into the carbon material.
According to some embodiments of the invention, in step (2), the suspension is dried and then calcined under an inert atmosphere. Preferably, the drying is rotary evaporation.
According to some embodiments of the invention, preferably, the inert atmosphere is provided by an inert gas selected from at least one of nitrogen, helium, argon and neon.
According to some embodiments of the invention, preferably, the firing conditions include: the temperature is 200-950 ℃ and the time is 2-6h; preferably, the flow rate of the inert gas is 5-200 mL/min.
According to some embodiments of the invention, in step (3), the product obtained by calcination in step (2) is washed and then dried. The mode of washing is not particularly limited, and a washing mode conventional in the art can be employed. Preferably, the washing comprises: dispersing the product obtained by roasting in the step (2) in an organic solvent.
According to some embodiments of the invention, preferably, the organic solvent is selected from at least one of ethanol, methanol and glycerol.
According to some embodiments of the invention, the preparation method takes low-cost lignin as a carbon source, uniformly mixes cupric salt, cupric carboxylate and lignin by utilizing the characteristic of high carbon content, and carries out roasting and activation under the mixing of alkali metal salts.
In a second aspect, the present invention provides a carbon material for adsorbing carbon monoxide produced by the production method of the first aspect.
According to some embodiments of the invention, the carbon material preferably has a carbon content of 40-80 wt%, preferably 50-70 wt%, based on the total weight of the carbon material.
According to some embodiments of the present invention, preferably, the monovalent copper salt is present in the carbon material in an amount of 20 to 50 wt%, preferably 25 to 45 wt%, based on the total weight of the carbon material; preferably, the monovalent copper salt is selected from CuCl and/or CuBr.
According to some embodiments of the invention, the carbon material preferably has an oxygen content of 1-10 wt%, preferably 1-8 wt%, based on the total weight of the carbon material.
According to some embodiments of the invention, the type and content of each component in the carbon material is determined by X-ray photoelectron spectroscopy (XPS) analysis. The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source is monochromized A1K alpha X-ray with power of 330W and basic vacuum of 3X 10 during analysis and test -9 mbar. In addition, the electron binding energy was corrected with the C1s peak (284.6 eV), and the post-peak splitting treatment software was XPSPEAK.
According to some embodiments of the invention, preferably, there are at least two mesoporous distribution peaks in the pore size distribution curve of the carbon material; more preferably, in the pore size distribution curve of the carbon material, a first mesoporous distribution peak exists at 2-10nm, and a second mesoporous distribution peak exists at 20-50 nm.
According to some embodiments of the invention, preferably, the mesoporous volume of the carbon material is 0.2-0.7cm 3 Preferably 0.25-0.65 cm/g 3 /g; preferably, the mesoporous volume of the carbon material is greater than 30%, preferably greater than 40%, of the total pore volume.
According to some embodiments of the invention, preferably, the carbon material has a BET specific surface area of 500-1000m 2 Preferably 500-900m 2 /g。
In the present invention, the term "mesoporous" is defined as pores having a pore diameter in the range of 2-50 nm.
In the present invention, the term "mesoporous distribution peak" refers to a mesoporous distribution peak on a pore distribution curve calculated according to the Barrett-Joyner-Halenda (BJH) method.
According to some embodiments of the invention, the pore structure properties of the material are detected by BET test methods. Specifically, the specific surface area and the pore volume of the material are measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the material are obtained by a Brunauer-Emmett-Taller (BET) method, and a mesoporous distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
According to some embodiments of the invention, the carbon material for adsorbing carbon monoxide has high specific surface area, rich pore structure, and high dispersity of the cuprous-based active component in the carbon material, is more beneficial to the application in the fields of adsorption and the like, and has good carbon monoxide adsorption performance.
In a third aspect, the present invention provides a method for adsorbing carbon monoxide, comprising:
contacting a gas containing carbon monoxide with a carbon material to adsorb carbon monoxide contained in the gas on the carbon material; wherein the carbon material is the carbon material of the second aspect.
According to some embodiments of the invention, preferably, the contacting conditions include: the temperature is 0-80 ℃ and the pressure is 50-150kPa; more preferably, the contacting is performed at normal temperature (25 ℃) and normal pressure (100 kPa (1 Bar)). During the contact process, the carbon material can absorb carbon monoxide to cause pressure drop and gradually reach adsorption equilibrium, so that the adsorbent with carbon dioxide is obtained.
According to some embodiments of the invention, preferably, the adsorption method further comprises heating and/or depressurizing the adsorbent having carbon dioxide adsorbed thereon, the heating and/or depressurizing being capable of desorbing carbon monoxide adsorbed on the carbon material, thereby recovering the carbon material and recycling the carbon material for use in the adsorption of carbon monoxide.
According to some embodiments of the invention, preferably, the heating conditions include: the temperature is 100-300 ℃ and the time is 0.5-3 hours.
According to some embodiments of the invention, preferably, the conditions of reduced pressure include: the pressure is 0-0.01kPa, and the time is 0.5-3 hours.
According to some embodiments of the present invention, in order to enhance the adsorption effect of the carbon material on carbon monoxide, it is preferable that the adsorption method further comprises, before the contacting, subjecting the carbon material to a heating treatment under an inert gas atmosphere or a reducing gas atmosphere, the heating treatment being capable of removing impurities adsorbed on the surface of the material, but ensuring that the metal active component does not undergo oxidation reaction.
According to some embodiments of the invention, the carbon material has an adsorption capacity of 45mL/g or more, and up to 67.8mL/g at normal temperature and normal pressure for carbon monoxide.
According to some embodiments of the invention, the carbon monoxide adsorption capacity of the nano metal composite adsorption material at normal temperature and normal pressure is measured by referring to GB/T19560-2008 'high pressure isothermal adsorption experiment method of coal'.
The present invention will be described in detail by examples. In the following examples and comparative examples:
unless otherwise specified, all reagents used in the present invention are analytically pure and commercially available.
The pore structure properties of the materials were examined by the BET test method. Specifically, the specific surface area and the pore volume of the material are measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the material are obtained by a Brunauer-Emmett-Taller (BET) method, and a mesoporous distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
The elements of the material surface were detected by X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source is monochromized A1K alpha X-ray with power of 330W and basic vacuum of 3X 10 during analysis and test -9 mbar. In addition, the electron binding energy was corrected with the C1s peak (284.6 eV), and the post-peak splitting treatment software was XPSPEAK.
Adsorption and desorption of carbon monoxide: the test is carried out by referring to GB/T19560-2008 'high pressure isothermal adsorption test method of coal'.
Examples 1-4 are provided to illustrate carbon materials for adsorbing carbon monoxide and methods of making the same.
Example 1
Step one, dissolving 3g of copper chloride and 3.8g of copper formate (the molar ratio of the copper chloride to the copper formate is 0.9:1) in deionized water, heating to 60 ℃ and stirring for 20 minutes to obtain a precursor solution;
adding 10g of lignin and 5g of potassium chloride into the precursor solution, stirring for 30 minutes at 60 ℃, and drying the obtained suspension by rotary evaporation to obtain a first material;
carbonizing the material I in a tube furnace under the protection of nitrogen at 800 ℃ (the flow rate of the nitrogen is 100 mL/min) for 120 minutes to obtain a material II;
and fourthly, dispersing the material II in ethanol, washing, filtering and drying to obtain the carbon material for adsorbing carbon monoxide.
Characterization of the materials:
FIG. 1 is N of the carbon material 2 Adsorption ofDesorption isotherm, fig. 2 is a BJH pore size distribution curve of the carbon material, from which it can be seen that the carbon material has two mesoporous distribution peaks at 3.6nm and 32.1 nm. The mesoporous volume of the carbon material is 0.28cm 3 Per g, 44% of the total pore volume; the BET specific surface area is shown in Table 1.
An X-ray photoelectron spectrum (XPS) diagram of the carbon material is shown in fig. 3, and it can be seen from the diagram that the XPS peak of CuCl exists in the carbon material obviously. The carbon material contained 61.7 wt% of carbon, 32 wt% of CuCl and 6.3 wt% of oxygen, based on the total weight of the carbon material.
Example 2
Step one, 4g of copper chloride and 4.5g of copper formate (the molar ratio of the copper chloride to the copper formate is 1.02:1) are dissolved in deionized water, and the temperature is raised to 60 ℃ and stirred for 20 minutes to obtain a precursor solution;
adding 10g of lignin and 8g of potassium chloride into the precursor solution, stirring for 30 minutes at 60 ℃, and drying the obtained suspension by rotary evaporation to obtain a first material;
carbonizing the material I in a tube furnace under the protection of nitrogen at 800 ℃ (the flow rate of the nitrogen is 100 mL/min) for 120 minutes to obtain a material II;
and fourthly, dispersing the material II in ethanol, washing, filtering and drying to obtain the carbon material for adsorbing carbon monoxide.
Characterization of the materials:
BET tests show that the carbon material has 2 mesoporous distribution peaks at 2.5nm and 37.2 nm. The mesoporous volume of the carbon material is 0.27cm 3 And/g, the proportion of the total pore volume is 41%; the BET specific surface area is shown in Table 1.
XPS test shows that the XPS peak of CuCl exists obviously in the carbon material. The carbon material contained 57.4 wt% of carbon, 41.4 wt% of CuCl and 1.2 wt% of oxygen, based on the total weight of the carbon material.
Example 3
Step one, 2.5g of copper chloride and 3g of copper acetate (the molar ratio of the copper chloride to the copper acetate is 1.13:1) are dissolved in deionized water, and the temperature is raised to 60 ℃ and stirred for 20 minutes to obtain a precursor solution;
adding 10g of lignin and 5g of sodium chloride into the precursor solution, stirring for 30 minutes at 60 ℃, and drying the obtained suspension by rotary evaporation to obtain a first material;
carbonizing the material I in a tubular furnace under the protection of nitrogen at 500 ℃ (the flow rate of the nitrogen is 100 mL/min) for 120 minutes to obtain a material II;
and fourthly, dispersing the material II in ethanol, washing, filtering and drying to obtain the carbon material for adsorbing carbon monoxide.
Characterization of the materials:
BET tests show that the carbon material has 2 mesoporous distribution peaks at 2nm and 24.6 nm. The mesoporous volume of the carbon material is 0.31cm 3 /g, 45% of the total pore volume; the BET specific surface area is shown in Table 1.
XPS test shows that the XPS peak of CuCl exists obviously in the carbon material. The carbon material contained 66.5 wt% of carbon, 27.1 wt% of CuCl and 6.4 wt% of oxygen, based on the total weight of the carbon material.
Example 4
Step one, dissolving 3g of copper bromide and 4.5g of cupric citrate (the molar ratio of the copper bromide to the cupric citrate is 1.25:1) in deionized water, heating to 60 ℃, and stirring for 20 minutes to obtain a precursor solution;
adding 10g of lignin and 2g of potassium chloride into the precursor solution, stirring for 30 minutes at 60 ℃, and drying the obtained suspension by rotary evaporation to obtain a first material;
carbonizing the material I in a tubular furnace under the protection of nitrogen at 700 ℃ (the flow rate of the nitrogen is 100 mL/min) for 120 minutes to obtain a material II;
and fourthly, the material II is discretely washed in glycerin, and then filtered and dried to obtain the carbon material for adsorbing carbon monoxide.
Characterization of the materials:
BET testThe carbon material is shown to have 2 mesoporous distribution peaks at 2.1nm and 46.5 nm. The mesoporous volume of the carbon material is 0.25cm 3 /g, a proportion of 57% of the total pore volume; the BET specific surface area is shown in Table 1.
XPS test shows that the XPS peak of CuBr exists obviously in the carbon material. The carbon material contained 68.7 wt% of carbon, 28.1 wt% of CuBr and 3.2 wt% of oxygen, based on the total weight of the carbon material.
Comparative example 1
Step one, dissolving 3g of copper chloride and 3.8g of copper formate (the molar ratio of the copper chloride to the copper formate is 0.9:1) in deionized water, heating to 60 ℃ and stirring for 20 minutes to obtain a precursor solution;
adding 10g of lignin and 8g of potassium chloride into the precursor solution, stirring for 30 minutes at 60 ℃, and drying the obtained suspension by rotary evaporation to obtain a first material;
and thirdly, carbonizing the material I in a tubular furnace under the protection of nitrogen at 800 ℃ (the flow rate of the nitrogen is 100 mL/min) for 120 minutes to obtain the carbon material for adsorbing carbon monoxide.
Characterization of the materials: the BET specific surface area of the carbon material is shown in Table 1. XPS test shows that the XPS peak of CuCl exists obviously in the carbon material. The carbon material contained 40.6 wt% of carbon based on the total weight of the carbon material.
Comparative example 2
Step one, dissolving 3g of copper chloride and 3.8g of copper formate (the molar ratio of the copper chloride to the copper formate is 0.9:1) in deionized water, heating to 60 ℃ and stirring for 20 minutes to obtain a precursor solution;
step two, adding 10g of lignin into the precursor solution, stirring for 30 minutes at 60 ℃, and drying the obtained suspension by rotary evaporation to obtain a material I;
and thirdly, carbonizing the material I in a tube furnace under the protection of nitrogen at 800 ℃ (the flow rate of the nitrogen is 100 mL/min) for 120 minutes to obtain a material II.
And fourthly, the material II is discretely washed in glycerin, and then filtered and dried to obtain the carbon material for adsorbing carbon monoxide.
Characterization of the materials: the BET specific surface area of the carbon material is shown in Table 1. XPS test shows that the XPS peak of CuCl exists obviously in the carbon material. The carbon material contained 52.1 wt% of carbon based on the total weight of the carbon material.
Test case
(a) Adsorption of carbon monoxide: filling the carbon materials prepared in examples 1 to 4 into an adsorption cylinder (with an inner diameter of 10mm, a height of 100mm and a filling length of 55 mm) of a BSD-PH high-pressure gas analyzer, respectively, then supplying 100% carbon monoxide gas into the adsorption cylinder at 25 ℃ and 100kPa (1 Bar), wherein the pressure of the adsorbent adsorbed by the gas is reduced, measuring the equilibrium pressure of the gas after the equilibrium pressure is reached, and calculating the adsorption capacity according to the pressure change of the system before and after adsorption to obtain the adsorption capacity (mL/g) of the carbon monoxide gas per unit adsorbent;
(b) Desorption of carbon monoxide: and (c) heating the adsorption cylinder which reaches adsorption equilibrium in the step (a) for 3 hours at the temperature of 300 ℃ under the condition of vacuum so as to desorb the carbon monoxide from the adsorbent.
The adsorption test and desorption test of carbon monoxide were repeated 5 times, and the average value was obtained, and the results are shown in table 1.
Comparative test example
The adsorption test and desorption test of carbon monoxide were performed in the same manner as in the test examples, except that the carbon materials prepared in comparative examples 1 to 2 were replaced with the adsorbents, respectively, and the results are shown in Table 1.
TABLE 1
The result shows that the carbon material obtained by the preparation method provided by the invention has good CO adsorption performance, and the adsorption capacity of the carbon material for carbon monoxide can reach more than 45mL/g and can reach 67.8mL/g at normal temperature and normal pressure; BET specific surface area up to 530m 2 And/g or more, carbon monoxide can be well adsorbed.
Comparative example 1 was obtained by subtracting the washing step from example 1, and the specific surface area of the carbon material was significantly reduced, and the carbon monoxide adsorbing ability was not provided.
Comparative example 2 was a carbon material in which alkali metal salt was not blended on the basis of example 1, so that the specific surface area of the carbon material was greatly reduced, and the carbon monoxide adsorption capacity was also affected.
Therefore, in the preparation method provided by the invention, the addition of the alkali metal salt is beneficial to activating the carbonization process of lignin, so that the lignin is formed into a structured material with high specific surface area, and meanwhile, the dispersity of the cuprous-based active component in the carbon material is improved, and the adsorption effect of the carbon material on carbon monoxide is further improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for preparing a carbon material for adsorbing carbon monoxide, the method comprising the steps of:
(1) Mixing cupric salt, cupric carboxylate, lignin and alkali metal salt in the presence of solvent to obtain suspension;
(2) Drying the suspension, and then roasting in an inert atmosphere;
(3) Washing the product obtained by roasting in the step (2), and then drying.
2. The production method according to claim 1, wherein in step (1), the mixing comprises:
(1-1) first mixing a cupric salt, a copper carboxylate and a solvent to obtain a precursor solution;
(1-2) second mixing the precursor solution with lignin and an alkali metal salt to obtain the suspension;
preferably, in step (1-1), the first mixing comprises heating and stirring; more preferably, the conditions for heating and stirring include: the temperature is 60-80 ℃ and the time is 10-20min;
preferably, in step (1-2), the conditions of the second mixing include: the process is carried out under the condition of stirring, the temperature is 60-80 ℃ and the time is 30-60min.
3. The preparation process according to claim 1 or 2, wherein the molar ratio of the cupric salt to the cupric carboxylate is 0.5-1.5:1, preferably 0.85-1.25:1, a step of;
preferably, the cupric salt is selected from copper chloride and/or copper bromide;
preferably, the copper carboxylate is selected from at least one of copper formate, copper acetate and copper citrate.
4. A production method according to any one of claims 1 to 3, wherein the mass ratio of the alkali metal salt to lignin is 0.2 to 2:1, preferably 0.5-1:1, a step of;
preferably, the alkali metal salt is a potassium salt and/or a sodium salt, more preferably at least one of potassium chloride, potassium nitrate, potassium sulfate, sodium chloride, sodium nitrate, and sodium sulfate, and still more preferably potassium chloride.
5. The production method according to any one of claims 1 to 4, wherein the lignin is alkali-washed lignin; preferably, the mass ratio of the cupric salt to lignin is 0.2-1:1, preferably 0.25 to 0.5:1.
6. the production method according to any one of claims 1 to 5, wherein in step (2), the drying is rotary evaporation;
preferably, the inert atmosphere is provided by an inert gas selected from at least one of nitrogen, helium, argon and neon;
preferably, the roasting conditions include: the temperature is 200-950 ℃ and the time is 2-6h; preferably, the flow rate of the inert gas is 5-200 mL/min.
7. The production method according to any one of claims 1 to 6, wherein in step (3), the washing comprises: dispersing the product obtained by roasting in the step (2) in an organic solvent;
preferably, the organic solvent is selected from at least one of ethanol, methanol and glycerin.
8. A carbon material for adsorbing carbon monoxide produced by the production method according to any one of claims 1 to 7;
preferably, the carbon material has a carbon content of 40 to 80 wt%, preferably 50 to 70 wt%, based on the total weight of the carbon material; the content of monovalent copper salt is 20 to 50 wt%, preferably 25 to 45 wt%; the oxygen content is 1-10 wt%, preferably 1-8 wt%;
preferably, the monovalent copper salt is selected from CuCl and/or CuBr;
preferably, there are at least two mesoporous distribution peaks in the pore size distribution curve of the carbon material;
preferably, in the pore size distribution curve of the carbon material, a first mesoporous distribution peak exists at 2-10nm, and a second mesoporous distribution peak exists at 20-50 nm.
9. The carbon material of claim 8, wherein the carbon material has a mesoporous volume of 0.2-0.7cm 3 Preferably 0.25-0.65 cm/g 3 /g；
Preferably, the mesoporous volume of the carbon material is greater than 30%, preferably greater than 40% of the total pore volume;
preferably, the BET specific surface area of the carbon material is 500-1000m 2 Preferably 500-900m 2 /g。
10. A method of adsorbing carbon monoxide, the method comprising:
contacting a gas containing carbon monoxide with a carbon material to adsorb carbon monoxide contained in the gas on the carbon material; wherein the carbon material is the carbon material of claim 8 or 9;
preferably, the adsorption method further comprises, before the contacting, subjecting the carbon material to a heat treatment under an inert gas atmosphere or a reducing gas atmosphere.
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