CN113426408B - A kind of hydrophobically modified biochar using natural organic acid and its preparation method and application - Google Patents

A kind of hydrophobically modified biochar using natural organic acid and its preparation method and application Download PDF

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CN113426408B
CN113426408B CN202011642245.6A CN202011642245A CN113426408B CN 113426408 B CN113426408 B CN 113426408B CN 202011642245 A CN202011642245 A CN 202011642245A CN 113426408 B CN113426408 B CN 113426408B
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王小红
黄皓旻
成海荣
叶光政
焦裕均
朱文富
姚帆
王钰钦
叶代启
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Abstract

本发明公开了一种利用天然有机酸疏水改性生物炭及其制备方法与应用。所述制备方法包括以下步骤:(1)把生物炭和过氧化氢溶液混合,进行软化、搅拌、过滤得到羟基化的生物炭;(2)把羟基化的生物炭、硼氢化钠、无水乙醇混合,进行搅拌、过滤、惰性气体气氛50‑100℃烘干、得到干燥的生物炭;(3)把干燥的生物炭加入到溶解有天然大分子有机酸、无水乙醇、脱水剂的溶液中加热搅拌,得到混合液;(4)把混合液过滤,接着用乙醇、去离子水冲洗,惰性气体气氛50‑100℃干燥,可获得改性后的生物炭。本发明的优点为操作简单、价格低廉、绿色环保、对炭材料孔径结构影响较小,在高湿环境下对挥发性有机物具有良好的吸附性能。

Figure 202011642245

The invention discloses a hydrophobically modified biochar using natural organic acid and a preparation method and application thereof. The preparation method comprises the following steps: (1) mixing biochar and hydrogen peroxide solution, softening, stirring and filtering to obtain hydroxylated biochar; (2) mixing the hydroxylated biochar, sodium borohydride, anhydrous Mixing with ethanol, stirring, filtering, and drying in an inert gas atmosphere at 50-100° C. to obtain dry biochar; (3) adding the dry biochar to a solution in which natural macromolecular organic acid, anhydrous ethanol, and dehydrating agent are dissolved (4) filter the mixed solution, then rinse with ethanol and deionized water, and dry in an inert gas atmosphere at 50-100° C. to obtain the modified biochar. The invention has the advantages of simple operation, low price, green environmental protection, little influence on the pore size structure of the carbon material, and good adsorption performance for volatile organic compounds in a high humidity environment.

Figure 202011642245

Description

一种利用天然有机酸疏水改性生物炭及其制备方法与应用A kind of hydrophobically modified biochar using natural organic acid and its preparation method and application

技术领域technical field

本发明属于多孔炭材料领域,特别是涉及一种利用天然有机酸疏水改性生物炭及其制备方法与应用。The invention belongs to the field of porous carbon materials, and in particular relates to a hydrophobically modified biochar using natural organic acid and a preparation method and application thereof.

背景技术Background technique

目前吸附技术和吸附-催化燃烧技术是中低浓度有机废气有效治理的主要技术。其中,吸附剂成为关键材料之一,而炭基多级孔材料由于来源广泛,如活性炭、生物炭、生物炭纤维等,价格低廉、性能优异等特点被广泛作为VOCs的吸附剂。但是,工程实践经验表明,常见炭基吸附剂在工程应用中面临着与水蒸气竞争吸附的难题,例如在汽车制造的喷漆工序中,湿式喷淋常用于去除多余的喷漆,从而增加其VOCs废气的湿度。另外,水性原辅材料替代溶剂性原辅材料的逐步推广,炭基吸附剂在VOCs和水蒸气选择性吸附方面的矛盾越来越突出。而炭基吸附剂VOCs吸附容量在高湿度条件下会大大降低,极易达到饱和状态,不利于有机废气的净化。At present, adsorption technology and adsorption-catalytic combustion technology are the main technologies for effective treatment of medium and low concentration organic waste gas. Among them, adsorbents have become one of the key materials, and carbon-based hierarchical porous materials are widely used as adsorbents for VOCs due to their wide range of sources, such as activated carbon, biochar, and biochar fibers, low price and excellent performance. However, engineering practical experience shows that common carbon-based adsorbents face the problem of competing with water vapor in engineering applications. For example, in the painting process of automobile manufacturing, wet spraying is often used to remove excess paint, thereby increasing its VOCs exhaust gas humidity. In addition, with the gradual promotion of water-based raw and auxiliary materials to replace solvent-based raw and auxiliary materials, the contradiction between carbon-based adsorbents in the selective adsorption of VOCs and water vapor has become more and more prominent. However, the adsorption capacity of carbon-based adsorbent VOCs will be greatly reduced under high humidity conditions, and it is easy to reach a saturated state, which is not conducive to the purification of organic waste gas.

对于材料疏水性方面,已有文献报道,使用功能性涂料能有效实现稳定的超疏水性,可应用于建筑环境控制、水动力减阻等方面。另外,有些涂料如有机硅烷和全氟化合物往往有毒、易燃、腐蚀性强、难以处理并破坏环境。然而,天然大分子有机酸改性的疏水性炭材料用在高湿环境中VOCs吸附的应用却鲜见报道。因此,研制具有高疏水性能的多级孔炭材料作为高效VOCs吸附剂,有望克服现有炭材料吸附容量低、与水蒸气竞争吸附性能差等不足,具有良好的应用前景。Regarding the hydrophobicity of materials, it has been reported in the literature that the use of functional coatings can effectively achieve stable superhydrophobicity, which can be applied to building environment control, hydrodynamic drag reduction, etc. In addition, some coatings such as organosilanes and perfluorinated compounds tend to be toxic, flammable, corrosive, difficult to handle and damage the environment. However, the application of natural macromolecular organic acid-modified hydrophobic carbon materials for VOCs adsorption in high-humidity environments is rarely reported. Therefore, the development of hierarchical porous carbon materials with high hydrophobic properties as high-efficiency VOCs adsorbents is expected to overcome the shortcomings of existing carbon materials such as low adsorption capacity and poor adsorption performance when competing with water vapor, and has good application prospects.

发明内容SUMMARY OF THE INVENTION

针对上述问题,本发明提供了一种利用天然有机酸疏水改性生物炭及其制备方法与应用。In view of the above problems, the present invention provides a hydrophobically modified biochar using natural organic acid and a preparation method and application thereof.

本发明的目的在于至少通过以下方案之一实现。The purpose of the present invention is to achieve at least one of the following solutions.

一种利用天然有机酸疏水改性生物炭的制备方法,包括以下步骤:A preparation method of hydrophobically modified biochar utilizing natural organic acid, comprising the following steps:

(1)把生物炭和过氧化氢溶液混合,进行搅拌、过滤得到羟基化的生物炭;(1) mixing biochar and hydrogen peroxide solution, stirring and filtering to obtain hydroxylated biochar;

(2)把步骤(1)所述羟基化的生物炭、硼氢化钠、无水乙醇混合,进行搅拌、过滤、惰性气体气氛50-100℃烘干、得到干燥的生物炭;(2) mixing the hydroxylated biochar in step (1), sodium borohydride, and dehydrated alcohol, stirring, filtering, and drying in an inert gas atmosphere at 50-100° C. to obtain dry biochar;

(3)把步骤(2)所述干燥的生物炭加入到溶解有天然大分子有机酸、无水乙醇、脱水剂的溶液中加热搅拌,得到混合液;(3) adding the dry biochar described in step (2) into the solution in which natural macromolecular organic acid, dehydrated alcohol, and dehydrating agent are dissolved, and heating and stirring to obtain a mixed solution;

(4)把步骤(3)所述的混合液过滤,沉淀物用乙醇、去离子水冲洗,惰性气体气氛50-100℃干燥,可获得改性后的生物炭。(4) Filter the mixed solution described in step (3), rinse the precipitate with ethanol and deionized water, and dry in an inert gas atmosphere at 50-100° C. to obtain the modified biochar.

进一步地,步骤(1)中,所述生物炭为椰子壳生物炭、甘蔗渣生物炭和核桃壳生物炭中的一种或多种;所述过氧化氢溶液的质量分数为5-30%。Further, in step (1), the biochar is one or more of coconut shell biochar, bagasse biochar and walnut shell biochar; the mass fraction of the hydrogen peroxide solution is 5-30% .

进一步地,步骤(1)中,所述搅拌时间为1-6h。Further, in step (1), the stirring time is 1-6h.

进一步地,步骤(2)中,所述羟基化的生物炭和硼氢化钠的质量比为10:1~0.1:1;所述无水乙醇的体积与羟基化的生物炭的质量的比值为1:1-1:50L/g;所述搅拌的时间为1-6h。Further, in step (2), the mass ratio of the hydroxylated biochar to sodium borohydride is 10:1 to 0.1:1; the ratio of the volume of the anhydrous ethanol to the mass of the hydroxylated biochar is 1:1-1:50L/g; the stirring time is 1-6h.

进一步地,步骤(3)中,所述天然大分子有机酸为肉桂酸、咖啡酸、肉豆蔻酸或月桂酸中的一种或多种。Further, in step (3), the natural macromolecular organic acid is one or more of cinnamic acid, caffeic acid, myristic acid or lauric acid.

进一步地,步骤(3)中,所述天然大分子有机酸的质量与无水乙醇的体积比为(1-20:1)g/L;所述脱水剂的用量为天然大分子有机酸用量的10-50wt%。Further, in step (3), the quality of the natural macromolecular organic acid and the volume ratio of dehydrated ethanol are (1-20:1) g/L; the consumption of the dehydrating agent is the consumption of the natural macromolecular organic acid 10-50wt%.

进一步地,步骤(3)中,所述搅拌的时间为6-24h。Further, in step (3), the stirring time is 6-24h.

上述的制备方法制备得到的利用天然有机酸疏水改性生物炭。The natural organic acid hydrophobically modified biochar is prepared by the above preparation method.

上述的利用天然有机酸疏水改性生物炭在吸附VOCs方面的应用。The application of the above-mentioned hydrophobically modified biochar using natural organic acids in the adsorption of VOCs.

进一步地,所述吸附VOCs的环境的相对湿度大于70%。Further, the relative humidity of the environment for adsorbing VOCs is greater than 70%.

本发明的基本原理是:天然大分子有机酸具有大量羧基,采用乙醇化学沉积法对有机酸与生物炭表面羟基官能团进行酯化反应生成化学键,其中反应过程中的脱水剂能促进羧基和羟基之间形成共价键而不被吸附在表面,从而使生物炭形成稳定的疏水结构。The basic principle of the present invention is: the natural macromolecular organic acid has a large number of carboxyl groups, and the ethanol chemical deposition method is used to carry out an esterification reaction between the organic acid and the hydroxyl functional group on the surface of the biochar to form a chemical bond, wherein the dehydrating agent in the reaction process can promote the carboxyl group and the hydroxyl group. Covalent bonds are formed between them without being adsorbed on the surface, so that the biochar forms a stable hydrophobic structure.

与现有技术相比,本发明具有如下优点:Compared with the prior art, the present invention has the following advantages:

(1)本发明的制备方法操作简单、价格低廉、绿色环保、疏水,对炭材料孔径结构影响较小;(1) The preparation method of the present invention is simple in operation, low in price, environmentally friendly, hydrophobic, and has little influence on the pore size structure of the carbon material;

(2)本发明制备的利用天然有机酸疏水改性生物炭在高湿环境下对挥发性有机物VOCs具有良好的吸附性能。(2) The hydrophobically modified biochar using natural organic acid prepared by the present invention has good adsorption performance for volatile organic VOCs in a high humidity environment.

附图说明Description of drawings

图1为本发明提供的利用天然有机酸疏水改性生物炭的制备方法的流程图;Fig. 1 is the flow chart of the preparation method of utilizing natural organic acid hydrophobically modified biochar provided by the present invention;

图2为实施例中生物炭改性前后的红外光谱图;Fig. 2 is the infrared spectrogram before and after biochar modification in the embodiment;

图3为实施例中生物炭改性前后在干燥环境下吸附VOCs的穿透曲线;Fig. 3 is the penetration curve of adsorbing VOCs in dry environment before and after biochar modification in the embodiment;

图4为实施例中生物炭改性前后在相对湿度为70%环境下吸附VOCs的穿透曲线。Figure 4 is the breakthrough curve of the adsorption of VOCs under the environment of relative humidity of 70% before and after biochar modification in the example.

具体实施方式Detailed ways

下面结合具体实施例和附图对本发明的具体实施作进一步详细说明,但本发明的实施方式不限于此。The specific implementation of the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings, but the implementation of the present invention is not limited thereto.

以下实施例制备利用天然有机酸疏水改性生物炭的方法参照图1所示的制备步骤。In the following examples, the method for preparing the hydrophobically modified biochar using natural organic acid refers to the preparation steps shown in FIG. 1 .

应用:将实施例1制备的改性前和改性后的生物炭,应用于环境分别为干燥的和相对湿度为70%的挥发性有机物的吸附,进行VOCs吸附性能测试实验;Application: The biochar before and after modification prepared in Example 1 was applied to the adsorption of volatile organic compounds in a dry environment and a relative humidity of 70%, respectively, and the VOCs adsorption performance test experiment was carried out;

(1)干燥环境挥发性有机物的吸附:先用GC测定VOCs和空气混合气体的VOCs浓度,让其稳定在100ppm,在吸附评价装置中装入0.05g吸附材料(生物炭),将VOCs和空气混合气体通入吸附材料,最后用气相色谱(GC)测定出口VOCs浓度,每个色谱图分析时间是8.5min,测定材料对VOCs的吸附容量。(1) Adsorption of volatile organic compounds in a dry environment: first measure the VOCs concentration of VOCs and air mixed gas by GC, let it stabilize at 100ppm, put 0.05g of adsorption material (biochar) in the adsorption evaluation device, mix VOCs and air The mixed gas was passed into the adsorption material, and finally, the concentration of VOCs at the outlet was determined by gas chromatography (GC). The analysis time of each chromatogram was 8.5 minutes, and the adsorption capacity of the material to VOCs was determined.

(2)相对湿度为70%环境挥发性有机物的吸附:先用GC和湿度计测定VOCs、水汽和空气混合气体的VOCs浓度和湿度,让其稳定在100ppm和70%相对湿度,最后用气相色谱(GC)测定出口VOCs浓度,每个色谱图分析时间是8.5min,测定材料对VOCs的吸附容量。(2) Adsorption of volatile organic compounds in an environment with a relative humidity of 70%: first use GC and a hygrometer to measure the VOCs concentration and humidity of VOCs, water vapor and air mixed gas, let it stabilize at 100ppm and 70% relative humidity, and finally use gas chromatography (GC) to measure the concentration of VOCs at the outlet, the analysis time of each chromatogram is 8.5min, and the adsorption capacity of the material to VOCs is measured.

实施例1Example 1

(1)取1.5g生物炭(标记为BC)到烧杯中,然后再添加50mL的质量分数为10%过氧化氢溶液进行混合进行软化,搅拌2h、过滤得到羟基化的生物炭。(1) Take 1.5 g of biochar (marked as BC) into a beaker, then add 50 mL of 10% hydrogen peroxide solution for mixing and softening, stir for 2 h, and filter to obtain hydroxylated biochar.

(2)再把羟基化的生物炭与硼氢化钠的质量比为1:1以及50mL无水乙醇混合,进行搅拌2h、过滤、80℃氮气气氛干燥60min、得到干燥的生物炭。(2) Mix the hydroxylated biochar with sodium borohydride in a mass ratio of 1:1 and 50 mL of absolute ethanol, stir for 2 hours, filter, and dry in a nitrogen atmosphere at 80°C for 60 minutes to obtain dry biochar.

(3)把0.5g步骤(2)中干燥的生物炭、1g肉豆蔻酸、0.4g脱水剂和100mL无水乙醇加入到圆底烧瓶中,75℃加热搅拌24h,得到混合液。(3) 0.5 g of biochar dried in step (2), 1 g of myristic acid, 0.4 g of dehydrating agent and 100 mL of absolute ethanol were added to a round-bottomed flask, heated and stirred at 75° C. for 24 h to obtain a mixed solution.

(4)最后把步骤(3)的混合液过滤后的沉淀物用乙醇和去离子水冲洗,80℃氮气气氛干燥60min,可获得改性生物炭(标记为BC-E)。(4) Finally, the filtered precipitate of the mixed solution in step (3) was rinsed with ethanol and deionized water, and dried in a nitrogen atmosphere at 80° C. for 60 min to obtain modified biochar (marked as BC-E).

以上实施例所得疏水改性后的官能团变化以及干湿条件下的VOCs吸附性能评价结果分别如下:The functional group changes after hydrophobic modification obtained in the above examples and the evaluation results of VOCs adsorption performance under dry and wet conditions are as follows:

图2利用红外光谱(FTIR)研究改性前后生物炭BC和BC-E表面官能团的差异,探究疏水改性活性炭表面发生的化学反应。结果显示有机酸中的-CH3等脂肪族化合物官能团信号仅出现在改性材料BC-E中,初步证明天然疏水物质能有效修饰至炭材料从而改变其表面基团。Figure 2 uses infrared spectroscopy (FTIR) to study the difference in the surface functional groups of biochars BC and BC-E before and after modification, and to explore the chemical reaction on the surface of hydrophobically modified activated carbon. The results show that the signals of aliphatic compounds such as -CH3 in organic acids only appear in the modified material BC-E, which preliminarily proves that natural hydrophobic substances can be effectively modified to carbon materials to change their surface groups.

不同相对湿度下BC和BC-E生物炭材料的VOCs吸附性能:VOCs adsorption performance of BC and BC-E biochar materials under different relative humidity:

表1为生物炭改性前后分别在干燥和相对湿度为70%条件下的VOCs吸附性能;Table 1 shows the adsorption performance of VOCs under the conditions of drying and relative humidity of 70% before and after biochar modification;

表1Table 1

Figure GDA0003207580450000041
Figure GDA0003207580450000041

图3为实施例中生物炭改性前后在干燥环境下吸附VOCs的穿透曲线;Fig. 3 is the penetration curve of adsorbing VOCs in dry environment before and after biochar modification in the embodiment;

图4为实施例中生物炭改性前后在相对湿度为70%环境下吸附VOCs的穿透曲线;Fig. 4 is the penetration curve of adsorbing VOCs under the environment of relative humidity of 70% before and after biochar modification in the embodiment;

结合图3、图4穿透曲线以及表1可以发现,在干燥VOCs环境中(RH=0%),BC对VOCs的吸附能力大于BC-E。当相对湿度从0%增加到70%时,没有经过改性的生物炭BC的吸附能力由380到212mg/g,下降了44%,在潮湿环境下对VOCs的吸附性能大大降低。而经过有机酸改性的生物炭BC-E的吸附能力由308到245mg/g,仅下降了20%。与BC相比,水分的存在对BC-E吸附VOCs的影响较小,疏水改性生物炭对VOCs的选择性增强。由以上结果可以看出,本发明所得疏水改性后的活性炭在高湿环境下活性炭对VOCs具有良好的吸附性能,大大减少了高湿环境中VOCs的处理成本。Combined with Figure 3, Figure 4 breakthrough curves and Table 1, it can be found that in a dry VOCs environment (RH=0%), the adsorption capacity of BC on VOCs is greater than that of BC-E. When the relative humidity increased from 0% to 70%, the adsorption capacity of unmodified biochar BC decreased by 44% from 380 to 212 mg/g, and the adsorption performance of VOCs in humid environment was greatly reduced. However, the adsorption capacity of biochar BC-E modified by organic acid decreased by only 20% from 308 to 245 mg/g. Compared with BC, the presence of moisture has less effect on the adsorption of VOCs by BC-E, and the selectivity of hydrophobically modified biochar to VOCs is enhanced. It can be seen from the above results that the hydrophobically modified activated carbon obtained in the present invention has good adsorption performance for VOCs in a high-humidity environment, and greatly reduces the treatment cost of VOCs in a high-humidity environment.

以上所述,仅为本发明的较佳实施例而已,并非对本发明做任何形式上的限定。凡本领域的技术人员利用本发明的技术方案对上述实施例作出的任何等同的变动、修饰或演变等,均仍属于本发明技术方案的范围内。The above descriptions are merely preferred embodiments of the present invention, and do not limit the present invention in any form. Any equivalent changes, modifications or evolutions made by those skilled in the art to the above embodiments by utilizing the technical solutions of the present invention still fall within the scope of the technical solutions of the present invention.

Claims (1)

1. The application of the hydrophobically modified biochar utilizing natural organic acid in the aspect of adsorbing VOCs is characterized in that the relative humidity of the environment for adsorbing VOCs is more than 70%;
the preparation method of the biochar hydrophobically modified by utilizing the natural organic acid comprises the following steps:
(1) mixing the biochar with a hydrogen peroxide solution, stirring and filtering to obtain hydroxylated biochar; the biochar is one or more of coconut shell biochar, bagasse biochar and walnut shell biochar; the mass fraction of the hydrogen peroxide solution is 5-30%; the stirring time is 1-6 h;
(2) mixing the hydroxylated biochar in the step (1), sodium borohydride and absolute ethyl alcohol, stirring, filtering, and drying at 50-100 ℃ in an inert gas atmosphere to obtain dried biochar; the mass ratio of the hydroxylated biochar to the sodium borohydride is (10: 1) - (0.1: 1); the ratio of the volume of the absolute ethyl alcohol to the mass of the hydroxylated biochar is (1: 1) - (1: 50) L/g; the stirring time is 1-6 h;
(3) adding the dried biochar in the step (2) into a solution in which natural organic acid, absolute ethyl alcohol and a dehydrating agent are dissolved, heating and stirring to obtain a mixed solution; the natural organic acid is one or more of myristic acid or lauric acid; the volume ratio of the mass of the natural organic acid to the absolute ethyl alcohol is (1-20): 1 g/L; the dosage of the dehydrating agent is 10-50wt% of the dosage of the natural organic acid; the stirring time is 6-24 h;
(4) and (4) filtering the mixed solution obtained in the step (3), washing the precipitate with ethanol and deionized water, and drying at 50-100 ℃ in an inert gas atmosphere to obtain modified biochar.
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US12291473B2 (en) 2021-07-05 2025-05-06 Inspired Water Technology Inc. Wastewater treatment system for improved primary treatment and volatile fatty acid generation

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CN114029044A (en) * 2021-11-09 2022-02-11 南昌航空大学 A kind of preparation method of modified nickel-iron layered double hydroxide composite nanometer photocatalyst
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Family Cites Families (7)

* Cited by examiner, † Cited by third party
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PL234828B1 (en) * 2017-11-15 2020-04-30 Pcc Mcaa Spolka Z Ograniczona Odpowiedzialnoscia Method for obtaining low- and/or medium-molecular polymer-based surface-active compounds with specified hydrophilic-lipophilic equilibrium
CN108380181B (en) * 2018-03-28 2021-01-26 绍兴文理学院 A kind of preparation method of hydrophobic activated carbon
CN110237822A (en) * 2019-07-09 2019-09-17 华南理工大学 A kind of environment-friendly hydrophobic modification method of activated carbon
CN110523383A (en) * 2019-08-22 2019-12-03 华南理工大学 Hydrophobic modified activated carbon for adsorbing organic matter and its preparation method and application
CN112023889A (en) * 2020-08-28 2020-12-04 西安工程大学 A kind of microwave-assisted method for in-situ one-step modification of activated carbon with oleic acid

Cited By (1)

* Cited by examiner, † Cited by third party
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