A method for improving snow lotus residue biochar, product and application

Abstract

The present invention discloses a method for improving saussurea sibiricum residue biochar, a product and an application thereof, and belongs to the field of biomass waste resource utilization. The specific improvement method comprises the following steps: adding saussurea sibiricum residue powder into an alkaline solution for immersion, then heating and pyrolyzing in the presence of an inert gas, and obtaining modified biochar after cooling. The present invention also discloses the modified biochar prepared by the above method, and discloses the application of the modified biochar in an adsorbent and in the adsorption of methyl orange and methyl red. The modification method provided by the present invention can improve the biochar yield, increase the microporous structure on the surface of the biochar and increase the density, promote the aromatization of the internal structure and the formation of oxygen-containing functional groups, and can be used for the adsorption of methyl red and methyl orange. It has high application value and development prospects, and provides a new use for the sustainable utilization of saussurea sibiricum resources.

Description

Technical Field

[0001] The present invention relates to the field of biomass waste resource utilization, and in particular to a method for improving saussurea ovata residue biochar, a product and an application thereof. Background Art

[0002] Biochar is a carbon-rich solid material formed by thermochemical conversion of biomass under anoxic or anaerobic conditions. Its large surface area and porous structure make it ideal for adsorbing organic pollutants and heavy metals from the environment, resulting in superior adsorption capacity compared to other adsorbents. Snow lotus (Saussurea DC) is a plant of the genus Saussurea in the Asteraceae family. The ancient Chinese medical text "Compendium of Materia Medica" (Supplementary Notes) states that snow lotus has a strong heat property, can replenish essence and yang, and dispel wind and dampness, making it a precious Chinese medicinal herb. Modern research indicates that it contains active substances such as flavonoids and lignans. Products made from snow lotus are also used in various fields, including medical treatment, beauty, and health supplements. Traditional Chinese medicine residues produced by traditional Chinese medicine companies are also part of the TCM resource. To ensure the sustainable utilization of this scarce resource, TCM residues can also be used in various industries, including medicine, agriculture, industry, and animal husbandry. However, methods for preparing biochar from snow lotus residues have not been reported.

[0003] Aromatic amine compounds released by azo dyes, such as 4-aminobiphenyl and 4-chloro-2-methylaniline, pose carcinogenic and mutagenic risks. The printing and textile industries still have shortcomings in the disposal of waste dyes, with approximately 15% of these dyes being discharged into the aquatic environment, causing pollution.

[0004] Therefore, how to provide a biochar prepared using Saussurea involucrata residue to treat azo dyes is a technical problem that needs to be solved urgently by those skilled in the art. Summary of the Invention

[0005] The purpose of the present invention is to provide a method, product and application of improving biochar from snow lotus residues to solve the problems existing in the above-mentioned prior art.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] A method for improving biochar from snow lotus residues comprises the following steps:

[0008] The powder of Saussurea involucrata residue is added into an alkaline solution for immersion, then heated and pyrolyzed in the presence of an inert gas, and the modified biochar is obtained after cooling.

[0009] Beneficial effects: The modifier can promote the biochar to produce specific adsorption capacity and high chemical affinity. The present invention uses the raw materials modified by alkali to perform pyrolysis at elevated temperature, which can not only increase the specific surface area of ​​the biochar, but also introduce oxidizing groups and increase the adsorption volume, making it more efficient and economical than the original carbon.

[0010] Preferably, the alkaline solution is a Na2CO3 solution with a mass concentration of 10%.

[0011] Beneficial effects: The sodium carbonate aqueous solution used in the present invention has stronger alkalinity and lower cost.

[0012] Preferably, the powder particle size of the snow lotus residue is 150-200 mesh;

[0013] The snow lotus medicinal residue is waste material of snow lotus Chinese medicinal materials or medicinal residue produced during the preparation of Chinese patent medicines mainly based on snow lotus;

[0014] The Chinese patent medicine comprises one of snow lotus oral liquid, snow lotus injection and snow lotus tablets;

[0015] The ratio of the added amount of the snow lotus medicinal residue powder to the alkaline solution is 1:8.

[0016] Beneficial effects: The method provided by the present invention can be used to reuse various residual medicinal residues whose main medicine is snow lotus on the market, and can provide a new application model for the medicinal residues of various Chinese patent medicines with snow lotus as the main medicine, such as snow lotus oral liquid, snow lotus injection, and snow lotus tablets.

[0017] Preferably, the immersion temperature is room temperature and the immersion time is 24 hours.

[0018] Beneficial effect: The present invention can achieve the desired effect by immersing at room temperature, and has the advantage of energy saving.

[0019] Preferably, the inert gas is nitrogen.

[0020] Beneficial effects: The nitrogen in the present invention can discharge oxygen and prevent oxygen from entering during the calcination process, thereby preventing oxidation of the tubular electric heating element, increasing the service life of the tubular resistance furnace, and also acting as a heat conduction medium.

[0021] Preferably, the temperature-raising pyrolysis process comprises the following steps:

[0022] The infused snow lotus residue powder is heated to 200-600° C. and pyrolyzed for 2 h.

[0023] Beneficial effect: The adsorption effects of the alkali-modified biochars at five temperatures of 200-600°C obtained in the present invention were compared with those of the biochars of Comparative Examples 1-5.

[0024] Preferably, the heating rate is 5°C / min.

[0025] Beneficial effects: The present invention can achieve temperature requirements efficiently and quickly in accordance with the operating procedures of the tube furnace and the principle of energy saving and consumption reduction.

[0026] The invention relates to modified biochar prepared by a method for improving biochar from saussurea ovata residue.

[0027] Beneficial effects: The preparation method of the present invention can greatly improve the adsorption efficiency of biochar and the utilization rate of Saussurea dasyphylla residue.

[0028] The invention discloses an application of modified biochar in the field of adsorbent.

[0029] Beneficial effects: The modified biochar in the present invention can achieve efficient adsorption of two types of organic pollutants, methyl orange and methyl red.

[0030] Application of modified biochar in the adsorption of methyl red and methyl orange.

[0031] Beneficial effects: The present invention tests the adsorption capacity and adsorption rate of the modified biochar obtained, and the results show that the prepared modified biochar has a good adsorption capacity for methyl red and methyl orange.

[0032] The present invention discloses a method, product, and application for improving biochar from saussurea ovata residue. The modification method provided herein can increase biochar yield, increase the number of microporous structures on the biochar surface and its density, and promote internal aromatization and the formation of oxygen-containing functional groups. Adsorption experiments show that the char prepared and modified under high-temperature conditions has significant adsorption advantages and can be used for the adsorption of methyl red and methyl orange. This method has high application value and development prospects, providing a new use for the sustainable utilization of saussurea ovata resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0034] Figure 1 The scanning electron micrographs of modified and unmodified medicinal residue carbons obtained at different pyrolysis temperatures in Example 1 of the present invention and Comparative Example 1 are shown;

[0035] Wherein, a is snow lotus residue powder, b is the unmodified biochar obtained in Comparative Example 1, c is the unmodified biochar obtained in Comparative Example 2, d is the unmodified biochar obtained in Comparative Example 3, e is the unmodified biochar obtained in Comparative Example 4, f is the unmodified biochar obtained in Comparative Example 5, g is the modified biochar obtained in Example 1, h is the modified biochar obtained in Example 2, i is the modified biochar obtained in Example 3, j is the modified biochar obtained in Example 4, and k is the modified biochar obtained in Example 5;

[0036] Figure 2 Fourier transform infrared spectra of two kinds of medicinal residue biochars prepared at different pyrolysis temperatures in Examples 1-5 of the present invention and Comparative Examples 1-5;

[0037] Wherein, a is the preparation of unmodified biochar from medicinal residue (SR) and comparative examples 1-5, and b is the preparation of modified biochar from examples 1-5;

[0038] Figure 3 This is the standard curve of methyl red solution;

[0039] Figure 4 This is the standard curve of methyl orange solution. DETAILED DESCRIPTION

[0040] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0041] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0042] Unless otherwise specified, all reagents involved in the embodiments of the present invention are commercially available products and can be purchased through commercial channels.

[0043] Materials and reagents used in the experiment: Snow lotus residue (Xinjiang Tianshanlian Pharmaceutical Co., Ltd., China);

[0044] Methyl orange (M812775, Shanghai MacLean Biochemical Technology Co., Ltd., China);

[0045] methyl red (M8270, Beijing Solebow Technology Co., Ltd., China);

[0046] XS-105 analytical balance, from Mehler Toledo, Switzerland;

[0047] Swinging Chinese medicine grinder (model: AK-1000A, Wenling Aoli Chinese Medicine Machinery Co., Ltd., China;

[0048] Eclipse Ni-U Nikon biological upright fluorescence microscope (Nikon Corporation, Japan);

[0049] Vacuum drying oven (DZF-6051, Yongguangming Medical Instrument Co., Ltd., Beijing, China);

[0050] vacuum tube furnace (OTF-1200X-S, Hefei Kejing Materials Technology Co., Ltd., China);

[0051] JSM-6390LV scanning electron microscope (SEM) JEOL, Japan; IRPrestige-21 Shimadzu Fourier transform infrared spectrometer (SHIMADZJ, Japan);

[0052] High-power digitally controlled ultrasonic cleaner (model: KQ-200KDE, Kunshan Ultrasonic Instrument Co., Ltd., China);

[0053] Near-infrared spectrometer (Ocen optics Spectrsuite, UK); pH meter (PHSJ-3F, Shanghai Leici, China);

[0054] Constant temperature shaking box (model: OMW44, Changsha Keelung Instrument Co., Ltd., China);

[0055] UV-visible spectrophotometer (model: UV-2700, Shimadzu Corporation, Japan).

[0056] Sodium carbonate, 95% ethanol, and hydrochloric acid were all of analytical grade, and water was distilled water.

[0057] Example 1

[0058] A method for improving biochar from snow lotus residues comprises the following steps:

[0059] (1) Grind the snow lotus residue into 150-200 mesh, add 10% Na2CO3 solution, mix in a ratio of 1:8, soak for 24 h, and dry to constant weight to obtain alkali-modified residue powder;

[0060] (2) The obtained alkali-modified medicinal residue powder was placed in a magnetic boat, placed in a vacuum tube furnace, and nitrogen was introduced at a flow rate of 50 mL / min. The temperature was raised to 200 °C at a heating rate of 5 °C / min and pyrolyzed for 2 h. After natural cooling, the modified (SBA) snow lotus biochar was obtained.

[0061] Example 2

[0062] A method for improving biochar from snow lotus residues is different from that in Example 1 in that the pyrolysis temperature in step (2) is 300° C., the pyrolysis time is 2 h, and modified (SBA) snow lotus biochar is obtained after natural cooling.

[0063] Example 3

[0064] A method for improving biochar from snow lotus residues is different from that in Example 1 in that the pyrolysis temperature in step (2) is 400° C., the pyrolysis time is 2 h, and modified (SBA) snow lotus biochar is obtained after natural cooling.

[0065] Example 4

[0066] A method for improving biochar from snow lotus residues is different from that in Example 1 in that the pyrolysis temperature in step (2) is 500° C., the pyrolysis time is 2 h, and modified (SBA) snow lotus biochar is obtained after natural cooling.

[0067] Example 5

[0068] A method for improving biochar from snow lotus residues is different from that in Example 1 in that the pyrolysis temperature in step (2) is 600° C., the pyrolysis time is 2 h, and modified (SBA) snow lotus biochar is obtained after natural cooling.

[0069] Comparative Examples 1-5

[0070] A method for improving biochar from saussurea sibiricum residue differs from Examples 1-5 in that the alkaline modification treatment in step (1) is not included, but the saussurea sibiricum residue powder is directly subjected to heating pyrolysis. Specifically, the method comprises the following steps:

[0071] The snow lotus residue was crushed to 150-200 mesh, placed in a magnetic boat, and placed in a vacuum tube furnace. Nitrogen was introduced at a flow rate of 50 mL / min, and the temperature was increased to 200°C, 300°C, 400°C, 500°C, and 600°C at a heating rate of 5°C / min for pyrolysis for 2 h. After natural cooling, unmodified snow lotus biochar (SBC) was obtained.

[0072] Comparative Example 6

[0073] A method for improving biochar of Saussurea dasyphylla residue is different from Example 1 only in that, in step (1), a 10% Na2CO3 solution is not used for alkaline modification treatment, but a 10% NaOH solution is used.

[0074] Comparative Example 7

[0075] A method for improving biochar of Saussurea dasyphylla residue is different from Example 1 only in that, in step (1), a 10% mass concentration of Na2CO3 solution is not used for alkaline modification treatment, but a 10% mass concentration of Ca(OH)2 solution is used.

[0076] Technical Effects

[0077] 1. Comparison of the yields of the two biochars

[0078] Yield calculation formula: Yield = (mass before burning / mass after burning) * 100%

[0079] The results are shown in Table 1.

[0080] Table 1. Comparison of the yields of the two carbons of the present invention

[0081]

[0082] It can be seen from Table 1 that the yields of both types of charcoal decrease with increasing charcoal production temperature, but the yields of the modified biochars obtained in Examples 1-5 are always higher than those of the unmodified biochars obtained in Comparative Examples 1-5.

[0083] 2. Effect of alkaline modification on the surface microstructure of biochar

[0084] The morphology and structure of each sample were analyzed under high magnification using a JSM-6390LV scanning electron microscope (SEM) from JEOL.

[0085] The experimental results are as follows Figure 1 As shown, as the pyrolysis temperature increases, the surface of the unmodified biochar obtained in Comparative Examples 1-5 becomes rolled up, the stacking of the lamellar structure gradually increases, the pore walls become thinner, and the pore structure gradually expands. However, the surface of the modified biochar in Examples 1-5 begins to roughen at 200°C, with more pores and a gradually increasing density between them. This intuitively makes the structure more compact, resulting in an increase in mass. The surface micropores are most dense at 600°C. This shows that the compact microporous structure of the modified biochar in Examples 1-5 of the present invention increases the contact area with the dye, thereby improving adsorption performance.

[0086] 3. Effect of modification on the spectral structure of biochar

[0087] Fourier transform infrared spectroscopy (FT-IR) was used to compare the changes in surface functional groups of the modified biochar obtained in Examples 1-5 and the unmodified biochar obtained in Comparative Examples 1-5 at pyrolysis temperatures of 200°C to 600°C. -1 FT-IR spectra were recorded between wavenumbers.

[0088] The experimental results are as follows Figure 2 As shown in the figure, the functional group types of the medicinal residue will change with the increase of carbonization temperature. -1 The broad peak at 3000-2810cm belongs to the stretching vibration of the OH bond, indicating the presence of hydroxyl groups. -1 The double peak at 1418cm is due to the stretching vibration of the CH bond of saturated hydrocarbons. As the temperature rises, the absorption intensity decreases and disappears at 500℃. -1 The bending vibration of the C-H bond is at 1620 cm -1 -1460cm -1 The multiple peaks are attributed to the stretching vibration of the C=C bond of aromatic hydrocarbons, 868cm -1 -677cm -1The peak corresponds to the aromatic CH stretching vibration. Therefore, there is the possibility of the presence of alcohol, phenolic hydroxyl group and carboxylic acid, methyl, methylene or methine and benzene ring. The absorption intensity increases and decreases with increasing temperature, indicating that the structure of the unmodified biochar in Comparative Examples 1-5 will break the bond when subjected to high temperature (see Appendix). Figure 2 (a) in the figure). However, in Examples 1-5, after modification with sodium carbonate, the absorption of saturated hydrocarbons by CH bonds was weakened, while the absorption of aromatics was enhanced and the carbon was resistant to high temperatures. This indicates that the modification promoted the aromatization and high temperature resistance of the original carbon. (Appendix Figure 2 (b) of the .

[0089] 4. Select stable concentrations of the two dye solutions

[0090] (1) Accurately weigh 1 mg of methyl orange and methyl red, dilute to 25 ml with distilled water and 95% ethanol, respectively. Perform a full wavelength scan under ultraviolet light from 200 to 800 nm and analyze to determine the maximum detection wavelength. The detection wavelengths were determined to be 463 nm and 495 nm, respectively.

[0091] (2) Accurately weigh 0.1 g each of methyl red and methyl orange and prepare a 0.1 mg / ml solution with distilled water and 95% ethanol, respectively. Set up a gradient to draw a standard curve and examine the concentration gradients of 4, 6, 8, 10, and 12 mg / L.

[0092] The experimental results are as follows Figure 3 , as shown in 4, the methyl red curve equation y=75.643x-0.2093(R 2 =0.9982), methyl orange curve equation y = 72.086x-0.0053 (R 2 =0.9998), and the linearity of the two dye solutions was good within the range of 4-12 mg / L.

[0093] 5. Adsorption performance experiment of modified carbon under fixed conditions

[0094] 10 ml of each of the methyl red and methyl orange dye solutions prepared above were measured, each with a concentration of 8 mg / L. 0.01 g of each biochar obtained in Examples 1-5 was weighed and mixed with the methyl red and methyl orange dye solutions, respectively. Each experiment was repeated in triplicate. The mixture was then shaken in a constant temperature shaker at 30°C and 180 rpm for 2 h. The mixture was filtered through a 0.45 μm microporous filter membrane and measured at 463 nm and 495 nm using a UV-2700 UV-visible spectrophotometer. The post-adsorption concentration was calculated. The adsorption capacity was described by the adsorption capacity and removal rate of MO and MR.

[0095] Adsorption capacity calculation formula: Adsorption capacity Qe = (initial concentration of dye solution - concentration of dye solution after adsorption) / adsorbent mass * adsorption volume

[0096] Removal rate calculation formula: Removal rate η = (initial concentration of dye solution - adsorption equilibrium concentration) / initial concentration of dye solution * 100%

[0097] The results are shown in Table 2.

[0098] Table 2. Comparison of the adsorption effect of the biochar obtained from Comparative Examples 1-5 and Examples 1-5 on two azo dye solutions

[0099]

[0100]

[0101] As shown in Table 2, the modified biochars prepared from saussurea ovata residue in Examples 1-5 and the unmodified biochars obtained in Comparative Examples 1-5 both exhibited adsorption properties for methyl orange and methyl red. However, as the pyrolysis temperature increased, and under the same initial dye liquor concentration, the modified biochars obtained in Examples 1-5 showed significantly stronger adsorption of both dyes than the unmodified biochars obtained in Comparative Examples 1-5, with a more pronounced adsorption effect for methyl red.

[0102] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for improving biochar from Saussurea involucrata residues, characterized in that: The following steps are involved: The powder of Saussurea involucrata residue is added into an alkaline solution for immersion, and then heated and pyrolyzed in the presence of an inert gas, and then cooled to obtain modified biochar; The powder particle size of the snow lotus residue is 150-200 mesh; The snow lotus medicinal residue is waste material of snow lotus Chinese medicinal materials or medicinal residue produced during the preparation of Chinese patent medicines mainly based on snow lotus; The Chinese patent medicine comprises one of snow lotus oral liquid, snow lotus injection and snow lotus tablets; The ratio of the added amount of the snow lotus residue powder to the alkaline solution is 1:8; The temperature-raising pyrolysis comprises the following steps: The infused snow lotus residue powder is heated to 200-600° C. and pyrolyzed for 2 h.

2. The method for improving biochar from Saussurea involucrata residue according to claim 1, wherein: The alkaline solution is a Na2CO3 solution with a mass concentration of 10%.

3. The method for improving biochar of Saussurea involucrata residue according to claim 1, wherein: The immersion temperature is room temperature and the immersion time is 24 hours.

4. The method for improving biochar from Saussurea involucrata residue according to claim 1, wherein: The inert gas is nitrogen.

5. The method for improving biochar from Saussurea involucrata residue according to claim 4, wherein: The heating rate is 5°C / min.

6. The modified biochar prepared by the method for improving biochar from Saussurea involucrata residue according to any one of claims 1 to 5.

7. Use of the modified biochar according to claim 6 in the field of adsorbents.

8. Use of the modified biochar according to claim 6 in the adsorption of methyl red and methyl orange.

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