Nyingzhi spruce cones active carbon and preparation method thereof

Abstract

The invention provides ganoderma lucidum spruce cones activated carbon and a preparation method thereof, and belongs to the technical field of activated carbon preparation. The invention provides a preparation method of activated carbon from Picea yunnanensis cones, which comprises the following steps: pretreating Picea yunnanensis cones to obtain pine cone powder; mixing and dipping the pine nut powder and an activator solution, carrying out solid-liquid separation, and activating the obtained solid to obtain an activated product; the activation is performed at the temperature of 550 DEG C for 1 hour or at the temperature of 600 DEG C for 1.5 hours; carbonizing the activated product to obtain the ganoderma lucidum spruce cones activated carbon; the carbonization temperature is 400 DEG C, and the carbonization time is 1 hour. The Nyingzhi spruce cones are fruits of spruces and are reproductive organs of the spruces, vascular bundles of the cones are developed compared with other organs, and activated carbon prepared from the cones is good in adsorption performance. The result of the embodiment shows that the iodine adsorption value of the prepared activated carbon for the Nyingzhi spruce cones reaches 982.1336 mg / g.

Description

Technical Field

[0001] The present invention belongs to the technical field of activated carbon preparation, and particularly relates to a Picea likiangensis var. linzhiensis cone activated carbon and a preparation method thereof. Background Art

[0002] According to statistics, the total global demand for activated carbon reached 5.4 million tons in 2021, and the global demand for activated carbon is expected to reach 9 million tons in 2029, with a compound growth rate of over 5%. The output of wood-based activated carbon in China is 354,000 tons, accounting for 36% of the total activated carbon output. Therefore, it is of great significance to environmental protection to expand the raw materials for preparing activated carbon other than forest trees.

[0003] The invention patent with the publication number of CN 103449431A discloses a method for preparing activated carbon from leaves, with an iodine adsorption value of 618.82 mg / g and poor adsorption performance. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a Picea likiangensis var. linzhiensis cone activated carbon and a preparation method thereof. The activated carbon prepared by the present invention has good adsorption performance, and the present invention uses fallen Picea likiangensis var. linzhiensis cones as raw materials, which can avoid forest destruction and soil erosion caused by deforestation in large areas.

[0005] In order to achieve the above purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing Picea likiangensis var. linzhiensis cone activated carbon, comprising the following steps:

[0007] Pre-treat the Picea likiangensis var. linzhiensis cones to obtain pine nut powder;

[0008] Mix and impregnate the pine nut powder with an activator solution, perform solid-liquid separation, and activate the obtained solid to obtain an activated product; the activation is carried out at 550 °C for 1 h or at 600 °C for 1.5 h;

[0009] Carbonize the activated product to obtain Picea likiangensis var. linzhiensis cone activated carbon; the carbonization temperature is 400 °C and the time is 1 h.

[0010] Preferably, the particle size of the pine nut powder is below 0.075 mm.

[0011] Preferably, the activator solution includes ZnCl2 solution; the concentration of the ZnCl2 solution is 5 mol / L.

[0012] Preferably, the solid-liquid ratio of the pine nut powder to the activator solution is (0.8 - 1) g: 1 mL.

[0013] Preferably, the time of the mixed impregnation is 24 h.

[0014] Preferably, the activation is carried out in a closed crucible.

[0015] Preferably, the carbonization is carried out in a closed crucible.

[0016] Preferably, the pretreatment comprises: removing surface impurities from the cones of Picea linzhiensis, and then sequentially washing, drying, crushing and sieving.

[0017] Preferably, the drying temperature is 105° C. and the drying time is 2 days.

[0018] The present invention provides Nyingchi spruce cone activated carbon prepared by the preparation method described in the above scheme.

[0019] The invention provides a method for preparing Nyingchi spruce cone activated carbon, comprising the following steps: pre-treating Nyingchi spruce cones to obtain pine cone powder; mixing and impregnating the pine cone powder with an activator solution, separating the solid and the liquid, activating the obtained solid to obtain an activated product; the activation is activated at 550°C for 1 hour, or activated at 600°C for 1.5 hours; carbonizing the activated product to obtain Nyingchi spruce cone activated carbon; the carbonization temperature is 400°C and the time is 1 hour. The Nyingchi spruce cone of the invention is the fruit of spruce, which is the reproductive organ of spruce. Its vascular bundle is more developed than other organs. The vascular bundle contains cellulose and lignin, which is a natural polymer with a three-dimensional network structure formed by connecting phenylpropane units through chemical bonds. The carbon content is as high as about 60%, which is the main component providing residual carbon in the carbonization and activation process of wood resource activated carbon. The activated carbon prepared after activation and carbonization has good adsorption performance. The results of the examples show that the iodine adsorption value of the Nyingchi spruce cone activated carbon prepared by the present invention reaches 982.1336 mg / g.

[0020] The cones of the Linzhi spruce of the present invention are from Tibet, whose forest area ranks fifth in China and whose forest stock volume ranks first in China. The Linzhi spruce is up to 50 meters high, with dark gray bark deeply cracked into irregular thick pieces, flat branches, tower-shaped crown, relatively flat leaflets, 4 to 7 white stomatal lines on each side of the ventral surface, no stomatal lines on each side of the back surface, or 1 to 2 extremely incomplete stomatal lines, ovate rectangular or cylindrical cones, gray-brown seeds, nearly ovate, seed wings obovate elliptical, light brown, flowering period from April to May, and cones mature from September to October. The distribution range of the Linzhi spruce is in the area of 2900 to 3700 meters above sea level, and a large number of cones naturally fall to the ground after maturity (seeds have fallen off). The invention uses fallen cones of Nyingchi spruce as raw materials, which are abundant in source and easy to collect, and can avoid forest destruction and soil erosion caused by felling trees in large areas; at the same time, it can turn waste into treasure, improve its economic added value, promote the development and utilization of Nyingchi spruce forest resources, and increase the income of farmers and herdsmen.

[0021] The preparation method provided by the invention is simple to operate. DETAILED DESCRIPTION

[0022] The present invention provides a method for preparing Nyingchi spruce cone activated carbon, comprising the following steps:

[0023] Pre-treating the cones of Picea linzhiensis to obtain pine cone powder;

[0024] The pine cone powder is mixed and impregnated with an activator solution, the solid and the liquid are separated, and the obtained solid is activated to obtain an activated product; the activation is activated at 550° C. for 1 hour, or at 600° C. for 1.5 hours;

[0025] The activated product is carbonized to obtain Nyingchi spruce cone activated carbon; the carbonization temperature is 400° C. and the time is 1 hour.

[0026] The cones of the Linzhi spruce of the present invention are from Tibet, whose forest area ranks fifth in China and whose forest stock volume ranks first in China. The Linzhi spruce is up to 50 meters high, with dark gray bark deeply cracked into irregular thick pieces, flat branches, tower-shaped crown, relatively flat leaflets, 4 to 7 white stomatal lines on each side of the ventral surface, no stomatal lines on each side of the back surface, or 1 to 2 extremely incomplete stomatal lines, ovate rectangular or cylindrical cones, gray-brown seeds, nearly ovate, seed wings obovate elliptical, light brown, flowering period from April to May, and cones mature from September to October. The distribution range of the Linzhi spruce is in the area of 2900 to 3700 meters above sea level, and a large number of cones naturally fall to the ground after maturity (seeds have fallen off). The invention uses fallen cones of Nyingchi spruce as raw materials, which are abundant in source and easy to collect, and can avoid forest destruction and soil erosion caused by felling trees in large areas; at the same time, it can turn waste into treasure, improve its economic added value, promote the development and utilization of Nyingchi spruce forest resources, and increase the income of farmers and herdsmen.

[0027] The invention pre-treats the cones of Picea linzhiensis to obtain pine cone powder.

[0028] In the present invention, the pretreatment preferably includes removing surface impurities from the cones of Picea linzhiensis, and then washing, drying, crushing and sieving in sequence.

[0029] The present invention has no special requirements for the number of times of the cleaning, as long as the impurities on the surface of the Nyingchi spruce cones can be removed. In the present invention, the drying temperature is preferably 105°C, and the time is preferably 2 days. In the present invention, the drying is preferably carried out in an oven. In the present invention, the screening is preferably through a 200 mesh sieve. In the present invention, the particle size of the pine cone powder is preferably less than 0.075 mm.

[0030] After the sieving is completed, the pine cone powder is preferably dried to a constant weight and stored in a dryer for later use. The drying of the present invention is preferably carried out in an oven.

[0031] After obtaining the pine pollen powder, the present invention mixes and impregnates the pine pollen powder with an activator solution, separates the solid from the liquid, and activates the obtained solid to obtain an activated product.

[0032] In the present invention, the activator solution preferably includes a ZnCl2 solution; the concentration of the ZnCl2 solution is preferably 5 mol / L. In the present invention, the solid-liquid ratio of the pine pollen powder to the activator solution is preferably (0.8 - 1) g: 1 mL, and more preferably (0.85 - 0.95) g: 1 mL.

[0033] In the present invention, the time of the mixing and impregnation is preferably 24 h, and the temperature is preferably room temperature. The mixing and impregnation in the present invention is preferably carried out in a crucible.

[0034] The present invention has no special requirements for the solid-liquid separation, and the well-known solid-liquid separation methods in the art can be used, such as filtration.

[0035] In the present invention, the activation is carried out at 550 °C for 1 h or at 600 °C for 1.5 h. The activation in the present invention is preferably carried out in a muffle furnace; the activation is preferably carried out in a sealed crucible. In the present invention, the activator solution has the function of eroding and dissolving the cellulose in the pine pollen powder, and can decompose and separate the hydrogen and oxygen contained in the hydrocarbons in the pine pollen powder, and escape in the form of small molecules such as H2O and CH4, thereby generating a large number of pores and forming a porous structure.

[0036] After completing the activation, the present invention preferably cools the obtained product to room temperature, and then sequentially carries out acid leaching and washing on the cooled product.

[0037] In the present invention, the solution for acid leaching preferably includes a hydrochloric acid solution; the time of acid leaching is preferably 30 min. In the present invention, the concentration of the hydrochloric acid solution is preferably 0.1 mol / L. In the present invention, the washing and filtration are carried out simultaneously, the washing is preferably carried out with distilled water, and the washing is preferably carried out until the filtrate is neutral. The present invention can remove the impurities and their surface oxides in the cooled product through acid leaching, and improve the adsorption capacity of the cones of Picea likiangensis var. linzhiensis.

[0038] After obtaining the activated product, the present invention carbonizes the activated product to obtain activated carbon from the cones of Picea likiangensis var. linzhiensis.

[0039] In the present invention, the carbonization preferably includes putting the activated product into a crucible, then covering the crucible lid tightly, and putting it into a muffle furnace for carbonization.

[0040] In the present invention, the carbonization temperature is 400°C and the time is 1 hour. The carbonization of the present invention is preferably carried out in a closed crucible. The present invention can remove volatile matter and moisture in the carbon material through carbonization, and can achieve complete carbonization after activation and carbonization.

[0041] After the carbonization is completed, the present invention preferably cools the obtained activated carbon to room temperature.

[0042] The present invention provides Nyingchi spruce cone activated carbon prepared by the preparation method described in the above scheme.

[0043] The cones of the Linzhi spruce of the present invention are the fruits of spruce, which are the reproductive organs of spruce. The vascular bundles of the cones are more developed than other organs, so the activated carbon prepared from the cones has good adsorption performance. The results of the embodiment show that the iodine adsorption value of the activated carbon prepared from the cones of the Linzhi spruce of the present invention reaches 982.1336 mg / g.

[0044] In order to further illustrate the present invention, the Nyingchi spruce cone activated carbon and the preparation method thereof provided by the present invention are described in detail below in combination with examples, but they should not be construed as limiting the protection scope of the present invention.

[0045] Example 1

[0046] Collecting Linzhi spruce cones and performing pretreatment; the pretreatment comprises: removing surface impurities from the Linzhi spruce cones, cleaning them, drying them in an oven at 105° C. for two days, crushing them after drying, passing them through a 200-mesh sieve to obtain pine cone powder, and then drying the pine cone powder in an oven at 80° C. to constant weight, and storing them in a desiccator for later use;

[0047] The pine cone powder is placed in a crucible, a 5 mol / L ZnCl2 solution is taken as an activator solution, the pine cone powder and the activator solution are mixed at a solid-liquid ratio of 1 g: 1 mL, and the mixture is immersed at room temperature for 24 hours. After filtration, the obtained solid is placed in a crucible, the crucible is sealed with a crucible cover, and the crucible is placed in a muffle furnace for activation. The activation temperature is 600° C., the activation time is 1.5 hours, and then the mixture is cooled to room temperature. After the activation is completed, the obtained product is sequentially soaked in 0.1 mol / L hydrochloric acid for 30 minutes, and then repeatedly washed with distilled water until the filtrate is neutral to obtain an activated product.

[0048] The activated product is placed in a crucible, the crucible is sealed with a lid, and the crucible is placed in a muffle furnace for carbonization. The carbonization temperature is 400° C., the carbonization time is 1 hour, and the heating is stopped and the mixture is cooled to room temperature to obtain activated carbon.

[0049] Comparative Examples 1 to 3

[0050] The preparation steps are the same as those in Example 1, except that the carbonization temperature and carbonization time are as follows: the carbonization temperature is 400 °C and the carbonization time is 2 h; the carbonization temperature is 350 °C and the carbonization time is 1 h; the carbonization temperature is 350 °C and the carbonization time is 2 h.

[0051] Example 2

[0052] The preparation steps are the same as those in Example 1, except that the activation temperature is 550 °C and the activation time is 1 h.

[0053] Comparative Examples 4 - 8

[0054] The preparation steps are the same as those in Example 1, except that the activation temperature and activation time are as follows: the activation temperature is 600 °C and the activation time is 1 h; the activation temperature is 600 °C and the activation time is 2 h; the activation temperature is 550 °C and the activation time is 2 h; the activation temperature is 500 °C and the activation time is 1 h; the activation temperature is 500 °C and the activation time is 2 h.

[0055] Example 3

[0056] The preparation steps are the same as those in Example 1, except that the pine pollen powder and the activator solution are mixed at a solid - liquid ratio of 4 g:5 mL.

[0057] Comparative Examples 9 - 11

[0058] The preparation steps are the same as those in Example 1, except that the solid - liquid ratios of the pine pollen powder and the activator solution are as follows: 2 g:1 mL; 2 g:3 mL; 4 g:3 mL.

[0059] Comparative Examples 12 - 13

[0060] The preparation steps are the same as those in Example 1, except that the concentrations of the activator solution ZnCl₂ solution are 3 mol / L and 1 mol / L in sequence.

[0061] Performance Test

[0062] Determination of iodine adsorption value: According to the method for determining iodine adsorption value (Test methods for wood - based activated carbon - Determination of iodine adsorption value, GB / T 12496.8 - 2015, National Standard of the People's Republic of China), the iodine adsorption value of the activated carbon is determined. The larger the iodine adsorption value, the stronger the adsorption capacity. The measured values of Example 1 and Comparative Examples 1 - 3 are shown in Table 1, the measured values of Example 2 and Comparative Examples 4 - 8 are shown in Table 2, the measured values of Example 3 and Comparative Examples 9 - 11 are shown in Table 3, and the measured values of Comparative Examples 12 - 13 are shown in Table 4. Among them, the filtrate concentration refers to the remaining filtrate concentration after calibration; the correction factor can be obtained by looking up the table according to the remaining filtrate concentration, and the national standard is attached with a correction factor table; the iodine amount refers to the amount of iodine adsorbed per gram of activated carbon.

[0063] Table 1 Carbonization Conditions and Iodine Adsorption Values of Example 1 and Comparative Examples 1-3

[0064]

[0065] As can be seen from Table 1, reducing the carbonization temperature or prolonging the carbonization time, or prolonging the carbonization time while reducing the carbonization temperature will all reduce the adsorption capacity of the activated carbon. When the carbonization temperature is 400 °C and the carbonization time is 1 h, the obtained activated carbon has the best adsorption performance.

[0066] Table 2 Activation Conditions and Iodine Adsorption Values of Example 2 and Comparative Examples 4-8

[0067]

[0068] As can be seen from the results of Table 2 and Example 1, there is no fixed rule between the activation temperature and time and the adsorption performance of the final activated carbon. When activating at 550 °C for 1 h or at 600 °C for 1.5 h, the obtained activated carbon has significantly higher adsorption performance than that obtained under other activation conditions.

[0069] Table 3 Solid-Liquid Ratio of Pine Nut Powder to Activator Solution and Iodine Adsorption Value of Activated Carbon in Example 3 and Comparative Examples 9-11

[0070]

[0071] As can be seen from Table 3 and Example 1, when only changing the solid-liquid ratio of pine nut powder to activator solution, the iodine adsorption value first increases and then decreases with the increase of the solid-liquid ratio value. When the solid-liquid ratio is 1 g:1 mL, the activated carbon has the highest iodine adsorption value and the best adsorption performance.

[0072] Table 4 Concentration of Activator Solution and Iodine Adsorption Value of Comparative Examples 12-13

[0073]

[0074] As can be seen from Table 4 and Example 1, when reducing the concentration of the zinc chloride solution, the adsorption performance of the obtained activated carbon decreases. When the concentration of the ZnCl2 solution is 5 mol / L, the activated carbon has the best adsorption performance.

[0075] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, not all embodiments. People can also obtain other embodiments according to these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing Nyingchi spruce cone activated carbon, comprising the following steps: Pre-treating the cones of Picea linzhiensis to obtain pine cone powder; The pine cone powder is mixed and impregnated with an activator solution, the solid and the liquid are separated, and the obtained solid is activated to obtain an activated product; The activation is performed at 550° C. for 1 h, or at 600° C. for 1.5 h; The activated product is carbonized to obtain Nyingchi spruce cone activated carbon; the carbonization temperature is 400° C. and the time is 1 hour.

2. The preparation method according to claim 1, characterized in that, The particle size of the pine cone powder is less than 0.075 mm.

3. The preparation method according to claim 1, wherein, The activator solution includes a ZnCl2 solution; the concentration of the ZnCl2 solution is 5 mol / L.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The solid-to-liquid ratio of the pine cone powder to the activator solution is (0.8-1) g:1 mL.

5. The preparation method according to any one of claims 1 to 3, characterized in that, The mixed impregnation time is 24 hours.

6. The preparation method according to claim 1, wherein The activation is carried out in a closed crucible.

7. The preparation method according to claim 1, wherein The carbonization is carried out in a closed crucible.

8. The preparation method according to claim 1 or 2, characterized in that, The pretreatment comprises: removing surface impurities from the cones of Nyingchi spruce, and then washing, drying, crushing and screening in sequence.

9. The preparation method according to claim 8, characterized in that, The drying temperature is 105° C. and the drying time is 2 days.

10. The Nyingchi spruce cone activated carbon prepared by the preparation method according to any one of claims 1 to 9.

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