CN115282947A - Method for preparing high-specific-surface-area metal/activated carbon composite material by using isosorbide residual tar - Google Patents

Method for preparing high-specific-surface-area metal/activated carbon composite material by using isosorbide residual tar Download PDF

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CN115282947A
CN115282947A CN202210244673.6A CN202210244673A CN115282947A CN 115282947 A CN115282947 A CN 115282947A CN 202210244673 A CN202210244673 A CN 202210244673A CN 115282947 A CN115282947 A CN 115282947A
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isosorbide
metal
specific surface
composite material
surface area
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CN115282947B (en
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单玉华
赵世丽
方慧
刘平
胡林玲
蔡志祥
刘玮
王碟
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Changzhou University
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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Abstract

The invention provides a method for preparing a metal/activated carbon composite material with high specific surface area by using isosorbide residual tar, which is characterized in that tar, urotropine, potassium nitrate and metal salt substances thereof, which are byproducts in the isosorbide production process, are fully mixed for a proper time at a proper temperature by adopting a proper machine, and the pre-mixed metal salt is reduced into metal in situ by utilizing the reducibility of high-temperature carbon, so that the metal/activated carbon composite material with high specific surface area is obtained. The additional use of a reducing agent is avoided, so that the preparation process of the metal/active carbon material is simple and efficient, the cost is reduced, and the emission is reduced.

Description

Method for preparing high-specific-surface-area metal/activated carbon composite material by using isosorbide residual tar
Technical Field
The invention relates to the technical field of preparation of metal/activated carbon composite materials, in particular to a technical method for preparing a metal/activated carbon composite material with a high specific surface area by using residual tar generated by the production of isosorbide.
Technical Field
Isosorbide is an important six-carbon platform compound derived from saccharides (starch cellulose), can be used for replacing petroleum-based monomers to prepare easily biodegradable materials such as polyester, polyurethane, polyamide and polyether, and can also be used for drug synthesis. Therefore, the isosorbide has great application prospect. However, in the process of producing isosorbide, depending on the catalyst used, 20 to 50% of tar is by-produced, and for example, the tar by-produced from isosorbide is a network-like macromolecule formed by intermolecular dehydration of sorbitol and intermolecular dehydration of the produced isosorbide under the action of an acid catalyst. In addition, these macromolecules continue to dehydrate under the action of acid catalysts to form polymeric compounds. [ xiu yu he, scientific notice, 2015, 60 (16): 1443].
The quality of the isosorbide byproduct tar is uniform, and the isosorbide byproduct tar has good fluidity. Easy post-processing treatment. Traditional biomass (such as agricultural waste) is uneven in composition, generally consists of lignin, cellulose, protein and ash, is poor in fluidity and is inconvenient for post-processing treatment.
How to properly treat the high-yield tar is an important factor for restricting the development of the isosorbide industry. The common method is incineration, which wastes biomass resources on the one hand and causes secondary pollution (large amounts of CO) on the other hand 2 Discharge). More sophisticated techniques are also used: such as thermal cracking, catalytic cracking plasma cracking technology [ lilehao, etc., chemical development, 2017, 36 (7): 2407), vaporizing the biomass tar. These methods are complicated and costly.
In addition, metal/activated carbon materialsIs a material with wide application in the fields of organic synthesis, preparation of energy-storage catalytic materials and the like. Generally by loading metal salts on activated carbon with high specific surface area and then using reducing gases (such as H) 2 、CH 4 CO, etc.) at high temperature to obtain the metal/active carbon composite material. The method has high cost and large discharge.
Disclosure of Invention
The invention aims to overcome the defects of high tar treatment cost, complex process and serious emission in the prior art. Provides a new method for utilizing isosorbide tar with more efficient resource utilization. Another object is to propose a novel and elegant method for the synthesis of "metal/activated carbon" materials with high specific surface area.
The technical scheme of the invention is as follows: the tar oil which is the byproduct in the production process of the isosorbide is mixed with the functional additive and the metal salt substance thereof according to a certain proportion at a proper temperature by adopting a proper machine to fully mix the materials for a proper time so as to uniformly mix the materials. The mixed material is subjected to a programmed temperature rise treatment in a nitrogen flow. The material after high-temperature pyrolysis is naturally cooled to the temperature near room temperature in nitrogen flow, and then the high-temperature pyrolysis material is washed by water in a proper mode, so that the metal/activated carbon composite material (M/C) which is high in dispersion, high in specific surface area and uniform in pore distribution is obtained. The material is preferably stored in a suitable inert medium.
Further, the functional additives are urotropin (hexamethylenetetramine) and potassium nitrate. The weight ratio of urotropine to potassium nitrate is 0.3-0.6: 1 (Wt).
Wherein the urotropine is decomposed at high temperature to generate gaseous formaldehyde and ammonia, and the generation of micropores is promoted. The generated formaldehyde and the furan ring-containing isosorbide byproduct tar are subjected to cross-linking reaction, so that the molecules of the carbonized precursor are larger, the generation of high specific surface area carbon is promoted, and the potassium nitrate is decomposed into potassium oxide and NO at high temperature X The gas promotes the generation of micropores, and the potassium oxide catalyzes the isosorbide tar to form carbon, so that the carbon with high specific surface area is obtained.
Further, salts with catalytic properties refer to: the metal salt may be a salt of a general metal such as iron, cobalt, copper, or nickel, or a salt of a noble metal such as ruthenium, rhodium, palladium, iridium, platinum, or silver.
The metal salt can be carbonate, nitrate, chloride, or organic acid salt.
Furthermore, the mass weight ratio of the isosorbide byproduct tar to the potassium nitrate and the metal salt is 100: 10-30: 1-20 (wt).
Further, the proper material mixing temperature is 60-100 ℃.
Further, the mechanical mixing method is to mix the materials by a ball mill or a wall breaking machine.
Wherein the proper time for mechanical mixing is different mixing times for different machines. Mixing for 2-4 h by a ball mill; stirring and mixing for 10-30 min by a wall breaking machine.
Furthermore, the temperature rising treatment procedure in the nitrogen flow is to make the material reach 650-850 ℃ from the room temperature to the vicinity of the room temperature at the temperature rising rate of 2-10 ℃/minute and keep the material at the high temperature for 1-4 hours. Then naturally cooling to be near room temperature in nitrogen flow, and discharging to obtain the high-temperature pyrolysis material.
Further, the washing of the high-temperature pyrolysis material by a proper mode is as follows: the weight ratio of water to the high-temperature pyrolysis material is 4-10: 1 (wt). And the washing is repeated for 3-5 times, and the washing process is strengthened by ultrasonic waves to remove the soluble impurities as much as possible.
The high-temperature pyrolysis material can be washed by a proper mode: the high-temperature pyrolysis material is filled into a packed column, and washing water continuously passes through a packing layer, so that water-soluble impurities are efficiently washed away at one time.
The high specific surface area "metal/activated carbon" composite material is preferably preserved in an appropriate inert medium in the presence of: purified water, C 1～4 Stored in alcohol to prevent the prepared M/C from being oxidized by air.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the scheme, the tar byproduct in the isosorbide production process is used as a carbon source for preparing the metal/activated carbon material with high specific surface area, so that resource utilization of a large amount of the tar byproduct is realized, the economic benefit of isosorbide production is improved, and the environmental pollution is reduced.
2. The invention adopts the scheme that a metal component precursor (namely a metal salt substance) and isosorbide tar are fully and uniformly heated before the temperature programming heat treatment, so as to obtain the metal/active carbon material with uniformly dispersed metal components.
3. The technical scheme of the invention is that urotropine and potassium nitrate which are functional additives are added. The high-temperature decomposition of the urotropine generates gaseous formaldehyde and ammonia to promote the generation of micropores, and the generated formaldehyde and the by-product tar of the isosorbide containing furan rings generate a cross-linking reaction to promote the generation of carbon with high specific surface area. Pyrolysis of potassium nitrate to potassium oxide and NO X The gas promotes the generation of micropores, and the potassium oxide catalyzes the isosorbide tar to form carbon, so that the carbon with high specific surface area is obtained. The synergistic effect generated by adding the urotropine and the potassium nitrate ensures that the isosorbide tar generates the activated carbon with high specific surface area under the condition of programmed temperature rise. And the pore channels are relatively uniform and distributed relatively intensively.
4. The invention utilizes the reducibility of high-temperature carbon to reduce the metal salt which is pre-mixed evenly into metal in situ, thereby obtaining the metal/active carbon material with high specific surface area. This avoids the additional use of H 2 、 CH 4 And reducing gases such as CO and the like are used as reducing agents, so that the preparation process of the metal/active carbon material is simple and efficient, the cost is reduced, and the emission is reduced.
Drawings
FIG. 1 is a schematic diagram of the condensation reaction of isosorbide residual tar and formaldehyde generated by the decomposition of urotropine under the catalysis of acid.
FIG. 2 is a drawing showing liquid nitrogen adsorption-desorption of the Pt/C composite material prepared in example 1.
FIG. 3 is a scanning electron microscope image of the Pt/C composite material prepared in example 1.
FIG. 4 is a drawing showing liquid nitrogen adsorption-desorption of the Pt/C composite material prepared in comparative example 1.
FIG. 5 is a scanning electron microscope image of the Pt/C composite material prepared in comparative example 1.
FIG. 6 is a drawing showing liquid nitrogen adsorption-desorption of the Pt/C composite material prepared in comparative example 2.
FIG. 7 is a scanning electron microscope image of the Pt/C composite material prepared in comparative example 2.
FIG. 8 is a drawing showing liquid nitrogen adsorption-desorption of the Pt/C composite material prepared in comparative example 3.
FIG. 9 is a scanning electron microscope image of the Pt/C composite material prepared in comparative example 3.
The analysis method comprises the following steps:
1. determination of specific surface area and pore volume of the material: liquid nitrogen adsorption method, ASAP 2010C type surface pore size adsorber, micromeritics corporation, usa;
2. analyzing metal elements on the surface of the material: SUPRA 5 model field emission scanning electron microscope, zeiss Instrument Inc. of Germany.
3. The byproduct tar in the production of the isosorbide is a byproduct in the production of the isosorbide by an acid catalytic dehydration method. Which contains 5% by weight of an acid catalyst (e.g. zinc chloride).
Detailed Description
Example 1: preparation of high specific surface area "Pt/C
100g of isosorbide tar, 9g of urotropin, 15g of potassium nitrate, 6g of chloroplatinic acid (37.5% Pt contained) were put in a ball mill and ground at 80 ℃ for 3 hours. And (3) placing the ball-milled material in a tube furnace, heating to 700 ℃ at a heating rate of 4 ℃/min in a nitrogen flow, keeping at 700 ℃ for 3h, naturally cooling to a temperature close to the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material. 44.9g of the obtained pyrolysis material and 250g of water are mixed, placed in an ultrasonic pool for treatment for 5 minutes and filtered. This water washing operation was then repeated 3 times, thereby obtaining a "Pt/C" material. And putting the obtained Pt/C material into purified water, and sealing and storing.
The specific surface area of the obtained "Pt/C" material was determined to be 780m by liquid nitrogen adsorption analysis 2 The pore volume was 0.91ml/g (see FIG. 2 for the adsorption-desorption diagram for liquid nitrogen). The pore diameter is 2-20 nm, and the pore diameter is mainly distributed at 4-10 nm. The surface was analyzed by scanning electron microscopy surface energy spectroscopy (SEM-EDS) to have a Pt content of 6.1% and a potassium content of 0.14% by weight (see FIG. 3 for a scanning electron micrograph at 10000 times). The analysis result shows that the Pt/C composite material with high specific surface is obtained.
Example 2: preparation of high specific surface area "Pd/C
100g of isosorbide tar, 5g of urotropin, 10g of potassium nitrate, 4g of palladium nitrate (41% Pd content) were put into a ball mill and ball-milled at 60 ℃ for 2 hours. And (3) placing the ball-milled material in a tube furnace, raising the temperature to 650 ℃ at the heating rate of 2 ℃/min in nitrogen flow, keeping the temperature at 650 ℃ for 4 hours, naturally cooling to the temperature close to the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material. 33.5g of the obtained high-temperature pyrolyzed material was mixed with 134g of water, and then placed in an ultrasonic bath to be treated for 5 minutes, filtered, and then such water washing operation was repeated 3 times, thereby obtaining a "Pd/C" material. And placing the obtained Pd/C material in purified water, and sealing and storing.
The specific surface area of the obtained 'Pd/C' material is determined to be 582 m by liquid nitrogen adsorption analysis 2 The pore volume is 0.56ml/g. The aperture is 2-25 nm, and the aperture is mainly distributed at 3-12 nm. Surface analysis by scanning electron microscopy (SEM-EDS) showed a Pd content of 4.8% and a potassium content of 0.21 wt%. The analysis result shows that the Pd/C composite material with high specific surface is obtained.
Example 3: preparation of high specific surface area "Ru/C
100g of isosorbide tar, 6g of urotropin, 20g of potassium nitrate, and 3g of ruthenium trichloride (37% by weight, ru contained) were put into a ball mill and ball-milled at 60 ℃ for 4 hours. And (3) placing the ball-milled material in a tube furnace, raising the temperature to 750 ℃ at the heating rate of 6 ℃/min in nitrogen flow, keeping the temperature at 750 ℃ for 2h, naturally cooling to the temperature close to the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
The obtained 44.5g of high-temperature pyrolysis material is mixed with 360g of water, then the mixture is placed in an ultrasonic pool for treatment for 5 minutes, and then the mixture is filtered. This water washing operation was then repeated 4 times, thus obtaining a "Ru/C" material. And putting the obtained Ru/C material into purified water, and sealing and storing.
The specific surface area of the obtained 'Ru/C' material is 591m determined by liquid nitrogen adsorption analysis 2 The pore volume was 0.71ml/g. The aperture is 2-20 nm, and the main distribution is 3-10 nm. The surface of the steel sheet was analyzed by scanning electron microscopy surface energy spectroscopy (SEM-EDS) to determine the content of Ru of 5.1% and the content of K of 0.1% by weight. The analysis result shows that the Ru/C composite material with high specific surface is obtained.
Example 4: preparation of high specific surface area "Rh/C
Placing 100g of isosorbide tar, 10g of urotropin, 25g of potassium nitrate, 1g of rhodium trichloride (39% Rh) in a wall breaking machine, and stirring at 100 deg.C for 20 minutes. And putting the stirred material into a tube furnace, raising the temperature to 750 ℃ at the heating rate of 8 ℃/min in nitrogen flow, keeping the temperature at 750 ℃ for 1h, naturally cooling to the temperature near the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
40.5g of the obtained high-temperature pyrolysis material and 405g of water are mixed, placed in an ultrasonic pool for treatment for 5 minutes and filtered. This water washing operation was then repeated 4 times, thereby obtaining "Rh/C" material. The obtained Rh/C material is put into purified water and sealed for storage.
The specific surface area of the obtained Rh/C material is determined to be 852m by liquid nitrogen adsorption analysis 2 The pore volume is 0.98ml/g. The aperture is 2-18 nm, and the aperture is mainly distributed between 3-9 nm. By scanning electron microscopy surface energy spectroscopy (SEM-EDS), the Rh content was 1.5% and the K content was 0.12% by weight. The analysis result shows that the Rh/C composite material with high specific surface is obtained.
Example 5: preparation of high specific surface area "Ag/C
100g of isosorbide tar, 12g of urotropin, 30g of potassium nitrate and 10g of silver nitrate (63% by weight of Ag) were placed in a cell-breaking machine and stirred at 100 ℃ for 20 minutes. And putting the stirred material into a tube furnace, raising the temperature to 650 ℃ at a heating rate of 5 ℃/min in nitrogen flow, keeping the temperature at 650 ℃ for 4 hours, naturally cooling to the temperature near the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
48.2g of the obtained high-temperature pyrolysis material and 300g of water are mixed, then are placed in an ultrasonic pool for treatment for 5 minutes, and are filtered. This water washing operation was then repeated 5 times, thereby obtaining an "Ag/C" material. And placing the obtained Ag/C material in purified water, and sealing and storing.
The specific surface area of the obtained Ag/C material is determined to be 983m by liquid nitrogen adsorption analysis 2 The pore volume is 1.09ml/g. The aperture is 2-25 nm, and the aperture is mainly distributed between 3-11 nm. The surface of the alloy was analyzed by scanning electron microscopy (SEM-EDS) for Ag content of 15.7% and K content of 0.17% by weight. The analysis result shows that the Ag/C composite material with high specific surface is obtained.
Example 6: preparation of high specific surface area "Ir/C
Placing 100g of isosorbide tar, 10g of urotropin, 20g of potassium nitrate, 3g of chloroiridic acid (39% Ir) in a wall breaking machine, and stirring at 100 deg.C for 10 minutes. And putting the stirred material into a tube furnace, heating to 800 ℃ at a heating rate of 10 ℃/min in nitrogen flow, keeping at 800 ℃ for 4h, naturally cooling to the temperature close to the room temperature in nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
39.5g of the obtained pyrolysis material was mixed with 400g of water, treated in an ultrasonic tank for 5 minutes, and filtered. This water washing operation was then repeated 5 times, thereby obtaining an "Ir/C" material. And placing the obtained Ir/C material in purified water, and sealing and storing.
The specific surface area of the obtained Ir/C material is 703m determined by liquid nitrogen adsorption analysis 2 The pore volume was 0.74ml/g. The aperture is 2-22 nm, and the aperture is mainly distributed between 3-9 nm. The Ir content and K content of the surface are respectively 4.7% and 0.09% (by weight) through the surface energy spectrum analysis of a scanning electron microscope (SEM-EDS). The analysis result shows that the Ir/C composite material with high specific surface is obtained.
Example 7: preparation of high specific surface area "Fe/C
Placing 100g isosorbide tar, 10g urotropin, 20g potassium nitrate, 20g ferric nitrate (containing 13.8% Fe) in the wall breaking machine, and stirring at 80 deg.C for 20 minutes. The stirred material was placed in a tube furnace and brought to 850 ℃ in a nitrogen stream at a heating rate of 10 ℃/min and held at 850 ℃ for 1h. Then naturally cooling to the temperature near room temperature in a nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
41g of the obtained high-temperature pyrolysis material is loaded into a glass filter column with the inner diameter of 20cm, 250g of water is dropped in the glass filter column within 1 hour to continuously wash the pyrolysis material, and therefore the Fe/C material is obtained. The resulting "Fe/C" material was placed in methanol and stored sealed.
The specific surface area of the obtained 'Pd/C' material is 866m by liquid nitrogen adsorption analysis 2 The pore volume was 0.96ml/g. The pore diameter is 2-20 nm, and the pore diameter is mainly distributed at 3-10 nm. The surface of the steel sheet was analyzed by scanning electron microscopy surface energy spectroscopy (SEM-EDS) to find that the Fe content was 9.3% and the K content was 0.08% by weight. The analysis result shows that the Fe/C composite material with high specific surface is obtained.
Example 8: preparation of high specific surface area "Co/C
100g of isosorbide tar, 15g of urotropin, 30g of potassium nitrate and 10g of cobalt succinate (33% by weight of Co) were placed in a cell-wall breaking machine and stirred at 100 ℃ for 20 minutes. And (3) placing the stirred material in a tube furnace, raising the temperature to 750 ℃ at the heating rate of 5 ℃/min in nitrogen flow, keeping the temperature at 750 ℃ for 3 hours, naturally cooling the material to the temperature close to the room temperature in nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
46.6g of the obtained high-temperature pyrolysis feed was charged into a glass filter column having an inner diameter of 20cm, and 250g of water was dropped in the column over 1 hour to continuously wash the pyrolysis feed, thereby obtaining a "Co/C" material. The obtained "Co/C" material was placed in ethanol and stored under sealed conditions.
The specific surface area of the obtained "Co/C" material is determined to be 1106m by liquid nitrogen adsorption analysis 2 The pore volume is 1.15ml/g. The pore diameter is 2-20 nm, and the pore diameter is mainly distributed at 3-11 nm. The surface Co content was 9.7% and the K content was 0.11% by weight as analyzed by scanning electron microscopy surface energy spectroscopy (SEM-EDS). The analysis result shows that the Co/C composite material with high specific surface is obtained.
Example 9: preparation of high specific surface area "Cu/C
100g of isosorbide tar, 8g of urotropin, 20g of potassium nitrate and 5g of basic copper carbonate (containing 57% Cu) were put in a ball mill and ground at 80 ℃ for 4 hours. And (3) placing the ball-milled material in a tube furnace, raising the temperature to 650 ℃ at the heating rate of 5 ℃/min in nitrogen flow, keeping the temperature at 650 ℃ for 2h, naturally cooling to the temperature close to the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
The obtained 42.0g of the high-temperature pyrolyzed material was mixed with 252g of water, and then placed in an ultrasonic bath to be treated for 5 minutes, filtered, and then such a water washing operation was repeated 4 times, thereby obtaining a "Cu/C" material. The obtained 'Cu/C' material is placed in isopropanol and sealed for storage.
The specific surface area of the obtained Cu/C material is determined to be 772m by liquid nitrogen adsorption analysis 2 The pore volume is 0.83ml/g. The pore diameter is 2-25 nm, and the pore diameter is mainly distributed at 3-10 nm. The surface was analyzed by scanning electron microscopy surface energy spectroscopy (SEM-EDS) to have a Cu content of 8.8% and a K content of 0.18% by weight. The analysis result shows that the yield is highSpecific surface Cu/C composite material.
Example 10: preparation of high specific surface area "Ni/C
100g of isosorbide tar, 10g of urotropin, 20g of potassium nitrite, and 20g of hydrated nickel nitrate (containing 20% Ni) were put into a ball mill and ground at 80 ℃ for 4 hours. And (3) placing the ball-milled material in a tube furnace, heating to 800 ℃ at the heating rate of 8 ℃/min in nitrogen flow, keeping at 800 ℃ for 2h, naturally cooling to the temperature close to the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
45.7g of the obtained pyrolysis material was mixed with 275g of water, treated in an ultrasonic tank for 5 minutes, and filtered. This water washing operation was then repeated 4 times, thereby obtaining a "Ni/C" material. The obtained 'Ni/C' material is put into n-butanol and sealed for storage.
The specific surface area of the obtained 'Ni/C' material is determined to be 845m by liquid nitrogen adsorption analysis 2 The pore volume was 1.1ml/g. The pore diameter is 2-20 nm, and the pore diameter is mainly distributed at 3-10 nm. The surface Ni content was 9.7% and K content was 0.19% by weight as analyzed by scanning electron microscopy surface energy spectroscopy (SEM-EDS). The analysis result shows that the Ni/C composite material with high specific surface is obtained.
Comparative example 1: preparation of 'Pt/C' composite material without adding functional additive
100g of isosorbide tar and 6g of chloroplatinic acid (37.5% by weight of Pt) were put in a ball mill and ground at 80 ℃ for 3 hours. And (3) placing the ball-milled material in a tube furnace, heating to 700 ℃ at a heating rate of 4 ℃/min in a nitrogen flow, keeping at 700 ℃ for 3h, naturally cooling to a temperature close to the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
34.6g of the obtained high-temperature pyrolysis material is mixed with 250g of water, then the mixture is placed in an ultrasonic pool for treatment for 5 minutes, and then filtration is carried out. This water washing operation was then repeated 3 times, thereby obtaining a "Pt/C" material. The obtained Pt/C material is put into purified water and sealed for storage.
The specific surface area of the obtained "Pt/C" material was determined to be 68m by liquid nitrogen adsorption analysis 2 The pore volume was 0.31ml/g (liquid nitrogen adsorption-desorption diagram is shown in FIG. 4). The pore diameter is distributed between 2nm and 90nm. Surface energy spectrum analysis (SEM-EDS) table by scanning electron microscopeThe Pt content of the surface was 4.8 wt% (see FIG. 5. At a magnification of 10000 times in a scanning electron microscope).
Compared with the result of the embodiment 1 of the invention, the method does not add urotropine and potassium nitrate, does not have the functions of decomposition, gasification, pore-forming and crosslinking, and has low carbonization rate of isosorbide tar, so that the prepared Pt/C composite material has small specific surface area; in addition, as can be seen from the liquid nitrogen adsorption-desorption curve, the material prepared without adding the functional additive has wide pore channel distribution.
Comparative example 2: preparation of 'Pt/C' composite material by only adding potassium nitrate
100g of isosorbide tar and 24g of KNO 3 6g of chloroplatinic acid (containing 37.5% by weight of Pt) was placed in a ball mill and ground at 80 ℃ for 3 hours. And (3) placing the ball-milled material in a tube furnace, heating to 700 ℃ at a heating rate of 4 ℃/min in a nitrogen flow, keeping at 700 ℃ for 3h, naturally cooling to a temperature close to the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
42.2g of the obtained pyrolysis material and 250g of water are mixed, then the mixture is placed in an ultrasonic pool for treatment for 5 minutes, and then filtration is carried out. This water washing operation was then repeated 3 times, thereby obtaining a "Pt/C" material. And putting the obtained Pt/C material into purified water, and sealing and storing.
The specific surface area of the obtained "Pt/C" material is 235m determined by liquid nitrogen adsorption analysis 2 The pore volume was 0.43ml/g (liquid nitrogen adsorption-desorption diagram is shown in FIG. 6). The pore diameter is 1-45 nm, and is mainly dispersed in 4-15 nm. The Pt content on the surface was 5.3 wt% by scanning electron microscopy surface energy spectroscopy (SEM-EDS) (scanning electron micrograph at 10000 times magnification is shown in FIG. 7).
Compared with the result of example 1, only potassium nitrate is added, the potassium oxide has the catalytic carbonization effect, but the urotropine does not have the decomposition pore-forming and crosslinking effects, so that the specific surface area of the prepared Pt/C composite material is relatively smaller.
Comparative example 3: preparation of 'Pt/C' composite material by adding urotropine only
100g of isosorbide tar, 24g of urotropin, 6g of chloroplatinic acid (37.5% by weight of Pt) were put into a ball mill and ground at 80 ℃ for 3 hours. And (3) placing the ball-milled material in a tube furnace, heating to 700 ℃ at a heating rate of 4 ℃/min in a nitrogen flow, keeping at 700 ℃ for 3h, naturally cooling to a temperature close to the room temperature in the nitrogen flow, and taking out the material to obtain the high-temperature pyrolysis material.
38.8g of the obtained high-temperature pyrolysis material and 250g of water are mixed, then are placed in an ultrasonic pool for treatment for 5 minutes, and are filtered. This water washing operation was then repeated 3 times, thereby obtaining a "Pt/C" material. And putting the obtained Pt/C material into purified water, and sealing and storing.
The specific surface area of the obtained "Pt/C" material is 188m determined by liquid nitrogen adsorption analysis 2 The pore volume was 0.21ml/g (liquid nitrogen adsorption-desorption diagram is shown in FIG. 8). The pore diameter is 1-25 nm, and the pore diameter is mainly distributed at 2-12 nm. The Pt content on the surface was 5.7 wt% by scanning electron microscopy surface energy spectroscopy (SEM-EDS) (scanning electron micrograph at 10000 times magnification is shown in FIG. 9).
Compared with the result of example 1, the specific surface area of the prepared Pt/C composite material is relatively smaller due to the fact that the addition of the urotropine only has the decomposition pore-forming and crosslinking effects of the urotropine but does not have the catalytic carbonization effect of the potassium oxide.
Comparison between comparative examples 2 and 3 and inventive example 1 shows that addition of urotropine and potassium nitrate produces synergistic effect, which greatly increases the specific surface area of the activated carbon produced by isosorbide tar under temperature programming.
Comparative example 4: h 2 Reduction method for preparing 'Pt/C' composite material
[ reference: lixian Run, etc. Catalytic science, 2008, 29 (3): 259]
50g of coconut shell activated carbon (environmental protection materials of Jiangsu Youhua, inc., specific surface area 960 m) 2 Per g, pore volume 0.68 ml/g), with 250ml of 5mol/L HNO 3 Oxidizing the water solution at 90 ℃ for 6h, filtering, washing, and drying at 60 ℃ to obtain the activated coconut shell activated carbon.
6g of chloroplatinic acid (containing 37.5% of Pt) was dissolved in 250ml of deionized water. The activated coconut shell activated carbon is added into chloroplatinic acid solution and stirred for 12 hours at room temperature. Suction filtering, and drying the solid at 80 ℃.
Placing the dried material in a tube furnace at 400 ml/min H 2 In a gas stream, the temperature is raised to 400 ℃ at a heating rate of 4 ℃/min and maintained at 400 ℃ for 2H, and then in H 2 Naturally cooling to near room temperature in the airflow, and taking out the material. And putting the obtained Pt/C material into purified water, and sealing and storing.
The specific surface area of the obtained Pt/C material is determined to be 945m by liquid nitrogen adsorption analysis 2 The pore volume was 0.63ml/g. The Pt content on the surface was 5.4 wt% as analyzed by scanning electron microscopy surface energy spectroscopy (SEM-EDS).
Compared with the results of example 1, the coconut shell activated carbon activation process and the Pt loading process both produced a large amount of waste liquid, and the reduction process consumed H 2 And (4) qi. The discharge of three wastes in the whole process is large. And the operation process is complicated.

Claims (11)

1. The method for preparing the metal/active carbon composite material with high specific surface area by using the isosorbide residual tar is characterized by comprising the following steps:
mechanically mixing the isosorbide byproduct tar with the functional additive and the metal salt substances thereof, carrying out in-process heating treatment on the mixed material in nitrogen flow for high-temperature pyrolysis, naturally cooling in the nitrogen flow after pyrolysis, washing with water to obtain a metal/active carbon composite material, and storing in an inert medium;
wherein the functional additive comprises urotropine and potassium nitrate.
2. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 1, characterized in that: the weight ratio of the urotropine to the potassium nitrate is 0.3-0.6: 1.
3. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 1, characterized in that: the metal salt is one or more of iron, cobalt, copper, nickel, ruthenium, rhodium, palladium, iridium, platinum and silver metal salt.
4. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 1, characterized in that: the metal salt is carbonate, nitrate, chloride or organic acid salt.
5. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 1, characterized in that: the weight ratio of the isosorbide byproduct tar to the potassium nitrate and the metal salt is 100: 10-30: 1-20.
6. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 1, characterized in that: the mechanical mixing temperature is 60-100 ℃.
7. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 1, characterized in that: the mechanical mixing method is to mix the materials by a ball mill or a wall breaking machine.
8. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 7, characterized in that: mixing for 2-4 h by a ball mill; stirring and mixing for 10-30 min by a wall breaking machine.
9. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 1, characterized in that: the temperature raising treatment procedure in nitrogen flow is that the temperature raising rate is 2-10 ℃/min, the temperature of the material reaches 650-850 ℃ from the room temperature, the material is kept at high temperature for 1-4 h, and then the material is naturally cooled to the room temperature in the nitrogen flow, and the high-temperature pyrolysis material is obtained.
10. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 1, characterized in that: the washing is that the weight ratio of water to the high-temperature pyrolysis material is 4-10: 1, the washing is repeated for 3-5 times, and the washing process is strengthened by ultrasonic waves, or the high-temperature pyrolysis material is filled into a filling column, washing water continuously passes through a packing layer, and water-soluble impurities are washed away.
11. The method for preparing the metal/activated carbon composite material with high specific surface area by using the isosorbide residual tar as claimed in claim 1, characterized in that: the preservation of the high specific surface area "metal/activated carbon" composite material in an inert medium means that: purified water and C1-4 alcohol are stored to prevent the prepared metal/active carbon composite material from being oxidized by air.
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