CN115738598B - Method for treating organic waste gas generated in shoemaking and gluing - Google Patents
Method for treating organic waste gas generated in shoemaking and gluing Download PDFInfo
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Abstract
The invention relates to the field of shoemaking gluing, in particular to a method for treating organic waste gas generated during shoemaking gluing, which comprises the following steps: step 1, collecting waste gas in a workshop for shoemaking and gluing in a negative pressure mode, leaching the collected waste gas by alkaline water, and drying to remove water to form pretreated waste gas; and 2, conveying the pretreated waste gas into a purifying and absorbing box for treatment, wherein a plurality of ultraviolet light sources and purifying and absorbing layers are arranged in the purifying and absorbing box, and discharging the waste gas out of the box after reaching the standard through purifying treatment of the purifying and absorbing layers, so that treatment is finished. Compared with the active carbon series products in the market, the purifying absorbent prepared by the invention is not only green and environment-friendly, but also has higher purifying efficiency and can be reused.
Description
Technical Field
The invention relates to the field of shoemaking gluing, in particular to a method for treating organic waste gas generated in shoemaking gluing.
Background
In the process of processing footwear products, shoemaking comprises a plurality of links, and common production processes comprise shoe shape development, vamp processing, sole production, surface-sole combination and the like, and the main production processes of various shoes comprise cutting, upper surface sewing, sole pasting molding, finishing and packaging. The source of pollution in the shoe industry is mainly from the forming shop, where various adhesives and treatments and cleaners are used, and thus a large amount of volatile organic waste gas is generated. If the organic waste gas is directly discharged into the atmosphere without treatment, the atmospheric pollution is caused, so that the organic waste gas generated in shoemaking is purified, and the requirements of standard emission are imperative.
The main component of the waste gas generated in shoemaking is organic waste gas, and various organic waste gas treatment methods exist at present, and the active carbon adsorption method and the combustion method are common. The activated carbon adsorption method is practical and wide, simple to operate and low in investment, but the activated carbon subjected to subsequent saturated adsorption needs to be subjected to complicated hazardous waste treatment; the treatment efficiency of the VOCs waste gas by the combustion method is high, but if the VOCs waste gas contains S, N and other elements, the waste gas generated after combustion is directly discharged outwards, so that secondary pollution can be caused. Therefore, a more effective and environment-friendly method for treating organic waste gas generated during shoemaking and gluing is needed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for treating organic waste gas for shoemaking gluing, which is efficient, environment-friendly and sustainable.
The aim of the invention is realized by adopting the following technical scheme:
a method for treating organic waste gas generated in shoe making and gluing comprises the following steps:
step 1, collecting waste gas in a workshop for shoemaking and gluing in a negative pressure mode, leaching the collected waste gas by alkaline water, and drying to remove water to form pretreated waste gas;
and 2, conveying the pretreated waste gas into a purifying and absorbing box for treatment, wherein a plurality of ultraviolet light sources and purifying and absorbing layers are arranged in the purifying and absorbing box, and discharging the waste gas out of the box after reaching the standard through purifying treatment of the purifying and absorbing layers, so that treatment is finished.
Preferably, a purification absorbent is disposed in the purification absorbent layer, and the preparation process of the purification absorbent includes:
(1) Preparing a carrier:
A1. taking three-dimensional carbon nanotube powder, and performing hydro-thermal treatment on ethylenediamine to obtain amino-crosslinked three-dimensional carbon nanotubes;
A2. preparing a sodium pyrophosphate solution by using anhydrous sodium pyrophosphate, and preparing a calcium chloride solution by using anhydrous calcium chloride;
A3. mixing and reacting the amino-crosslinked three-dimensional carbon nanotube, sodium pyrophosphate solution and calcium chloride solution to obtain calcium pyrophosphate/three-dimensional carbon nanotube;
(2) Load carrier:
B1. mixing bismuth salt and yttrium salt in deionized water, simultaneously adding pyridine-2, 6-dicarboxylic acid, and stirring to form a pre-reaction solution;
B2. adding calcium pyrophosphate/three-dimensional carbon nano tubes into the pre-reaction liquid, and carrying out hydrothermal reaction to finally obtain the purifying absorbent.
Preferably, the purity of the three-dimensional carbon nanotube powder is more than 99.9%, the diameter is 20-30nm, and the length is 10-30 μm.
Preferably, the synthesis process of A1 includes:
weighing three-dimensional carbon nanotube powder, mixing in deionized water, adding ethylenediamine, ultrasonically forming uniform mixed solution, pouring into a reaction kettle, performing heat preservation at 80-100deg.C for 15-25 hr, collecting solid in the reaction kettle, washing and drying to obtain amino crosslinked three-dimensional carbon Nanotube (NH) 2 -t-CNT)。
Preferably, in the A1 process, the mass ratio of the three-dimensional carbon nano tube powder to the ethylenediamine to the deionized water is 1:0.2-0.4:100-200.
Preferably, in the A2 process, the mass ratio of anhydrous sodium pyrophosphate to deionized water is 1:15-25, and the mass ratio of anhydrous calcium chloride to deionized water is 1:20-30.
Preferably, the reaction process of A3 comprises:
mixing amino crosslinked three-dimensional carbon nanotube with sodium pyrophosphate solution at room temperature, forming uniform mixed solution under ultrasonic condition, placing on magnetic stirrer, stirring while gradually adding calcium chloride solution, stirring at room temperature for 12-20 hr, heating to 90-100deg.C until the water solution is evaporated to dryness, collecting the rest solid, dialyzing to remove free ions, and drying to obtain calcium pyrophosphate/three-dimensional carbon nanotube.
Preferably, in the A3 process, the mass ratio of the amino-crosslinked three-dimensional carbon nano tube, the sodium pyrophosphate solution and the calcium chloride solution is 1:32-48:40-50.
Preferably, in the process of B1, bismuth salt is bismuth nitrate pentahydrate, yttrium salt is yttrium nitrate hexahydrate, and the mass ratio of bismuth salt, yttrium salt, pyridine-2, 6-dicarboxylic acid and deionized water is 0.26-0.32:0.39-0.44:0.6:100.
Preferably, in the B2 process, the mass ratio of the calcium pyrophosphate/the three-dimensional carbon nano tube to the pre-reaction liquid is 1:22-40.
The beneficial effects of the invention are as follows:
1. the invention provides a more effective treatment method for organic waste gas generated by gluing in the prior shoemaking, which is mainly characterized in that the prepared purifying absorbent has better purifying and absorbing effects on the organic waste gas containing aldehydes and benzene.
2. The purification absorbent prepared by the invention takes calcium pyrophosphate/three-dimensional carbon nano tube (CP/t-CNT) as a carrier material, and the surface of the purification absorbent is loaded with the pyridyl bismuth yttrium complex as a carrier by a high-pressure hydrothermal loading mode.
3. The purification absorbent prepared by the invention is different from the existing purification material in that firstly, the carrier calcium pyrophosphate/three-dimensional carbon nano tube is not conventional carbon fiber or activated carbon, but is a carbon nano tube with a three-dimensional porous structure, and calcium pyrophosphate grows on the surface of the three-dimensional carbon nano tube in an in-situ synthesis mode to obtain a modified three-dimensional carbon nano tube carrier; and secondly, the load is a complex of metal bismuth and yttrium, and the complex adopts pyridine-2, 6-dicarboxylic acid containing carboxyl, and the complex is subjected to hydrothermal complexing on the surface of the carrier, so that the purifying absorbent is formed.
4. Calcium pyrophosphate is mainly used as an additive such as a filler or a neutralizer in the market, but has a better promotion effect on the purification and absorption of subsequent organic waste gas after being synthesized on a three-dimensional carbon nano tube in situ in the invention, which is also an advantage of the invention which is different from the conventional purification material. In addition, the mutual coordination effect between the supported metal bismuth/yttrium/pyridine complex and the carrier also shows very bright eyes, and the effect which cannot be achieved by other metal composite materials or single metal is obtained.
5. Compared with the active carbon series products in the market, the purifying absorbent prepared by the invention is not only green and environment-friendly, but also has higher purifying efficiency and can be reused.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is an SEM image of a purified absorbent prepared according to example 1 of the present invention.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention will be further described with reference to the following examples.
Example 1
A method for treating organic waste gas generated in shoe making and gluing comprises the following steps:
step 1, collecting waste gas in a workshop for shoemaking and gluing in a negative pressure mode, leaching the collected waste gas by alkaline water, and drying to remove water to form pretreated waste gas;
and 2, conveying the pretreated waste gas into a purifying and absorbing box for treatment, wherein a plurality of ultraviolet light sources and purifying and absorbing layers are arranged in the purifying and absorbing box, and discharging the waste gas out of the box after reaching the standard through purifying treatment of the purifying and absorbing layers, so that treatment is finished.
Preferably, a purification absorbent is disposed in the purification absorbent layer, and the preparation process of the purification absorbent includes:
(1) Preparing a carrier:
A1. weighing three-dimensional carbon nanotube powder, mixing in deionized water, adding ethylenediamine, ultrasonically forming uniform mixed solution, pouring into a reaction kettle, performing heat preservation at 90 ℃ for 20h, collecting solid in the reaction kettle, washing and drying to obtain amino-crosslinked three-dimensional carbon Nanotube (NH) 2 -t-CNT)；
Wherein the purity of the three-dimensional carbon nano tube powder is more than 99.9%, the diameter is 20-30nm, and the length is 10-30 mu m. The mass ratio of the three-dimensional carbon nano tube powder to the ethylenediamine to the deionized water is 1:0.3:150.
A2. Weighing anhydrous sodium pyrophosphate and deionized water, mixing in a beaker, and stirring to form a uniform sodium pyrophosphate solution; weighing anhydrous calcium chloride and deionized water, mixing in a beaker, and stirring to form a uniform calcium chloride solution;
wherein, the mass ratio of anhydrous sodium pyrophosphate to deionized water is 1:20, and the mass ratio of anhydrous calcium chloride to deionized water is 1:25.
A3. Mixing amino-crosslinked three-dimensional carbon nanotubes with sodium pyrophosphate solution in room temperature, forming uniform mixed solution under ultrasonic conditions, placing on a magnetic stirrer, starting stirring, gradually adding calcium chloride solution, stirring at room temperature for 15h, heating to 100 ℃ until the water solution is evaporated to dryness, collecting the remaining solid, removing free ions through dialysis, and drying to obtain calcium pyrophosphate/three-dimensional carbon nanotubes (CP/t-CNT);
wherein the mass ratio of the amino-crosslinked three-dimensional carbon nano tube, the sodium pyrophosphate solution and the calcium chloride solution is 1:41:45.
(2) Load carrier:
B1. sequentially adding bismuth nitrate pentahydrate and yttrium nitrate hexahydrate into deionized water, magnetically stirring to form a uniform solution, then adding pyridine-2, 6-dicarboxylic acid, magnetically stirring for 45min to form a pre-reaction solution;
wherein the mass ratio of bismuth nitrate pentahydrate, yttrium nitrate hexahydrate, pyridine-2, 6-dicarboxylic acid and deionized water is 0.29:0.42:0.6:100.
B2. Adding calcium pyrophosphate/three-dimensional carbon nano tube into the pre-reaction liquid, uniformly mixing by ultrasonic, pouring into a reaction kettle, preserving heat at 140 ℃ for 56 hours, naturally cooling to room temperature, collecting solid in the reaction kettle, washing with water for three times, and drying to constant weight to obtain a purification absorbent;
wherein the mass ratio of the calcium pyrophosphate/the three-dimensional carbon nano tube to the pre-reaction liquid is 1:32.
Example 2
The difference between the treatment method of organic waste gas for shoemaking and gluing and the embodiment 1 is that: the purification absorbent is prepared by different processes.
The preparation process of the purification absorbent comprises the following steps:
(1) Preparing a carrier:
A1. weighing three-dimensional carbon nanotube powder, mixing in deionized water, adding ethylenediamine, ultrasonically forming uniform mixed solution, pouring into a reaction kettle, performing heat preservation at 80deg.C for 15 hr, collecting solid in the reaction kettle, washing and drying to obtain amino crosslinked three-dimensional carbon Nanotube (NH) 2 -t-CNT)；
Wherein the purity of the three-dimensional carbon nano tube powder is more than 99.9%, the diameter is 20-30nm, and the length is 10-30 mu m. The mass ratio of the three-dimensional carbon nano tube powder to the ethylenediamine to the deionized water is 1:0.2:100.
A2. Weighing anhydrous sodium pyrophosphate and deionized water, mixing in a beaker, and stirring to form a uniform sodium pyrophosphate solution; weighing anhydrous calcium chloride and deionized water, mixing in a beaker, and stirring to form a uniform calcium chloride solution;
wherein, the mass ratio of anhydrous sodium pyrophosphate to deionized water is 1:15, and the mass ratio of anhydrous calcium chloride to deionized water is 1:20.
A3. Mixing amino-crosslinked three-dimensional carbon nanotubes with sodium pyrophosphate solution in room temperature, forming uniform mixed solution under ultrasonic conditions, placing on a magnetic stirrer, starting stirring, gradually adding calcium chloride solution, stirring at room temperature for 12h, heating to 90 ℃ until the water solution is evaporated to dryness, collecting the remaining solid, removing free ions through dialysis, and drying to obtain calcium pyrophosphate/three-dimensional carbon nanotubes (CP/t-CNT);
wherein the mass ratio of the amino-crosslinked three-dimensional carbon nano tube, the sodium pyrophosphate solution and the calcium chloride solution is 1:32:40.
(2) Load carrier:
B1. sequentially adding bismuth nitrate pentahydrate and yttrium nitrate hexahydrate into deionized water, magnetically stirring to form a uniform solution, then adding pyridine-2, 6-dicarboxylic acid, magnetically stirring for 30min to form a pre-reaction solution;
wherein the mass ratio of bismuth nitrate pentahydrate, yttrium nitrate hexahydrate, pyridine-2, 6-dicarboxylic acid and deionized water is 0.26:0.39:0.6:100.
B2. Adding calcium pyrophosphate/three-dimensional carbon nano tube into the pre-reaction liquid, uniformly mixing by ultrasonic, pouring into a reaction kettle, preserving heat at 120 ℃ for 48 hours, naturally cooling to room temperature, collecting solid in the reaction kettle, washing with water for three times, and drying to constant weight to obtain a purification absorbent;
wherein the mass ratio of the calcium pyrophosphate/the three-dimensional carbon nano tube to the pre-reaction liquid is 1:22.
Example 3
The preparation process of the purification absorbent comprises the following steps:
(1) Preparing a carrier:
A1. weighing three-dimensional carbon nanotube powder, mixing in deionized water, adding ethylenediamine, ultrasonically forming uniform mixed solution, pouring into a reaction kettle, performing heat preservation at 100deg.C for 25 hr, collecting solid in the reaction kettle, washing and drying to obtain amino crosslinked three-dimensional carbon Nanotube (NH) 2 -t-CNT)；
Wherein the purity of the three-dimensional carbon nano tube powder is more than 99.9%, the diameter is 20-30nm, and the length is 10-30 mu m. The mass ratio of the three-dimensional carbon nano tube powder to the ethylenediamine to the deionized water is 1:0.4:200.
A2. Weighing anhydrous sodium pyrophosphate and deionized water, mixing in a beaker, and stirring to form a uniform sodium pyrophosphate solution; weighing anhydrous calcium chloride and deionized water, mixing in a beaker, and stirring to form a uniform calcium chloride solution;
wherein, the mass ratio of anhydrous sodium pyrophosphate to deionized water is 1:25, and the mass ratio of anhydrous calcium chloride to deionized water is 1:30.
A3. Mixing amino-crosslinked three-dimensional carbon nanotubes with sodium pyrophosphate solution in room temperature, forming uniform mixed solution under ultrasonic conditions, placing on a magnetic stirrer, starting stirring, gradually adding calcium chloride solution, stirring at room temperature for 20h, heating to 100 ℃ until the water solution is evaporated to dryness, collecting the remaining solid, removing free ions through dialysis, and drying to obtain calcium pyrophosphate/three-dimensional carbon nanotubes (CP/t-CNT);
wherein the mass ratio of the amino-crosslinked three-dimensional carbon nano tube, the sodium pyrophosphate solution and the calcium chloride solution is 1:48:50.
(2) Load carrier:
B1. sequentially adding bismuth nitrate pentahydrate and yttrium nitrate hexahydrate into deionized water, magnetically stirring to form a uniform solution, then adding pyridine-2, 6-dicarboxylic acid, magnetically stirring for 60min to form a pre-reaction solution;
wherein the mass ratio of bismuth nitrate pentahydrate, yttrium nitrate hexahydrate, pyridine-2, 6-dicarboxylic acid and deionized water is 0.32:0.44:0.6:100.
B2. Adding calcium pyrophosphate/three-dimensional carbon nano tube into the pre-reaction liquid, uniformly mixing by ultrasonic, pouring into a reaction kettle, preserving heat at 160 ℃ for 72 hours, naturally cooling to room temperature, collecting solid in the reaction kettle, washing with water for three times, and drying to constant weight to obtain a purification absorbent;
wherein the mass ratio of the calcium pyrophosphate/the three-dimensional carbon nano tube to the pre-reaction liquid is 1:40.
Comparative example 1
The three-dimensional carbon nanotube powder in example 1 was directly used as a purification absorbent.
Comparative example 2
A purification absorbent was only calcium pyrophosphate/three-dimensional carbon nanotube (CP/t-CNT) prepared in example 1.
Comparative example 3
Unlike the support of example 1, the purification absorbent was prepared as follows:
(1) Preparing a carrier:
the three-dimensional carbon nanotube powder in example 1 was used as a carrier;
(2) Load carrier:
B1. sequentially adding bismuth nitrate pentahydrate and yttrium nitrate hexahydrate into deionized water, magnetically stirring to form a uniform solution, then adding pyridine-2, 6-dicarboxylic acid, magnetically stirring for 45min to form a pre-reaction solution;
wherein the mass ratio of bismuth nitrate pentahydrate, yttrium nitrate hexahydrate, pyridine-2, 6-dicarboxylic acid and deionized water is 0.29:0.42:0.6:100.
B2. Adding three-dimensional carbon nanotube powder into the pre-reaction liquid, uniformly mixing by ultrasonic, pouring into a reaction kettle, preserving heat at 140 ℃ for 56 hours, naturally cooling to room temperature, collecting solid in the reaction kettle, washing with water for three times, and drying to constant weight to obtain a purification absorbent;
wherein the mass ratio of the three-dimensional carbon nano tube powder to the pre-reaction liquid is 1:32.
Comparative example 4
A purifying absorbent, the loaded metal complexing agent is yttrium-pyridine complex, and the preparation process is as follows:
(1) Preparing a carrier:
the procedure was the same as in example 1.
(2) Load carrier:
B1. weighing yttrium nitrate hexahydrate, adding the yttrium nitrate hexahydrate into deionized water, magnetically stirring the yttrium nitrate hexahydrate into uniform solution, adding pyridine-2, 6-dicarboxylic acid into the solution, magnetically stirring the solution for 45 minutes to form a pre-reaction solution;
wherein the mass ratio of yttrium nitrate hexahydrate, pyridine-2, 6-dicarboxylic acid and deionized water is 0.71:0.6:100.
B2. Adding calcium pyrophosphate/three-dimensional carbon nano tube into the pre-reaction liquid, uniformly mixing by ultrasonic, pouring into a reaction kettle, preserving heat at 140 ℃ for 56 hours, naturally cooling to room temperature, collecting solid in the reaction kettle, washing with water for three times, and drying to constant weight to obtain a purification absorbent;
wherein the mass ratio of the calcium pyrophosphate/the three-dimensional carbon nano tube to the pre-reaction liquid is 1:32.
Comparative example 5
A purifying absorbent, the supported metal complexing agent is bismuth-pyridine complex only, and the preparation process is as follows:
(1) Preparing a carrier:
the procedure was the same as in example 1.
(2) Load carrier:
B1. weighing bismuth nitrate pentahydrate, adding the bismuth nitrate pentahydrate into deionized water, magnetically stirring the bismuth nitrate pentahydrate into uniform solution, then adding pyridine-2, 6-dicarboxylic acid, magnetically stirring the bismuth nitrate pentahydrate for 45min to form pre-reaction liquid;
wherein the mass ratio of bismuth nitrate pentahydrate, pyridine-2, 6-dicarboxylic acid and deionized water is 0.71:0.6:100.
B2. Adding calcium pyrophosphate/three-dimensional carbon nano tube into the pre-reaction liquid, uniformly mixing by ultrasonic, pouring into a reaction kettle, preserving heat at 140 ℃ for 56 hours, naturally cooling to room temperature, collecting solid in the reaction kettle, washing with water for three times, and drying to constant weight to obtain a purification absorbent;
wherein the mass ratio of the calcium pyrophosphate/the three-dimensional carbon nano tube to the pre-reaction liquid is 1:32.
In order to more clearly illustrate the content of the present invention, the purified absorbents prepared in example 1 and comparative examples 1 to 5 of the present invention were tested and compared.
In table 1, the experimental conditions were: in the airtight case of 5L, throw in multiple organic volatile waste gas, include: formaldehyde at a concentration of 50ppm, benzene at a concentration of 200ppm and trichloroethylene at a concentration of 200 ppm. The amount of the purified absorbent in each of example 1 and comparative example 1/2/3/4/5 was 1g. The sealed box is irradiated by ultraviolet light (UV), the irradiation wavelength is 342nm, and the power is 50W. The irradiation time is 10-20min, the temperature is 25 ℃, and the purification efficiency is calculated by detecting the concentration of organic waste gas in the sealed box at fixed time, wherein the calculation mode is as follows:
purification efficiency (%) = (start-dosing concentration-timing detection concentration)/start-dosing concentration×100%.
The results are shown in Table 1:
table 1 comparison of purification performance of purification absorbents
As can be seen from the data in table 1 above, the purification absorbent obtained in example 1 had higher purification efficiency under the same conditions, i.e., when the mixed gas containing three kinds of exhaust gases of formaldehyde, benzene and trichloroethylene was treated, the purification rate of benzene was 96.3%, the purification rate of trichloroethylene was 94.9%, and the purification rate of formaldehyde was 99.1% in 20 minutes. Comparative example 1 is a conventional three-dimensional carbon nanotube having substantially only adsorption and absorption effects; comparative example 2 is a three-dimensional carbon nanotube after treatment, although the purification rate data is improved, the improvement is not obvious; comparative example 3 has a higher purification rate at 10min but does not reach the level of example 1 at 20min, most probably because the carrier materials are prepared differently, resulting in a decrease in efficiency over time, although having a better purification rate in the early stage; the comparison of the single metals in comparative example 4 and comparative example 5 shows that the purification rate is still different from that in example 1, and the effect alone is not as good as that after mixing and proportioning.
In addition, after the purifying absorbent prepared in the embodiment 1 of the invention is repeatedly used for 5 times, the absorption and purification efficiency of formaldehyde, benzene and trichloroethylene waste gas can still reach more than 90%, which shows that the recycling effect is better.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. A method for treating organic waste gas generated in shoemaking and gluing is characterized by comprising the following steps:
step 1, collecting waste gas in a workshop for shoemaking and gluing in a negative pressure mode, leaching the collected waste gas by alkaline water, and drying to remove water to form pretreated waste gas;
step 2, delivering the pretreated waste gas into a purifying and absorbing box for treatment, wherein a plurality of ultraviolet light sources and purifying and absorbing layers are arranged in the purifying and absorbing box, and discharging the waste gas out of the box after reaching the standard through purifying treatment of the purifying and absorbing layers, thus finishing treatment;
the purification absorbing layer is internally provided with a purification absorbing agent, and the preparation process of the purification absorbing agent comprises the following steps:
(1) Preparing a carrier:
A1. taking three-dimensional carbon nanotube powder, and performing hydro-thermal treatment on ethylenediamine to obtain amino-crosslinked three-dimensional carbon nanotubes;
A2. preparing a sodium pyrophosphate solution by using anhydrous sodium pyrophosphate, and preparing a calcium chloride solution by using anhydrous calcium chloride;
A3. mixing and reacting the amino-crosslinked three-dimensional carbon nanotube, sodium pyrophosphate solution and calcium chloride solution to obtain calcium pyrophosphate/three-dimensional carbon nanotube;
(2) Load carrier:
B1. mixing bismuth salt and yttrium salt in deionized water, simultaneously adding pyridine-2, 6-dicarboxylic acid, and stirring to form a pre-reaction solution;
B2. adding calcium pyrophosphate/three-dimensional carbon nano tubes into the pre-reaction liquid, and carrying out hydrothermal reaction to finally obtain the purifying absorbent.
2. The method for treating organic waste gas generated in shoe-making and gluing according to claim 1, wherein the purity of the three-dimensional carbon nanotube powder is more than 99.9%, the diameter is 20-30nm, and the length is 10-30 μm.
3. The method for treating organic waste gas generated in shoe-making and gluing according to claim 1, wherein the synthesis process of A1 comprises the following steps:
weighing three-dimensional carbon nanotube powder, mixing in deionized water, adding ethylenediamine, ultrasonically forming uniform mixed solution, pouring into a reaction kettle, performing heat preservation at 80-100deg.C for 15-25 hr, collecting solid in the reaction kettle, washing and drying to obtain amino crosslinked three-dimensional carbon Nanotube (NH) 2 -t-CNT）。
4. The method for treating organic waste gas generated in shoe-making and gluing according to claim 3, wherein in the process A1, the mass ratio of the three-dimensional carbon nanotube powder to the ethylenediamine to the deionized water is 1:0.2-0.4:100-200.
5. The method for treating organic waste gas generated in shoe-making and gluing according to claim 1, wherein in the process of A2, the mass ratio of anhydrous sodium pyrophosphate to deionized water is 1:15-25, and the mass ratio of anhydrous calcium chloride to deionized water is 1:20-30.
6. The method for treating organic waste gas generated in shoe-making and gluing according to claim 1, wherein the reaction process of A3 comprises:
mixing amino crosslinked three-dimensional carbon nanotube with sodium pyrophosphate solution at room temperature, forming uniform mixed solution under ultrasonic condition, placing on magnetic stirrer, stirring while gradually adding calcium chloride solution, stirring at room temperature for 12-20 hr, heating to 90-100deg.C until the water solution is evaporated to dryness, collecting the rest solid, dialyzing to remove free ions, and drying to obtain calcium pyrophosphate/three-dimensional carbon nanotube.
7. The method for treating organic waste gas generated in shoe-making and gluing according to claim 1, wherein in the process of A3, the mass ratio of the amino-crosslinked three-dimensional carbon nano tube to the sodium pyrophosphate solution to the calcium chloride solution is 1:32-48:40-50.
8. The method for treating organic waste gas generated in shoe-making and gluing according to claim 1, wherein in the process of B1, bismuth salt is bismuth nitrate pentahydrate, yttrium salt is yttrium nitrate hexahydrate, and the mass ratio of bismuth salt, yttrium salt, pyridine-2, 6-dicarboxylic acid to deionized water is 0.26-0.32:0.39-0.44:0.6:100.
9. The method for treating organic waste gas generated in shoe-making and gluing according to claim 1, wherein the mass ratio of calcium pyrophosphate/three-dimensional carbon nano tube to pre-reaction liquid in the process of B2 is 1:22-40.
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