CN106006638A - Preparation method of high-penetration microporous granular active carbon - Google Patents

Abstract

The invention relates to a preparation method of highly penetrating microporous granular activated carbon, which belongs to the technical field of waste recycling or reprocessing. After the waste wool fiber is treated in sulfuric acid solution, it is acid-rolled and baked for carbonization, impurities are removed, then neutralized, non-ionic detergent is added to remove fat and sweat, and finally washed and dried to obtain a clean wool fiber. Activated carbon fibers are obtained by pre-carbonization and activation. Applying the invention to the recovery and reuse of non-spinnable wool fibers or waste wool fiber materials to prepare activated carbon has the advantages of high specific surface area, high compatibility during use, good adsorption capacity, and uniform void volume distribution.

Description

A kind of preparation method of highly penetrating microporous granular activated carbon

technical field

The invention relates to a preparation method of highly penetrating microporous granular activated carbon, which belongs to the technical field of waste recycling or reprocessing.

Background technique

The amount of waste fiber resources is huge, and improper disposal will not only cause environmental pollution, but also increase processing costs and waste resources. Using appropriate methods to reprocess waste textile fibers not only meets the requirements of relevant laws and regulations in our country, but also has the rationality of waste utilization and resource recovery. Waste wool fibers include non-spinnable wool fibers (such as pig hair, human hair, chicken hair, wool or rabbit fur scraps, camel hair, alpaca wool, cashmere needle hair, etc.) , back wool, selvage, waste wool yarn scraps, old wool clothing, old sweaters, etc.). According to the latest data released at the 82nd Annual Conference of the International Wool Textile Organization, the global wool production in 2013/2014 is expected to be 1.1 million tons of net wool, which also reflects the huge amount of waste wool fiber resources. Therefore, how to properly dispose or reuse waste wool fiber resources is an important issue currently facing.

Regarding the utilization of waste wool fiber resources, there are mainly two utilization directions: one is to adopt the method of opening, cleaning, screening, direct utilization or textile processing to form usable textiles, such as Chinese patent CN102167418B discloses the utilization of The adsorption reactor with waste wool fiber as filler removes ethinyl estradiol pollutants in sewage; the second is cleaning and dissolving to form keratin liquid purification and utilization or regeneration spinning and textile processing to form textiles or crush and carbonize to make adsorption substances The chemical and physical method, such as Chinese patent CN 102161485 B, uses waste wool to prepare tubular activated carbon, but the disadvantages of this patent are that the tubular structure is easy to burst into pieces, and the penetrability of activated micropores on the outer wall is poor, resulting in a small specific surface area of activated carbon. The adsorption capacity is poor; in addition, this patent only uses water to wash the waste wool, which cannot remove the fat and impurities in the wool, which is not conducive to the generation of activated micropores, thereby affecting the improvement of the specific surface area of the activated carbon. Cashmere needle hair is produced in the depilation process of goats. It has a wide range of diameter distribution and uneven thickness distribution. The thicker fibers can reach 170 μm, and the fiber cross-section has both solid and porous structures. It is a typical waste wool fiber. Representatives, there are few reports on the application of this waste material.

Based on this, this application is made.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preparing highly penetrating microporous granular activated carbon by using cashmere needle hair fiber, which can obtain high penetrating microporous granular activated carbon while reducing the environmental pressure on waste treatment, and turn waste into Treasure, in line with the principle of maximizing the utilization of resources.

The present invention adopts following technical route:

A kind of method utilizing cashmere needle wool fiber to prepare highly penetrating microporous activated carbon, comprises the steps:

Step 1. The pretreatment stage of cashmere needle wool fiber, that is, the waste wool fiber is treated in 2.5%-5.0% sulfuric acid solution, and after acid rolling, it is baked and carbonized at 100°C-115°C, and then the vegetable is removed by a charcoal crusher. Weeds, then neutralized, adding non-ionic detergent to remove the grease and sweat of waste wool fibers, and finally washing with hot water at 35-55°C and drying to obtain clean cashmere needle wool fibers;

Step 2, the pre-carbonization stage of cashmere needle hair fibers, that is, use a calender to cut the clean cashmere needle hair fibers into 5mm-15mm short hairs, place them in a quartz tubular muffle furnace under nitrogen protection, and heat up to Between 200°C and 255°C, pre-carbonize for 30 minutes to 90 minutes, take it out after cooling to room temperature, and obtain pre-carbonized products with different structures;

Step 3, the carbonization-activation stage of the pre-carbonized product, that is, the pre-carbonized product and the activator are mixed in a certain proportion according to the mass ratio, placed in a quartz tubular muffle furnace under the protection of nitrogen, and after 30 minutes of nitrogen gas, the temperature is raised to 500°C-900°C ℃, then keep warm for 60 to 150 minutes, cool to room temperature, take out, wash with 80 ℃ hot water until the pH value of the cleaning solution is between 5.8 and 7.5, filter and dry to obtain activated carbon made of cashmere needle wool fiber.

Wherein, the cashmere needle wool fiber in the step 1 is a typical representative of waste wool fiber, and other non-spinnable wool fibers (such as pig hair, human hair, chicken hair, wool or rabbit hair leftovers, camel hair, alpaca hair, etc. ) and waste wool fiber materials (such as wool back silk, wool back, selvage, waste wool yarn scraps, old woolen clothing, old sweaters, etc.) in the textile mill to replace cashmere needle wool fibers for the preparation of penetrating microporous granular activated carbon; cashmere The pretreatment process of the guard hair fiber pretreatment stage is: grass-containing waste wool fiber→soaking, acid rolling→baking→decarbonization→neutralization→degreasing→drying→discarding and cleaning wool; non-ionic detergent refers to Lissapol TN 450, one of Teric N10, Antarox C0630 and FK-9502 non-ionic detergents; the process control of the degreasing washing process is: the concentration is between 0.5% and 2%, the liquor ratio is 1:15-55, and the temperature is 45°C- 60°C, washing times 2 times, washing time distribution is 10min, 5min;

The heating rate in the step 2 is 5-15°C/min;

The mixing mass ratio of the pre-carbonized product and the activator in the step 3 should be less than 2; the heating rate is 5-15°C/min; the activator refers to K ₂ CO ₃ , Na ₂ CO ₃ , Li ₂ CO ₃ , H ₃ One of PO ₄ , KOH, NaOH, KOH- K ₂ CO ₃ , NaOH- Na ₂ CO ₃ .

The beneficial effects of the present invention are:

The present invention utilizes the pretreatment process to remove the fat and moisture on the surface of the waste wool fiber well, which is beneficial to the formation of the microporous structure in the pre-carbonization and carbonization-activation process; moreover, by controlling the pre-carbonization and carbonization-activation process, the waste Wool fiber granular activated carbon has a highly penetrating, activated micropore, and stable network structure, which greatly increases the specific surface area of activated carbon and enhances the adsorption capacity. It will be used as an efficient adsorbent in the treatment of heavy metals, organic dyes, and harmful chemicals. Purification of harmful gases such as , water and formaldehyde, etc. On the one hand, it reduces the environmental pollution caused by the treatment of waste wool fibers, and reduces the cost of waste wool treatment. At the same time, it turns waste resources into treasures and enriches the treatment and utilization of waste resources. way.

This application controls the process of pre-carbonization, pre-carbonization-activation, and uses cashmere needle hair fiber as raw material to prepare highly penetrating microporous granular activated carbon, and can also prepare high penetrating microporous granular activated carbon from cashmere needle hair. The process is applied to the treatment and application of other waste wool fibers, which will help reduce the pressure on the environment for waste disposal, and provide more effective ways for the rational use of waste wool fibers, thereby increasing the added value of product utilization.

Description of drawings

Fig. 1 is a schematic diagram of the processing flow of the present invention;

Fig. 2 is a schematic diagram of the state before the pretreatment of discarded cashmere needle hair in the present application;

Fig. 3 is the state schematic diagram after the pretreatment of discarded cashmere needle hair in the present application;

Fig. 4 is the scanning electron micrograph of discarded cashmere needle hair granular activated carbon after carbonization-activation under the first implementation state of the present application;

Fig. 5 is a partially enlarged view of part A in Fig. 4;

Fig. 6 is a scanning electron micrograph of activated carbon of discarded cashmere needle hair particles after carbonization-activation in the second implementation state of the present application;

Fig. 7 is a partially enlarged view of part B in Fig. 6;

Fig. 8 is a scanning electron micrograph of activated carbon of discarded cashmere needle hair particles after carbonization-activation in the third implementation state of the present application;

FIG. 9 is a partially enlarged view of part C in FIG. 8 .

detailed description

Taking cashmere needle hair in waste wool fiber materials as an example, the present invention is further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

The treatment process of this embodiment can be referred to as shown in Figure 1. The waste cashmere needle hair fiber is placed in a 3.0% sulfuric acid solution for sulfuric acid treatment. After acid rolling, it is baked and carbonized at 110°C, and then the plant weeds are removed by a charcoal crusher. Then neutralize, add Teric N10 non-ionic detergent (concentration 1.5%, bath ratio 1:35, temperature 50°C, wash twice, the time distribution of the two washes is 10min, 5min) to remove the grease and sweat of cashmere needle wool fibers, and finally Wash with hot water at 40°C and dry to obtain clean cashmere needle wool fibers. Comparing Figure 2 and Figure 3, it can be seen that the fiber wool after purification treatment is bright and tidy, and has high gloss; The guard hair fiber is cut into short hairs of 15 mm, placed in a quartz tubular muffle furnace under the protection of nitrogen, and then heated to 255°C at 15°C/min for 30 minutes, pre-carbonized for 30 minutes, cooled to room temperature, and then taken out to obtain Pre-carbonized product; then mix the pre-carbonized product with Na ₂ CO ₃ activator at a certain ratio of 1:1 according to the mass ratio, and place it in a quartz tubular muffle furnace under the protection of nitrogen gas. Raise the temperature to 500°C, keep it warm for 100 minutes, cool to room temperature, take it out, wash with 80°C hot water until the pH of the cleaning solution is about 6.8, filter and dry to obtain activated carbon made of cashmere needle wool fiber.

Figure 4 and Figure 5 are scanning electron microscope images of cashmere needle hair granular activated carbon prepared by the method described in this example under different magnifications, and it can be observed that some cashmere needle hair granular activated carbon with active micropores, but the activation effect is not sufficient , and the activated pores are smaller. According to the measurement, its BET specific surface area is 370.04m ² ·g ^-1 , and the average pore volume is 0.138cm ³ ·g ^-1 .

Example 2

The treatment process of this embodiment can be referred to as shown in Figure 1. The waste cashmere needle hair fiber is placed in 3.5% sulfuric acid solution for sulfuric acid treatment, and after acid rolling, it is baked and carbonized at 105°C, and then the plant weeds are removed by a charcoal crusher. Then neutralize, add Lissapol TN 450 non-ionic detergent (concentration 1%, bath ratio 1:50, temperature 55°C, wash twice, the time distribution of the two washes is 10min, 5min) to remove the grease and sweat of cashmere needle wool fiber, Finally, wash it with hot water at 40°C and dry it to obtain clean cashmere needle wool fiber. Comparing Figure 2 and Figure 3, it can be seen that the fiber wool color after purification treatment is bright and tidy, and has high gloss; Cashmere needle hair fibers are cut into short hairs of 10 mm, placed in a quartz tubular muffle furnace under the protection of nitrogen, and then heated to 250°C at 5°C/min for 30 minutes, pre-carbonized for 60 minutes, cooled to room temperature, and then taken out Obtain the pre-carbonized product; then mix the pre-carbonized product with the K ₂ CO ₃ activator at a mass ratio of 4:2, place it in a quartz tubular muffle furnace under the protection of nitrogen, and raise the temperature at 5°C/min after blowing nitrogen for 30 minutes To 500°C, keep warm for 150 minutes, cool to room temperature, take out, wash with 80°C hot water until the pH of the cleaning solution is about 6.2, filter and dry to obtain activated carbon made of cashmere needle wool fiber.

Fig. 6 and Fig. 7 are the scanning electron micrographs of cashmere needle hair granular activated carbon prepared by the method described in this example under different magnifications. It can be observed that granular activated carbon with a large number of activated micropores is formed inside, and the carbonized exterior is completed. The scale structure layer and other skin layers are wrapped, which affects the adsorption effect of activated carbon to a certain extent, but the activated microporous structure begins to appear in some parts of the outer wrapping layer. According to the measurement, its BET specific surface area is 526.54m ² ·g ^-1 , and the average pore volume is 0. 201cm ³ ·g ^-1 .

Example 3

The treatment process of this embodiment can be referred to as shown in Figure 1. The waste cashmere needle hair fiber is placed in 3.5% sulfuric acid solution for sulfuric acid treatment, and after acid rolling, it is baked and carbonized at 105°C, and then the plant weeds are removed by a charcoal crusher. Then neutralize, add Lissapol TN 450 non-ionic detergent (concentration 1%, bath ratio 1:50, temperature 55°C, wash twice, the time distribution of the two washes is 10min, 5min) to remove the grease and sweat of cashmere needle wool fiber, Finally, wash it with hot water at 40°C and dry it to obtain the waste net wool fiber. Comparing Figure 2 and Figure 3, it can be seen that the fiber wool color after purification treatment is bright and tidy, and has a high gloss; The guard hair fiber is cut into short hairs of 5 mm, placed in a quartz tubular muffle furnace under the protection of nitrogen, and after 30 minutes of blowing nitrogen, the temperature is raised to 240°C at 10°C/min, pre-carbonized for 60 minutes, cooled to room temperature, and then taken out to obtain Pre-carbonized product; then mix the pre-carbonized product with Na ₂ CO ₃ -NaOH composite activator at a mass ratio of 4:2, place it in a quartz tubular muffle furnace under the protection of nitrogen, and pass nitrogen for 30 minutes, then set the temperature at 5°C/ The temperature was raised to 600°C for 1 minute, and then kept for 120 minutes, cooled to room temperature, taken out, washed with 80°C hot water until the pH value of the cleaning solution was about 6.0, filtered and dried to obtain activated carbon made of cashmere needle wool fiber.

Fig. 8 and Fig. 9 are the scanning electron micrographs of cashmere needle hair granular activated carbon prepared by the method described in this embodiment under different magnifications. It can be observed that a large amount of granular activated carbon with activated micropores is formed, and the activated carbon of large particles is decomposed into relatively large particles. There are many granular activated carbons with small particle sizes, and the skin layers such as the wool scale layer have obtained more activated microporous structures after carbonization, which helps to increase the specific surface area of activated carbon. According to the measurement, its BET specific surface area is 736.9m ² ·g ^-1 , and the average pore volume is 0. 291cm ³ ·g ^-1 .

As can be seen from the above preparation process, the preparation effect is the best in the state of Example 3. The activated carbon prepared under this scheme has a high specific surface area, high compatibility during use, good adsorption capacity, and uniform void volume distribution.

The above content is a further detailed description of the technical solutions provided in conjunction with the preferred embodiments of the present invention. It cannot be determined that the specific implementation of the present invention is only limited to the above descriptions. For those of ordinary skill in the technical field of the present invention, On the premise of not departing from the inventive concept of the present invention, some simple deduction or replacement can also be made, which should be regarded as belonging to the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of highly penetrating microporous granular activated carbon is characterized in that, with waste wool fiber as raw material, carries out the processing of following steps: (1) Purification pretreatment: After the waste wool fibers are treated in sulfuric acid solution, acid-rolled and baked for carbonization, impurities are removed, then neutralized, non-ionic detergent is added to remove fat and sweat, and finally washed with water at 35-55°C. Then dry to obtain the net wool fiber; (2) Pre-carbonization: Cut the clean wool fiber into pieces, raise the temperature to 200°C-255°C under the protection of nitrogen, perform pre-carbonization treatment for 30-90min, and cool to room temperature to obtain the pre-carbonized product; (3) Activation: Mix the pre-carbonized product and activator in proportion, raise the temperature to 500°C-900°C under the protection of nitrogen, keep it warm for 60-150min, cool to room temperature, wash until the pH value of the cleaning solution is 5.8-7.5, filter and dry dry to get the finished activated carbon. 2. A method for preparing highly penetrating microporous granular activated carbon according to claim 1, characterized in that: in step (1), the concentration of the sulfuric acid solution is 2.5-5.0%; the baking carbonization temperature is 100- 115°C. 3. A method for preparing highly penetrating microporous granular activated carbon as claimed in claim 1, characterized in that, in step (1), the non-ionic detergent is Lissapol TN 450, Teric N10 and Antarox C0630. 4. the preparation method of a kind of highly penetrating microporous granular activated carbon as claimed in claim 1, is characterized in that, described degreasing washing process technology control is as follows: the concentration of nonionic detergent is 0.5-2%, bath Ratio 1:10-30, temperature 45°C-55°C. 5. The preparation method of a kind of highly penetrating microporous granular activated carbon as claimed in any one of claims 1-4, characterized in that: washing is carried out at least twice in the described degreasing washing process, and the washing time distribution is 10min , 5min. 6. The method for preparing highly penetrating microporous granular activated carbon according to claim 1, characterized in that: in step (2), the heating rate is 5-15°C/min. 7. A method for preparing highly penetrating microporous granular activated carbon according to claim 1, characterized in that: in step (3), the activator is KOH, NaOH, K2CO3, Na2CO3, Li ₂ CO ₃ , H ₃ PO4 , KOH-K2CO3, NaOH-Na2CO3. 8. The method for preparing highly penetrating microporous granular activated carbon according to claim 1, characterized in that: in step (3), the heating rate is 5-15°C/min. 9. A method for preparing highly penetrating microporous granular activated carbon according to claim 1, 7 or 8, characterized in that: in step (3), the mixing mass ratio of the pre-carbonized product to the activator is less than 2. 10 . The method for preparing highly penetrating microporous granular activated carbon according to claim 1 , wherein the waste wool fibers are cashmere needle wool fibers, non-spinnable wool fibers or waste wool fiber materials. 11 .