WO2020052502A1 - Porous biomass adsorbing material, and preparation method and application thereof - Google Patents

Porous biomass adsorbing material, and preparation method and application thereof Download PDF

Info

Publication number
WO2020052502A1
WO2020052502A1 PCT/CN2019/104754 CN2019104754W WO2020052502A1 WO 2020052502 A1 WO2020052502 A1 WO 2020052502A1 CN 2019104754 W CN2019104754 W CN 2019104754W WO 2020052502 A1 WO2020052502 A1 WO 2020052502A1
Authority
WO
WIPO (PCT)
Prior art keywords
biomass
sodium hydroxide
porous
aqueous solution
mixed aqueous
Prior art date
Application number
PCT/CN2019/104754
Other languages
French (fr)
Chinese (zh)
Inventor
李澧
吕晓兰
张瑜
陈泰文
杨亚莉
Original Assignee
江苏省农业科学院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 江苏省农业科学院 filed Critical 江苏省农业科学院
Publication of WO2020052502A1 publication Critical patent/WO2020052502A1/en
Priority to AU2020103640A priority Critical patent/AU2020103640A4/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Definitions

  • the invention belongs to the field of sewage treatment, in particular to the field of chroma wastewater treatment, and relates to a porous porous adsorbent material and a preparation method and application thereof.
  • Chroma is an important indicator of water pollution. Substances that contain chromophores, conjugated structures, and chromophoric groups can cause the color of water to increase.
  • Chroma sewage has the characteristics of complex composition, deep chroma, high salinity, strong acidity and alkalinity.
  • the composition is complicated. Chroma sewage contains not only colored organic substances, but also some colored heavy metal ions such as iron, copper, and manganese, which have strong carcinogenic and mutagenic effects on humans and fish.
  • Deep chroma The organic matter in chroma sewage is mostly based on aromatic groups such as benzene, naphthalene, anthracene, quinone, etc. The chroma is deep, the light is difficult to enter the river, and plants (algae, etc.) cannot perform photosynthesis, which seriously affects the ecological environment discharged into waters ) High salinity.
  • Chroma sewage contains inorganic salts such as chlorides and sulfides, with high concentration and high toxicity. 4) High chemical oxygen demand (COD) and poor biodegradability.
  • Organic compounds such as benzene, naphthalene, anthraquinone, aniline, nitro, and phenols have low BOD / COD values and poor microbial degradation capacity.
  • the main decolorization methods of chroma sewage include flocculation method, oxidation method, biochemical method and adsorption method.
  • the flocculation method uses the flocculant to compress the electric double layer, electric neutralization, bridge action, and net capture sedimentation to realize the decolorization of high-color wastewater.
  • the flocculation process is mature and the decolorization effect is stable.
  • the oxidation method is to use oxidants to destroy the chromophores of organic matter, and to realize the decolorization of high-color wastewater.
  • Fenton method has strong oxidation ability, mild reaction conditions, and wide application range.
  • the photocatalytic oxidation method has the advantages of high energy efficiency, high decolorization efficiency, and complete sludge degradation.
  • the electrochemical oxidation method does not require chemical reagents, does not produce sludge, and is non-toxic to the degradation industry.
  • the treated sewage can be directly discharged. Therefore, improving the catalytic performance, decolorization stability, and reducing energy consumption of electrode materials are the key research directions of electrochemical oxidation methods.
  • the biochemical method is a method for decoloring high-color wastewater by using microorganisms to degrade colored substances.
  • Microorganisms have the ability to selectively decompose colored substances. Therefore, the overall decolorization effect of single-group microorganisms on color wastewater is poor.
  • Adsorption method is a method of removing high chroma substances in chroma sewage by means of physical adsorption, chemical adsorption, exchange adsorption, etc. It has the advantages of simple adsorption method and stable decoloring effect.
  • the most commonly used color adsorbent for porous activated carbon However, after the adsorption is saturated, the activated carbon needs to be regenerated by hot steam, which is complicated and expensive. Therefore, it is of great scientific and market value to develop a new type of biomass adsorbent with high abundance of active groups, low price, safety, non-toxicity, and no secondary pollution.
  • Cellulose molecules are long-chain molecules composed of glucopyranose monomers, with a large number of hydroxyl groups on the surface.
  • the cellulose-based functional materials reported in the literature make full use of the active hydroxyl groups in the cellulose monomer, and perform multi-step modification to finally achieve the purpose of functionalizing the cellulose-based materials.
  • the purpose of the present invention is to provide a kind of anionic dye that can absorb many kinds of anionic dyes in view of the disadvantages of high existing cellulose, complicated modification and modification process, tedious, time-consuming, low modification efficiency, introduction of organic groups with potential safety hazards, and the like.
  • the porous adsorption material does not require post-modification, and introduces amine groups on the main chain of biomass molecules in one step to realize the functionalization of biomass porous materials, which can realize industry Purification of food high chroma wastewater.
  • a biomass porous adsorption material which is prepared by the following methods: irradiating biomass material in air with an irradiation dose of not less than 10 kGy; dispersing the biomass material after irradiation treatment in a mixed aqueous solution of sodium hydroxide and urea Or in a mixed aqueous solution of sodium hydroxide and thiourea, freeze at -30 ° C to 0 ° C for 30 minutes to 10 hours to ensure that sodium hydroxide, urea / thiourea can dissolve cellulose (sodium hydroxide, urea / thiourea aqueous solution can reach Dissolve below 0 ° C), stir at room temperature (2000-3000 rpm) for 5-30 minutes, and then filter to obtain a biomass sol; gelatinize the biomass sol to obtain a biomass gel, and wash it to neutrality to obtain Amidated porous biomass adsorption material.
  • Step (1) The biomass material is irradiated in the air, and the irradiation dose is not less than 10kGy;
  • Step (2) Disperse the irradiated biomass material in a mixed aqueous solution of sodium hydroxide and urea or a mixed aqueous solution of sodium hydroxide and thiourea, and freeze at -12 ° C to 0 ° C for 30 minutes to 10 hours. After freezing, Stir at room temperature for 5-30 minutes (3000 rpm) and filter to obtain a biomass sol;
  • step (3) the biomass sol is gelled to obtain a biomass gel, which is washed to neutrality to obtain an amidated porous biomass adsorption material.
  • the biomass material is cotton, straw, wheat straw, or the like.
  • the radiation rays are gamma rays emitted when the radionuclide 60 Co or 137 Cs decays, and the high-energy electron beam is generated by the high-energy electron accelerator.
  • the irradiation dose is preferably 20-200 kGy, and more preferably 40-100 kGy.
  • step (2) the irradiated biomass material is shredded.
  • the magnetically stirred biomass material is dispersed in a mixed aqueous solution of sodium hydroxide and urea or a mixed aqueous solution of sodium hydroxide and thiourea using magnetic stirring.
  • the stirring time is 5-15 minutes, and the rotation speed is 1000-3000 rpm.
  • the mass ratio of the irradiated biomass material and the mixed aqueous solution of sodium hydroxide and urea or the mixed aqueous solution of sodium hydroxide and thiourea is 5-10: 90-95, and preferably 5:95.
  • the mass ratio of sodium hydroxide, urea, and water in the mixed aqueous solution of sodium hydroxide and urea is 3 to 10: 5 to 15:75 to 92, and preferably 3 to 8:10 to 15:77 to 87.
  • the mass ratio of sodium hydroxide, thiourea, and water in the mixed aqueous solution of sodium hydroxide and thiourea is 3 to 10: 5 to 15:75 to 92, and preferably 3 to 8:10 to 15:77 to 87.
  • step (3) the biomass sol is allowed to stand for gelation at 20 to 80 ° C. for 12 to 72 hours to obtain a biomass gel.
  • the normal temperature according to the present invention is 20 to 35 ° C.
  • Another object of the present invention is to provide the application of the biomass porous adsorbent material in the prevention and treatment of chromatic waste water.
  • the chromaticity sewage contains copper ion, iron ion, cobalt ion, manganese ion, methyl orange, acid black, acid red, acid blue, methylene blue, methyl green, caramel color, carmine, lemon yellow, and sunset At least one of yellow and bright blue.
  • the chromaticity wastewater is non-ferrous heavy metal wastewater, dye wastewater or pigment wastewater.
  • the invention adopts irradiation to effectively destroy the fiber internal structure of the raw material biomass material, and the biomass adsorption material does not need to be modified.
  • an amine group is introduced into the main chain of the biomass molecule to realize the functionalization of the porous material of the biomass.
  • the specific performance is:
  • the removal rate of 10 mL, 500 mg / L of methylene blue and methyl green per gram of porous material is not less than 70%.
  • the removal rate of 10 mL, 500 mg / L ferric chloride, copper sulfate, manganese chloride, and cobalt chloride per gram of porous material is not less than 70%.
  • the removal rate of 10mL, 500mg / L caramel, carmine, lemon yellow, sunset yellow, and bright blue per gram of porous material is not less than 70%.
  • FIG. 1 is a sol photograph of Xinjiang long-staple cotton of Example 1.
  • FIG. 1 is a sol photograph of Xinjiang long-staple cotton of Example 1.
  • FIG. 2 is a microscopic morphology of the material of Example 1; wherein A is a SEM image of a biomass porous material prepared by irradiating 10kGy long-staple cotton, magnified 10000 times; B is a biomass porous material prepared by irradiating 40kGy long-staple cotton SEM image of 10000 times magnification; C is SEM image of biomass porous material prepared by irradiating 80kGy long-staple cotton, magnified 10,000 times; D is SEM image of raw Xinjiang long-staple cotton, magnified 500 times; E is unradiated Photograph of Xinjiang long-staple cotton treated with sodium hydroxide / urea.
  • FIG. 3 is a diagram showing the removal effect of methyl orange by the irradiated long-staple cotton porous adsorbent in Example 1.
  • FIG. 3 is a diagram showing the removal effect of methyl orange by the irradiated long-staple cotton porous adsorbent in Example 1.
  • FIG. 4 is a diagram showing the removal effect of methyl green by the irradiated long-staple cotton porous adsorbent in Example 1.
  • FIG. 4 is a diagram showing the removal effect of methyl green by the irradiated long-staple cotton porous adsorbent in Example 1.
  • FIG. 5 is a diagram showing the removal effect of copper sulfate by the irradiated long-staple cotton porous adsorbent in Example 1.
  • FIG. 5 is a diagram showing the removal effect of copper sulfate by the irradiated long-staple cotton porous adsorbent in Example 1.
  • FIG. 6 is a diagram showing the removal effect of caramel pigment in a porous long-staple cotton absorbent material according to Example 1;
  • FIG. 7 is a diagram showing the removal effect of carmine pigment by the irradiated long-staple cotton porous adsorbent in Example 1.
  • FIG. 7 is a diagram showing the removal effect of carmine pigment by the irradiated long-staple cotton porous adsorbent in Example 1.
  • FIG. 8 is a diagram showing the removal effect of acid black 1 by a porous straw adsorbent in Example 2 in irradiation.
  • FIG. 9 is a diagram showing the removal effect of methylene blue by a porous straw adsorbent in Example 2 in irradiation.
  • FIG. 10 is a diagram showing the removal effect of ferric chloride by the porous straw adsorbing material in Example 2 of Example 2.
  • FIG. 11 is a diagram showing the removal effect of lemon yellow by irradiation of the straw porous adsorbent in Example 2;
  • FIG. 12 is a diagram showing the removal effect of sunset yellow of the straw porous adsorbent in Example 2 on irradiation.
  • FIG. 13 is a diagram showing the removal effect of acid fuchsin by the irradiated wheat straw porous adsorbent in Example 3.
  • FIG. 14 is a diagram showing the removal effect of acid blue by the wheat straw porous adsorbent in Example 3.
  • FIG. 15 is a diagram showing the removal effect of cobalt chloride by a wheat straw porous adsorbent in Example 3;
  • FIG. 16 is a diagram showing the removal effect of manganese chloride by the irradiated wheat straw porous adsorbent in Example 3.
  • Raw material Xinjiang long-staple cotton, with a fiber length of 38-39.7 mm and a fineness of 7510 m / g.
  • the unirradiated Xinjiang long-staple cotton was used as a control.
  • the results showed that the non-irradiated Xinjiang long-staple cotton was insoluble in a mixed aqueous solution of sodium hydroxide and urea at low temperature (Fig. 1), and was frozen at -12 ° C.
  • the fiber SEM is shown in Figure 2E. Comparing the micro-morphology of the raw long-staple cotton fiber ( Figure 2D), it can be found that the micro-morphology of the fiber has not changed significantly. It can be seen that unirradiated long-staple cotton cannot be used to prepare porous materials by the method of the present invention. Comparing the long-staple cotton fibers in FIG.
  • the porous adsorption material prepared in this embodiment has a large number of micron-sized holes, which effectively increases the specific surface area of the material. It shows that irradiation can effectively destroy the internal structure of virgin fibers, and thus prepare cellulose-based porous adsorption materials.
  • a methyl orange solution was prepared at a concentration of 1000 mg / L.
  • the UV absorption spectrum of the supernatant shows that the removal of methyl orange by the porous long-staple cotton absorbent material can reach at least 176.9 mg / g, which is much higher than the removal of methyl orange by raw long-staple cotton. 13.7 mg / g.
  • a 500 mg / L methyl green solution was prepared.
  • the UV absorption spectrum of the supernatant shows that the removal of methyl green by the porous long-staple cotton absorbent material can reach at least 71.8 mg / g, which is much higher than the removal of methyl green by the raw long-staple cotton. 5.2mg / g.
  • a copper sulfate solution was prepared at a concentration of 1000 mg / L.
  • the atomic absorption spectrum of the supernatant shows that the removal of copper sulfate by the porous long-staple cotton absorbent material can reach at least 146.7 mg / g, which is much higher than the removal of copper sulfate by raw long-staple cotton. / g.
  • a caramel pigment solution was prepared at a concentration of 1000 mg / L. Weigh 0.1g of the three types of irradiated long-staple cotton porous adsorption materials prepared in this example, add 50mL of a 1000mg / L caramel pigment solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 6, the UV absorption spectrum of the supernatant showed that the amount of caramel pigment removed from the porous long-staple cotton absorbent material was greater than 381.6 mg / g, which was much higher than the amount of caramel pigment removed from raw long-staple cotton 24.8 mg / g. .
  • a carmine pigment solution was prepared at a concentration of 500 mg / L. Weigh 0.1g of three irradiated long-staple cotton porous adsorption materials prepared in this example, add 20mL of 500mg / L carmine pigment solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 7, the UV absorption spectrum of the supernatant shows that the amount of carmine pigment removed by the irradiated long-staple cotton porous adsorbent material is greater than 74.9 mg / g, which is much higher than that of the raw material long-staple cotton. / g.
  • Raw materials straw, cellulose content 30-40%.
  • An acid black 1 solution was prepared at a concentration of 1000 mg / L. Weigh 0.02g of the three kinds of irradiated straw porous materials prepared in this example, and use the chopped raw straw as a control, add 20mL of 1000mg / L acid black 1 solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 8, the UV absorption spectrum of the supernatant shows that the removal of acid black 1 by the porous straw adsorbent can reach at least 772.4 mg / g, which is much higher than the removal of acid black 1 by raw straw 48.9 mg / g. .
  • a methylene blue solution was prepared at a concentration of 500 mg / L.
  • the UV absorption spectrum of the supernatant showed that the removal of methylene blue by the irradiated straw porous adsorbent can reach at least 72.9 mg / g, which is much higher than the removal of methylene blue by the raw straw of 3.4 mg / g.
  • a lemon yellow pigment solution was prepared at a concentration of 500 mg / L. Weigh 0.1g of three irradiated straw porous adsorption materials prepared in this example, add 20mL 500mg / L lemon yellow pigment solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 11, the UV absorption spectrum of the supernatant showed that the amount of lemon yellow pigment removed by the irradiated straw porous adsorbent was greater than 81.3 mg / g, which was much higher than the amount of lemon yellow removed by the raw straw 2.9 mg / g.
  • Raw materials wheat straw, cellulose content 30-40%.
  • An acid fuchsin solution was prepared at a concentration of 1000 mg / L. Weigh 0.1g of the three irradiated wheat straw porous materials prepared in this example, and use the chopped raw wheat straw as a control, add 10mL of 1000mg / L acid red solution, and shake horizontally for 2 hours (200 rpm) . As shown in Figure 13, the UV absorption spectrum of the supernatant shows that the removal of acid fuchsin by the irradiated wheat straw porous adsorbent material is greater than 85.8 mg / g, which is much higher than the removal of acid fuchsin by raw wheat straw 6.2 mg / g. .
  • An acid blue solution was prepared at a concentration of 1000 mg / L.
  • the ultraviolet absorption spectrum of the supernatant showed that the amount of acid blue removed by the irradiated wheat straw porous adsorbent was greater than 90.2 mg / g, which was much higher than the amount of acid blue removed by the raw wheat straw 5.9 mg / g.
  • a cobalt chloride solution was prepared at a concentration of 1000 mg / L.
  • the atomic absorption spectrum of the supernatant shows that the removal amount of cobalt chloride by the irradiated wheat straw porous adsorption material can reach at least 167.4 mg / g, which is much higher than the removal amount of raw material straw by 8.7 mg / g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A porous biomass adsorbing material, and a preparation method and application thereof. The porous biomass adsorbing material is prepared by the following method: irradiating a biomass material in air with no less than 10 kGy of irradiation dose; dispersing the irradiated biomass material in a mixed aqueous solution of sodium hydroxide and urea or a mixed aqueous solution of sodium hydroxide and thiourea, stirring at a normal temperature after freezing, and filtering to obtain a biomass sol; subjecting the biomass sol to gelatinization to obtain a biomass gel, and washing to neutral to obtain an amidated porous biomass adsorbing material. The biomass adsorbing material has the advantages that no post-modification is required, an amino group can be introduced into a main chain of a biomass molecule by one step, functionalization of the porous biomass material is implemented, and purification of high-chroma wastewater of industries and food can be implemented.

Description

一种生物质多孔吸附材料及其制备方法与应用Biomass porous adsorption material, preparation method and application thereof 技术领域Technical field
本发明属于污水处理领域，尤其是属于色度废水处理领域，涉及一种生物质多孔吸附材料及其制备方法与应用。The invention belongs to the field of sewage treatment, in particular to the field of chroma wastewater treatment, and relates to a porous porous adsorbent material and a preparation method and application thereof.
背景技术Background technique
随着我国经济、社会的迅速发展，水体污染日趋严重，严重影响水中生物、人类的健康。色度是水体水质污染的一个重要指标。结构上含有发色基团、共轭结构和助色基团的物质都能引起水体色度升高。With the rapid development of China's economy and society, water pollution has become increasingly serious, seriously affecting the health of aquatic life and humans. Chroma is an important indicator of water pollution. Substances that contain chromophores, conjugated structures, and chromophoric groups can cause the color of water to increase.
色度污水具有成分复杂、色度深、盐度高、酸碱性强等特点。1)成分复杂。色度污水中不仅包含有色的有机物，还有铁、铜、锰等一些有色重金属离子，对人类、鱼类有强致癌、致突变作用。2)色度深。色度污水中的有机物多以苯、奈、蒽、醌等芳香基团为母体，色度深，光线难以进入河流，植物(藻类等)不能进行光合作用，严重影响排入水域的生态环境3)盐度高。色度污水中多含有氯化物、硫化物等无机盐，浓度高、毒性大。4)化学需氧量(COD)高、可生化性差。苯系、奈系、蒽醌系、苯胺系、硝基系、酚类等有机物的生化需氧量(BOD)/COD的值较低，微生物降解能力差。Chroma sewage has the characteristics of complex composition, deep chroma, high salinity, strong acidity and alkalinity. 1) The composition is complicated. Chroma sewage contains not only colored organic substances, but also some colored heavy metal ions such as iron, copper, and manganese, which have strong carcinogenic and mutagenic effects on humans and fish. 2) Deep chroma. The organic matter in chroma sewage is mostly based on aromatic groups such as benzene, naphthalene, anthracene, quinone, etc. The chroma is deep, the light is difficult to enter the river, and plants (algae, etc.) cannot perform photosynthesis, which seriously affects the ecological environment discharged into waters ) High salinity. Chroma sewage contains inorganic salts such as chlorides and sulfides, with high concentration and high toxicity. 4) High chemical oxygen demand (COD) and poor biodegradability. Organic compounds such as benzene, naphthalene, anthraquinone, aniline, nitro, and phenols have low BOD / COD values and poor microbial degradation capacity.
目前色度污水的主要脱色方法有：絮凝法、氧化法、生化法和吸附法。絮凝法是通过絮凝剂压缩双电层、电中和、桥梁作用和网捕沉降等机理，实现高色度污水的脱色。絮凝法工艺成熟，脱色效果稳定。但絮凝沉降后产生的淤泥无法回收，造成环境的二次污染。氧化法是利用氧化剂破坏有机物的发色基团，实现高色度污水的脱色。其中，Fenton法氧化能力强，反应条件温和，适用范围广。但处理过程中会产生大量需要焚烧处理的淤泥，造成环境的二次污染。光催化氧化法具有能效高、脱色效率高、淤泥降解彻底等优点。但催化剂的分离与回收难，增加了安全隐患，限制了光催化氧化技术的应用。电化学氧化法无需化学试剂、不产生淤泥、降解产业无毒害，处理后污水可直接排放。因此，提升电极材料的催化性能、脱色稳定性，降低能耗，是电化学氧化法的重点研究方向。生化法是利用微生物降解有色物质实现高色度污水的脱色的方法，微生物对有色物质的分解具有选择性，因此单一族群微生物对色度污水的总体脱色效果较差。吸附法是依靠物理吸附、化学吸附、交换吸附等方式去除色度污水中高色度物质的方法，具有吸附方法简单、脱色效果稳定等优点。多孔活性炭最常用的色度吸附剂。但是，吸附饱和后需通过热蒸汽再生活性炭，步骤繁琐、费用高昂。因此，开发一种具有高丰度活性基团、价格低廉、安全无毒、不造成二次污染的新型生物质吸附剂 极具科学价值和市场价值。At present, the main decolorization methods of chroma sewage include flocculation method, oxidation method, biochemical method and adsorption method. The flocculation method uses the flocculant to compress the electric double layer, electric neutralization, bridge action, and net capture sedimentation to realize the decolorization of high-color wastewater. The flocculation process is mature and the decolorization effect is stable. However, the sludge produced after flocculation and settlement cannot be recovered, causing secondary pollution to the environment. The oxidation method is to use oxidants to destroy the chromophores of organic matter, and to realize the decolorization of high-color wastewater. Among them, Fenton method has strong oxidation ability, mild reaction conditions, and wide application range. However, a large amount of sludge that needs to be incinerated will be generated during the process, causing secondary pollution to the environment. The photocatalytic oxidation method has the advantages of high energy efficiency, high decolorization efficiency, and complete sludge degradation. However, it is difficult to separate and recover the catalyst, which increases hidden safety hazards and limits the application of photocatalytic oxidation technology. The electrochemical oxidation method does not require chemical reagents, does not produce sludge, and is non-toxic to the degradation industry. The treated sewage can be directly discharged. Therefore, improving the catalytic performance, decolorization stability, and reducing energy consumption of electrode materials are the key research directions of electrochemical oxidation methods. The biochemical method is a method for decoloring high-color wastewater by using microorganisms to degrade colored substances. Microorganisms have the ability to selectively decompose colored substances. Therefore, the overall decolorization effect of single-group microorganisms on color wastewater is poor. Adsorption method is a method of removing high chroma substances in chroma sewage by means of physical adsorption, chemical adsorption, exchange adsorption, etc. It has the advantages of simple adsorption method and stable decoloring effect. The most commonly used color adsorbent for porous activated carbon. However, after the adsorption is saturated, the activated carbon needs to be regenerated by hot steam, which is complicated and expensive. Therefore, it is of great scientific and market value to develop a new type of biomass adsorbent with high abundance of active groups, low price, safety, non-toxicity, and no secondary pollution.
纤维素分子是由吡喃葡萄糖单体组成的长链分子，表面含有大量的羟基。目前文献报导的纤维素基功能材料，均充分利用了纤维素单体中的活性羟基，对其进行多步修饰，最终实现纤维素基材料功能化的目的。如，在纤维素分子表面引入季胺链，实现吸附阴离子染料的能力 [1]；通过接枝共聚丙烯酸、丙烯酰胺、N,N--亚甲基双丙烯酰胺，合成表面酰铵化的纤维素吸附剂，实现去除阴离子染料酸性蓝93(AB93)和阳离子染料亚甲基蓝(MB)的目的 [2]。但是，纤维素的修饰改性是一个相对复杂、繁琐的步骤，具有耗时长，修饰效率低等缺点。同时，在纤维素的修饰过程中不可避免的引入多种有机试剂，不仅污染环境，还在纤维素主体结构上引入了不可降解的物质对环境造成二次污染。另外，高纯纤维素的价格较高，不利于工业化生产。 Cellulose molecules are long-chain molecules composed of glucopyranose monomers, with a large number of hydroxyl groups on the surface. At present, the cellulose-based functional materials reported in the literature make full use of the active hydroxyl groups in the cellulose monomer, and perform multi-step modification to finally achieve the purpose of functionalizing the cellulose-based materials. For example, the introduction of quaternary amine chains on the surface of cellulose molecules to achieve the ability to adsorb anionic dyes [1] ; by graft copolymerization of acrylic acid, acrylamide, and N, N-methylenebisacrylamide, the surface ammonium fiber was synthesized Elemental adsorbent to remove the anionic dye Acid Blue 93 (AB93) and the cationic dye methylene blue (MB) [2] . However, cellulose modification is a relatively complicated and tedious step, which has the disadvantages of long time consuming and low modification efficiency. At the same time, many organic reagents are inevitably introduced in the cellulose modification process, which not only pollutes the environment, but also introduces non-degradable substances on the cellulose main structure to cause secondary pollution to the environment. In addition, the price of high-purity cellulose is high, which is not conducive to industrial production.
参考文献：references:
[1]Liqiang Jin,Qiucun Sun,Qinghua Xu,Yongjian Xu.Adsorptive removal of anionic dyes from aqueous solutions using microgel based on nanocellulose and polyvinylamine[J].Bioresource Technology,2015,197:348-355.[1] Liqiang Jin, Qiucun Sun, Qinghua Xu, Yongjian Xu.Adsorptive removal of anionic solutions from aqueous solutions using microgel based on nanocellulose and polyvinylamine [J] .Bioresource Technologies, 2015, 197: 348-348
[2]Liu L,Gao Z Y,Su X P,et al.Adsorption Removal of Dyes from Single and Binary Solutions Using a Cellulose-based Bioadsorbent[J].Acs Sustainable Chemistry,2015,3(3):150205104824003.[2] Liu, Gao, Z, Y, Su, X, P, et al. Adsorption, Removal, and Dyes from Single and Binary SolutionsUsing a Cellulose-based Bioadsorbent [J] .AcousSustainable, Chemistry, 2015, 3 (3): 150205104003
发明内容Summary of the Invention
本发明的目的是针对现有纤维素价格较高、修饰改性工艺较复杂、繁琐、耗时长，修饰效率低、引入具有安全隐患的有机基团等缺点，提供一种可以吸附多种阴离子染料、重金属离子、色素的生物质多孔吸附剂材料的制备方法及应用，该多孔吸附材料无需后修饰，一步在生物质分子主链上引入胺基，实现生物质多孔材料的功能化，可以实现工业、食品高色度废水的净化。The purpose of the present invention is to provide a kind of anionic dye that can absorb many kinds of anionic dyes in view of the disadvantages of high existing cellulose, complicated modification and modification process, tedious, time-consuming, low modification efficiency, introduction of organic groups with potential safety hazards, and the like. And application method of biomass porous adsorbent material for heavy metal ions and pigments, the porous adsorption material does not require post-modification, and introduces amine groups on the main chain of biomass molecules in one step to realize the functionalization of biomass porous materials, which can realize industry Purification of food high chroma wastewater.
本发明的目的是通过以下技术方案实现的：The object of the present invention is achieved by the following technical solutions:
一种生物质多孔吸附材料，它是由以下方法制得：空气中辐照生物质材料，辐照剂量不低于10kGy；将经过辐照处理的生物质材料分散于氢氧化钠和尿素混合水溶液或氢氧化钠和硫脲混合水溶液中，-30℃～0℃下冰冻30分钟～10小时，确保氢氧化钠、尿素/硫脲能够溶解纤维素(氢氧化钠、尿素/硫脲水溶液能到在0℃以下溶解)，冷冻后常温搅拌(2000～3000转/分钟)5～30分钟，过滤，得到生物质溶胶；生物质溶胶经凝胶化得到生物质凝胶，水洗至中性，得到酰胺化的多孔生物质吸附材料。A biomass porous adsorption material, which is prepared by the following methods: irradiating biomass material in air with an irradiation dose of not less than 10 kGy; dispersing the biomass material after irradiation treatment in a mixed aqueous solution of sodium hydroxide and urea Or in a mixed aqueous solution of sodium hydroxide and thiourea, freeze at -30 ° C to 0 ° C for 30 minutes to 10 hours to ensure that sodium hydroxide, urea / thiourea can dissolve cellulose (sodium hydroxide, urea / thiourea aqueous solution can reach Dissolve below 0 ° C), stir at room temperature (2000-3000 rpm) for 5-30 minutes, and then filter to obtain a biomass sol; gelatinize the biomass sol to obtain a biomass gel, and wash it to neutrality to obtain Amidated porous biomass adsorption material.
本发明所述的生物质多孔吸附材料的制备方法，其特征在于包括以下步骤：The method for preparing a porous biomass adsorption material according to the present invention is characterized by including the following steps:
步骤(1)、空气中辐照生物质材料，辐照剂量不低于10kGy；Step (1): The biomass material is irradiated in the air, and the irradiation dose is not less than 10kGy;
步骤(2)、将经过辐照处理的生物质材料分散于氢氧化钠和尿素混合水溶液或氢氧化钠和硫脲混合水溶液中，-12℃～0℃下冰冻30分钟～10小时，冷冻后常温搅拌5～30分钟(3000转/分钟)，过滤，得到生物质溶胶；Step (2) Disperse the irradiated biomass material in a mixed aqueous solution of sodium hydroxide and urea or a mixed aqueous solution of sodium hydroxide and thiourea, and freeze at -12 ° C to 0 ° C for 30 minutes to 10 hours. After freezing, Stir at room temperature for 5-30 minutes (3000 rpm) and filter to obtain a biomass sol;
步骤(3)、生物质溶胶经凝胶化得到生物质凝胶，水洗至中性，得到酰胺化的多孔生物质吸附材料。In step (3), the biomass sol is gelled to obtain a biomass gel, which is washed to neutrality to obtain an amidated porous biomass adsorption material.
步骤(1)中，所述的生物质材料为棉花、稻草、麦秆等。In step (1), the biomass material is cotton, straw, wheat straw, or the like.
辐照射线为放射性核素 60Co或 137Cs衰变时放射出的γ射线，其中高能电子束由高能电子加速器产生。 The radiation rays are gamma rays emitted when the radionuclide 60 Co or 137 Cs decays, and the high-energy electron beam is generated by the high-energy electron accelerator.
所述的辐照剂量优选为20-200kGy，进一步优选为40-100kGy。The irradiation dose is preferably 20-200 kGy, and more preferably 40-100 kGy.
步骤(2)中，经过辐照的生物质材料切碎。常温下，采用磁力搅拌将经过辐照处理的生物质材料分散于氢氧化钠和尿素混合水溶液或氢氧化钠和硫脲混合水溶液中，搅拌时间5-15分钟，转速1000-3000转/分钟。In step (2), the irradiated biomass material is shredded. At room temperature, the magnetically stirred biomass material is dispersed in a mixed aqueous solution of sodium hydroxide and urea or a mixed aqueous solution of sodium hydroxide and thiourea using magnetic stirring. The stirring time is 5-15 minutes, and the rotation speed is 1000-3000 rpm.
所述的经过辐照处理的生物质材料与氢氧化钠和尿素混合水溶液或氢氧化钠和硫脲混合水溶液的质量比为5～10:90～95，优选为5:95。The mass ratio of the irradiated biomass material and the mixed aqueous solution of sodium hydroxide and urea or the mixed aqueous solution of sodium hydroxide and thiourea is 5-10: 90-95, and preferably 5:95.
所述的氢氧化钠和尿素混合水溶液中氢氧化钠、尿素与水的质量比为3～10:5～15:75～92，优选为3～8:10～15:77～87。The mass ratio of sodium hydroxide, urea, and water in the mixed aqueous solution of sodium hydroxide and urea is 3 to 10: 5 to 15:75 to 92, and preferably 3 to 8:10 to 15:77 to 87.
所述的氢氧化钠和硫脲混合水溶液中氢氧化钠、硫脲与水的质量比为3～10:5～15:75～92，优选为3～8:10～15:77～87。The mass ratio of sodium hydroxide, thiourea, and water in the mixed aqueous solution of sodium hydroxide and thiourea is 3 to 10: 5 to 15:75 to 92, and preferably 3 to 8:10 to 15:77 to 87.
步骤(3)中，所述的生物质溶胶在20～80℃下静置12～72小时凝胶化得到生物质凝胶。In step (3), the biomass sol is allowed to stand for gelation at 20 to 80 ° C. for 12 to 72 hours to obtain a biomass gel.
本发明所述的常温为20～35℃。The normal temperature according to the present invention is 20 to 35 ° C.
本发明的另一个目的是提供所述的生物质多孔吸附材料在防治色度污水中的应用。Another object of the present invention is to provide the application of the biomass porous adsorbent material in the prevention and treatment of chromatic waste water.
所述的色度污水中含有铜离子、铁离子、钴离子、锰离子、甲基橙、酸性黑、酸性红、酸性蓝、亚甲基蓝、甲基绿、焦糖色素、胭脂红、柠檬黄、日落黄、亮蓝中的至少一种。The chromaticity sewage contains copper ion, iron ion, cobalt ion, manganese ion, methyl orange, acid black, acid red, acid blue, methylene blue, methyl green, caramel color, carmine, lemon yellow, and sunset At least one of yellow and bright blue.
优选的，所述的色度污水为有色重金属污水、染料废水或色素废水。Preferably, the chromaticity wastewater is non-ferrous heavy metal wastewater, dye wastewater or pigment wastewater.
本发明的有益效果：The beneficial effects of the present invention:
本发明采用辐照能够有效破坏原料生物质材料的纤维内部结构，生物质吸附材料无需后修饰，一步在生物质分子主链上引入胺基，实现生物质多孔材料的功能化，同时由于生物质吸附材料存在大量微米级的孔洞，有效增加了材料的比表面积，同时可以实现工业、食品高 色度废水的净化。具体表现为：The invention adopts irradiation to effectively destroy the fiber internal structure of the raw material biomass material, and the biomass adsorption material does not need to be modified. In one step, an amine group is introduced into the main chain of the biomass molecule to realize the functionalization of the porous material of the biomass. There are a large number of micron-sized holes in the adsorbent material, which effectively increases the specific surface area of the material, and at the same time, it can realize the purification of industrial and food high-chroma wastewater. The specific performance is:
(1)、2小时内，每克多孔材料对甲基橙、酸性黑、酸性红、酸性蓝的去除率不小于75％；(1) Within 2 hours, the removal rate of methyl orange, acid black, acid red and acid blue per gram of porous material is not less than 75%;
(2)、2小时内，每克多孔材料对10mL、500mg/L亚甲基蓝、甲基绿的去除率不小于70％。(2) Within 2 hours, the removal rate of 10 mL, 500 mg / L of methylene blue and methyl green per gram of porous material is not less than 70%.
(3)、2小时内，每克多孔材料对10mL、500mg/L氯化铁、硫酸铜、氯化锰、氯化钴的去除率不小于70％。(3) Within 2 hours, the removal rate of 10 mL, 500 mg / L ferric chloride, copper sulfate, manganese chloride, and cobalt chloride per gram of porous material is not less than 70%.
(4)、2小时内，每克多孔材料对10mL、500mg/L焦糖色素、胭脂红、柠檬黄、日落黄、亮蓝的去除率不小于70％。(4) Within 2 hours, the removal rate of 10mL, 500mg / L caramel, carmine, lemon yellow, sunset yellow, and bright blue per gram of porous material is not less than 70%.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1新疆长绒棉的溶胶照片。FIG. 1 is a sol photograph of Xinjiang long-staple cotton of Example 1. FIG.
图2为实施例1材料的微观形貌图；其中A为辐照10kGy长绒棉制备的生物质多孔材料的SEM图，放大10000倍；B为辐照40kGy长绒棉制备的生物质多孔材料的SEM图，放大10000倍；C为辐照80kGy长绒棉制备的生物质多孔材料的SEM图，放大10000倍；D为原料新疆长绒棉的SEM图，放大500倍；E为未经辐照的新疆长绒棉经氢氧化钠/尿素处理后的SEM图。FIG. 2 is a microscopic morphology of the material of Example 1; wherein A is a SEM image of a biomass porous material prepared by irradiating 10kGy long-staple cotton, magnified 10000 times; B is a biomass porous material prepared by irradiating 40kGy long-staple cotton SEM image of 10000 times magnification; C is SEM image of biomass porous material prepared by irradiating 80kGy long-staple cotton, magnified 10,000 times; D is SEM image of raw Xinjiang long-staple cotton, magnified 500 times; E is unradiated Photograph of Xinjiang long-staple cotton treated with sodium hydroxide / urea.
图3实施例1辐照长绒棉多孔吸附材料对甲基橙的去除效果图。FIG. 3 is a diagram showing the removal effect of methyl orange by the irradiated long-staple cotton porous adsorbent in Example 1. FIG.
图4实施例1辐照长绒棉多孔吸附材料对甲基绿的去除效果图。FIG. 4 is a diagram showing the removal effect of methyl green by the irradiated long-staple cotton porous adsorbent in Example 1. FIG.
图5实施例1辐照长绒棉多孔吸附材料对硫酸铜的去除效果图。FIG. 5 is a diagram showing the removal effect of copper sulfate by the irradiated long-staple cotton porous adsorbent in Example 1. FIG.
图6实施例1辐照长绒棉多孔吸附材料对焦糖色素的去除效果图。FIG. 6 is a diagram showing the removal effect of caramel pigment in a porous long-staple cotton absorbent material according to Example 1;
图7实施例1辐照长绒棉多孔吸附材料对胭脂红色素的去除效果图。FIG. 7 is a diagram showing the removal effect of carmine pigment by the irradiated long-staple cotton porous adsorbent in Example 1. FIG.
图8实施例2辐照稻草多孔吸附材料对酸性黑1的去除效果图。FIG. 8 is a diagram showing the removal effect of acid black 1 by a porous straw adsorbent in Example 2 in irradiation.
图9实施例2辐照稻草多孔吸附材料对亚甲基蓝的去除效果图。FIG. 9 is a diagram showing the removal effect of methylene blue by a porous straw adsorbent in Example 2 in irradiation.
图10实施例2辐照稻草多孔吸附材料对氯化铁的去除效果图。FIG. 10 is a diagram showing the removal effect of ferric chloride by the porous straw adsorbing material in Example 2 of Example 2.
图11实施例2辐照稻草多孔吸附材料对柠檬黄的去除效果图。FIG. 11 is a diagram showing the removal effect of lemon yellow by irradiation of the straw porous adsorbent in Example 2;
图12实施例2辐照稻草多孔吸附材料对日落黄的去除效果图。FIG. 12 is a diagram showing the removal effect of sunset yellow of the straw porous adsorbent in Example 2 on irradiation.
图13实施例3辐照麦秆多孔吸附材料对酸性品红的去除效果图。FIG. 13 is a diagram showing the removal effect of acid fuchsin by the irradiated wheat straw porous adsorbent in Example 3.
图14实施例3辐照麦秆多孔吸附材料对酸性蓝的去除效果图。FIG. 14 is a diagram showing the removal effect of acid blue by the wheat straw porous adsorbent in Example 3;
图15实施例3辐照麦秆多孔吸附材料对氯化钴的去除效果图。FIG. 15 is a diagram showing the removal effect of cobalt chloride by a wheat straw porous adsorbent in Example 3;
图16实施例3辐照麦秆多孔吸附材料对氯化锰的去除效果图。FIG. 16 is a diagram showing the removal effect of manganese chloride by the irradiated wheat straw porous adsorbent in Example 3.
具体实施方式detailed description
通过具体实施方式对本发明的技术方案作进一步说明。The technical solution of the present invention is further described through specific embodiments.
实施例1Example 1
原材料：新疆长绒棉，纤维长度为38-39.7毫米，细度7510米/克。Raw material: Xinjiang long-staple cotton, with a fiber length of 38-39.7 mm and a fineness of 7510 m / g.
1、 60Co-γ-射线辐照新疆长绒棉 1.60 Co-γ-ray irradiation of Xinjiang long-staple cotton
称取3份500g的新疆长绒棉装入大小适宜的塑料袋中，自然、室温条件下采用 60Co-γ-射线辐照，辐照辐射钴源强度为9.99x10 15Bq，辐照剂量分别为10kGy、40kGy和80kGy。辐照后样品常温贮藏备用。 Three 500g Xinjiang long-staple cottons were weighed and placed in a suitable plastic bag. 60 Co-γ-rays were irradiated under natural and room temperature conditions. The intensity of the cobalt source was 9.99x10 15 Bq. The irradiation doses were respectively 10kGy, 40kGy, and 80kGy. After irradiation, the samples were stored at room temperature for future use.
2、制备多孔材料2. Preparation of porous materials
称取5g的经过辐照处理的新疆长绒棉，搅拌(1000转/分钟)分散在95g的氢氧化钠和尿素的混合水溶液(氢氧化钠、尿素和水的质量比为3:12:85)中，-12℃下冰冻30分钟，经过辐照处理的3份新疆长绒棉溶解，冰冻后常温搅拌(2000转/分钟)5分钟，真空抽滤去除不溶物，得到透明的长绒棉溶胶(图1)。长绒棉溶胶在50℃下静置36小时得到长绒棉凝胶，纯水清洗至中性，得到辐照长绒棉多孔吸附材料。Weigh 5g of Xinjiang long-staple cotton after irradiation treatment and stir (1000 rpm) to disperse in a mixed aqueous solution of 95g sodium hydroxide and urea (the mass ratio of sodium hydroxide, urea and water is 3:12:85 ), Frozen at -12 ° C for 30 minutes, 3 parts of Xinjiang long-staple cotton after dissolution were dissolved, and stirred at room temperature (2000 rpm) for 5 minutes after freezing, and vacuum-filtered to remove insoluble matter to obtain transparent long-staple cotton Sol (Figure 1). The long-staple cotton sol was left to stand at 50 ° C for 36 hours to obtain a long-staple cotton gel. The long-staple cotton sol was washed with pure water to neutrality to obtain an irradiated long-staple cotton porous adsorption material.
以未经过辐照的新疆长绒棉作为对照，结果表明，未辐照的新疆长绒棉在低温下不能溶于氢氧化钠和尿素的混合水溶液(图1)，经过-12℃下冰冻后的纤维SEM见图2E，对比原料长绒棉纤维的微观形貌图(图2D)，可以发现纤维的微观形貌没有明显变化。可见，未辐照的长绒棉不能通过本发明方法制备多孔材料。对比图2D中长绒棉纤维，可以看到，本实施例制得的多孔吸附材料存在大量微米级的孔洞，有效增加了材料的比表面积。说明辐照能够有效的破坏原始纤维的内部结构，从而制备纤维素基多孔吸附材料。The unirradiated Xinjiang long-staple cotton was used as a control. The results showed that the non-irradiated Xinjiang long-staple cotton was insoluble in a mixed aqueous solution of sodium hydroxide and urea at low temperature (Fig. 1), and was frozen at -12 ° C. The fiber SEM is shown in Figure 2E. Comparing the micro-morphology of the raw long-staple cotton fiber (Figure 2D), it can be found that the micro-morphology of the fiber has not changed significantly. It can be seen that unirradiated long-staple cotton cannot be used to prepare porous materials by the method of the present invention. Comparing the long-staple cotton fibers in FIG. 2D, it can be seen that the porous adsorption material prepared in this embodiment has a large number of micron-sized holes, which effectively increases the specific surface area of the material. It shows that irradiation can effectively destroy the internal structure of virgin fibers, and thus prepare cellulose-based porous adsorption materials.
配制浓度为1000mg/L的甲基橙溶液。分别称取0.1g本实施例制得的3种辐照长绒棉多孔吸附材料，以原料新疆充绒棉作为对照，加入20mL1000mg/L的甲基橙溶液，水平震荡2小时(200转/分钟)。如图3，上清液的紫外吸收光谱显示，辐照长绒棉多孔吸附材料对甲基橙的去除量至少可达176.9mg/g，远高于原料长绒棉对甲基橙的去除量13.7mg/g。A methyl orange solution was prepared at a concentration of 1000 mg / L. Weigh 0.1g of three kinds of irradiated long-staple cotton porous adsorbent materials prepared in this example, and take Xinjiang raw material-filled cotton as a control, add 20mL of 1000mg / L methyl orange solution, and shake horizontally for 2 hours (200 rpm) ). As shown in Figure 3, the UV absorption spectrum of the supernatant shows that the removal of methyl orange by the porous long-staple cotton absorbent material can reach at least 176.9 mg / g, which is much higher than the removal of methyl orange by raw long-staple cotton. 13.7 mg / g.
配制浓度为500mg/L的甲基绿溶液。分别称取0.1g本实施例制得的4种辐照长绒棉多孔吸附材料，加入20mL 500mg/L的甲基绿溶液，水平震荡2小时(200转/分钟)。如图4，上清液的紫外吸收光谱显示，辐照长绒棉多孔吸附材料对甲基绿的去除量至少可达71.8mg/g，远高于原料长绒棉对甲基绿的去除量5.2mg/g。A 500 mg / L methyl green solution was prepared. Weigh 0.1g of four irradiated long-staple cotton porous adsorption materials prepared in this example, add 20mL of 500mg / L methyl green solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 4, the UV absorption spectrum of the supernatant shows that the removal of methyl green by the porous long-staple cotton absorbent material can reach at least 71.8 mg / g, which is much higher than the removal of methyl green by the raw long-staple cotton. 5.2mg / g.
配制浓度为1000mg/L的硫酸铜溶液。分别称取0.1g本实施例制得的3种辐照长绒棉多孔吸附材料，加入20mL1000mg/L的硫酸铜溶液，水平震荡2小时(200转/分钟)。如图5，上清液的原子吸收光谱显示，辐照长绒棉多孔吸附材料对硫酸铜的去除量至少可达 146.7mg/g，远高于原料长绒棉对硫酸铜的去除量7.1mg/g。A copper sulfate solution was prepared at a concentration of 1000 mg / L. Weigh 0.1g of three irradiated long-staple cotton porous adsorption materials prepared in this example, add 20mL of 1000mg / L copper sulfate solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 5, the atomic absorption spectrum of the supernatant shows that the removal of copper sulfate by the porous long-staple cotton absorbent material can reach at least 146.7 mg / g, which is much higher than the removal of copper sulfate by raw long-staple cotton. / g.
配制浓度为1000mg/L的焦糖色素溶液。分别称取0.1g本实施例制得的3种辐照长绒棉多孔吸附材料，加入50mL 1000mg/L的焦糖色素溶液，水平震荡2小时(200转/分钟)。如图6，上清液的紫外吸收光谱显示，辐照长绒棉多孔吸附材料对焦糖色素的去除量大于381.6mg/g，远高于原料长绒棉对焦糖色素的去除量24.8mg/g。A caramel pigment solution was prepared at a concentration of 1000 mg / L. Weigh 0.1g of the three types of irradiated long-staple cotton porous adsorption materials prepared in this example, add 50mL of a 1000mg / L caramel pigment solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 6, the UV absorption spectrum of the supernatant showed that the amount of caramel pigment removed from the porous long-staple cotton absorbent material was greater than 381.6 mg / g, which was much higher than the amount of caramel pigment removed from raw long-staple cotton 24.8 mg / g. .
配制浓度为500mg/L的胭脂红色素溶液。分别称取0.1g本实施例制得的3种辐照长绒棉多孔吸附材料，加入20mL 500mg/L的胭脂红色素溶液，水平震荡2小时(200转/分钟)。如图7，上清液的紫外吸收光谱显示，辐照长绒棉多孔吸附材料对胭脂红色素的去除量大于74.9mg/g，远高于原料长绒棉对胭脂红色素的去除量6.6mg/g。A carmine pigment solution was prepared at a concentration of 500 mg / L. Weigh 0.1g of three irradiated long-staple cotton porous adsorption materials prepared in this example, add 20mL of 500mg / L carmine pigment solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 7, the UV absorption spectrum of the supernatant shows that the amount of carmine pigment removed by the irradiated long-staple cotton porous adsorbent material is greater than 74.9 mg / g, which is much higher than that of the raw material long-staple cotton. / g.
实施例2Example 2
原材料：稻草，纤维素含量30-40％。Raw materials: straw, cellulose content 30-40%.
1、 60Co-γ-射线辐照稻草 1.60 Co-γ-ray irradiation straw
称取3份500g的稻草装入大小适宜的塑料袋中，自然、室温条件下采用 60Co-γ-射线辐照，辐照辐射钴源强度为9.99x1015Bq，辐照剂量分别为20kGy、50kGy和100kGy。辐照后样品常温贮藏备用。 Weigh 3 portions of 500g of straw into a suitable plastic bag, and irradiate with 60 Co-γ-rays under natural and room temperature conditions. The intensity of the cobalt source is 9.99x1015Bq. 100kGy. After irradiation, the samples were stored at room temperature for future use.
2、制备多孔材料2. Preparation of porous materials
称取5g经过辐照处理的稻草，切碎，搅拌(1000转/分钟)分散在95g的氢氧化钠和硫脲的混合水溶液(氢氧化钠、硫脲和水的质量比为5:9:86)中，冰冻后0℃下搅拌(3000转/分钟)30分钟，真空抽滤去除不溶物，得到透明的稻草溶胶。稻草溶胶在30℃下静置72小时得到稻草凝胶，纯水清洗至中性，得到辐照稻草多孔吸附材料。Weigh 5g of irradiated straw, chopped, stirred (1000 rpm) and dispersed in 95g of a mixed aqueous solution of sodium hydroxide and thiourea (the mass ratio of sodium hydroxide, thiourea and water is 5: 9: 86), after freezing, stir (3000 rpm) at 0 ° C for 30 minutes, and remove insoluble matter by vacuum filtration to obtain a transparent straw sol. The straw sol was left to stand at 30 ° C. for 72 hours to obtain a straw gel, and the pure water was washed to neutrality to obtain a irradiated straw porous adsorption material.
配制浓度为1000mg/L的酸性黑1溶液。分别称取0.02g本实施例制得的3种辐照稻草多孔材料，采用切碎的原料稻草后作为对照，加入20mL1000mg/L的酸性黑1溶液，水平震荡2小时(200转/分钟)。如图8，上清液的紫外吸收光谱显示，辐照稻草多孔吸附材料对酸性黑1的去除量至少可达772.4mg/g，远高于原料稻草对酸性黑1的去除量48.9mg/g。An acid black 1 solution was prepared at a concentration of 1000 mg / L. Weigh 0.02g of the three kinds of irradiated straw porous materials prepared in this example, and use the chopped raw straw as a control, add 20mL of 1000mg / L acid black 1 solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 8, the UV absorption spectrum of the supernatant shows that the removal of acid black 1 by the porous straw adsorbent can reach at least 772.4 mg / g, which is much higher than the removal of acid black 1 by raw straw 48.9 mg / g. .
配制浓度为500mg/L的亚甲基蓝溶液。分别称取0.1g本实施例制得的3种辐照稻草多孔材料，加入20mL 500mg/L的亚甲基蓝溶液，水平震荡2小时(200转/分钟)。如图9，上清液的紫外吸收光谱显示，辐照稻草多孔吸附材料对亚甲基蓝的去除量至少可达72.9mg/g，远高于原料稻草对亚甲基蓝的去除量3.4mg/g。A methylene blue solution was prepared at a concentration of 500 mg / L. Weigh 0.1g of the three kinds of irradiated straw porous materials prepared in this example, add 20mL of 500mg / L methylene blue solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 9, the UV absorption spectrum of the supernatant showed that the removal of methylene blue by the irradiated straw porous adsorbent can reach at least 72.9 mg / g, which is much higher than the removal of methylene blue by the raw straw of 3.4 mg / g.
配制浓度为1000mg/L的氯化铁溶液。分别称取0.1g本实施例制得的3种辐照稻草多孔吸附材料，加入20mL1000mg/L的氯化铁溶液，水平震荡2小时(200转/分钟)。如图10， 上清液的原子吸收光谱显示，辐照稻草多孔吸附材料对氯化铁的去除量至少可达178.2mg/g，远高于原料稻草对氯化铁的去除量9.4mg/g。Prepare a ferric chloride solution with a concentration of 1000 mg / L. Weigh 0.1g of the three kinds of irradiated straw porous adsorption materials prepared in this example, add 20mL of 1000mg / L ferric chloride solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 10, the atomic absorption spectrum of the supernatant shows that the amount of ferric chloride removed by the irradiated straw porous adsorbent can reach at least 178.2 mg / g, which is much higher than the amount of ferric chloride removed by raw straw 9.4 mg / g. .
配制浓度为500mg/L的柠檬黄色素溶液。分别称取0.1g本实施例制得的3种辐照稻草多孔吸附材料，加入20mL 500mg/L的柠檬黄色素溶液，水平震荡2小时(200转/分钟)。如图11，上清液的紫外吸收光谱显示，辐照稻草多孔吸附材料对柠檬黄色素的去除量大于81.3mg/g，远高于原料稻草对柠檬黄的去除量2.9mg/g。A lemon yellow pigment solution was prepared at a concentration of 500 mg / L. Weigh 0.1g of three irradiated straw porous adsorption materials prepared in this example, add 20mL 500mg / L lemon yellow pigment solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 11, the UV absorption spectrum of the supernatant showed that the amount of lemon yellow pigment removed by the irradiated straw porous adsorbent was greater than 81.3 mg / g, which was much higher than the amount of lemon yellow removed by the raw straw 2.9 mg / g.
配制浓度为500mg/L的日落黄色素溶液。分别称取0.1g本实施例制得的3种辐照稻草多孔吸附材料，加入20mL 500mg/L的日落黄色素溶液，水平震荡2小时(200转/分钟)。如图12，上清液的紫外吸收光谱显示，辐照稻草多孔吸附材料对日落黄色素的去除量大于84.6mg/g，远高于原料稻草对日落黄的去除量3.1mg/g。Prepare a sunset yellow pigment solution with a concentration of 500mg / L. Weigh 0.1g of three kinds of irradiated straw porous adsorption materials prepared in this example, add 20mL of 500mg / L sunset yellow pigment solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 12, the UV absorption spectrum of the supernatant showed that the amount of sunset yellow pigment removed by the irradiated straw porous adsorbent material was more than 84.6 mg / g, which was much higher than the amount of 3.1 yellow yellow rice straw removed by sunset.
实施例3Example 3
原材料：麦秆，纤维素含量30-40％。Raw materials: wheat straw, cellulose content 30-40%.
1、 60Co-γ-射线辐照麦秆 1, 60 Co-γ- ray irradiation straw
分别称取3份500g的稻草装入大小适宜的塑料袋中，自然、室温条件下采用 60Co-γ-射线辐照，辐照辐射钴源强度为9.99x10 15Bq，辐照剂量分别为30kGy、50kGy和150kGy。辐照后样品常温贮藏备用。 Three 500g straws were weighed into plastic bags of appropriate size, and 60 Co-γ-rays were irradiated under natural and room temperature conditions. The intensity of the cobalt source was 9.99x10 15 Bq, and the irradiation doses were 30kGy. , 50kGy, and 150kGy. After irradiation, the samples were stored at room temperature for future use.
2、制备多孔材料2. Preparation of porous materials
称取5g经过辐照处理的辐照麦秆，切碎，搅拌(1000转/分钟)分散在95g的氢氧化钠和尿素的混合水溶液(氢氧化钠、尿素和水的质量比为7:14:79)中，-5℃下静置30分钟，冰冻后常温搅拌(3000转/分钟)5分钟，真空抽滤去除不溶物，得到透明的麦秆溶胶。麦秆溶胶在30℃下静置28小时得到麦秆凝胶，纯水清洗至中性，得到辐照麦秆多孔吸附材料。Weigh 5 g of the irradiated wheat straw after irradiation treatment, chopped, stirred (1000 rpm) and dispersed in 95 g of a mixed aqueous solution of sodium hydroxide and urea (the mass ratio of sodium hydroxide, urea and water is 7:14 : 79), stand still at -5 ° C for 30 minutes, and stir at room temperature (3000 rpm) for 5 minutes after freezing, and vacuum filter to remove insolubles to obtain a transparent wheat straw sol. The straw sol was left to stand at 30 ° C for 28 hours to obtain a straw gel, and the pure straw was washed to neutrality to obtain a porous straw absorbing material.
配制浓度为1000mg/L的酸性品红溶液。分别称取0.1g本实施例制得的3种辐照麦秆多孔材料，采用切碎的原料麦秆后作为对照，加入10mL1000mg/L的酸性红溶液，水平震荡2小时(200转/分钟)。如图13，上清液的紫外吸收光谱显示，辐照麦秆多孔吸附材料对酸性品红的去除量大于85.8mg/g，远高于原料麦秆对酸性品红的去除量6.2mg/g。An acid fuchsin solution was prepared at a concentration of 1000 mg / L. Weigh 0.1g of the three irradiated wheat straw porous materials prepared in this example, and use the chopped raw wheat straw as a control, add 10mL of 1000mg / L acid red solution, and shake horizontally for 2 hours (200 rpm) . As shown in Figure 13, the UV absorption spectrum of the supernatant shows that the removal of acid fuchsin by the irradiated wheat straw porous adsorbent material is greater than 85.8 mg / g, which is much higher than the removal of acid fuchsin by raw wheat straw 6.2 mg / g. .
配制浓度为1000mg/L的酸性蓝溶液。分别称取0.1g本实施例制得的3种辐照麦秆多孔吸附材料，加入10mL 1000mg/L的酸性蓝溶液，水平震荡2小时(200转/分钟)。如图14，上清液的紫外吸收光谱显示，辐照麦秆多孔吸附材料对酸性蓝的去除量大于90.2mg/g，远高于原料麦秆对酸性蓝的去除量5.9mg/g。An acid blue solution was prepared at a concentration of 1000 mg / L. Weigh 0.1g of three irradiated wheat straw porous adsorption materials prepared in this example, add 10mL 1000mg / L acid blue solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 14, the ultraviolet absorption spectrum of the supernatant showed that the amount of acid blue removed by the irradiated wheat straw porous adsorbent was greater than 90.2 mg / g, which was much higher than the amount of acid blue removed by the raw wheat straw 5.9 mg / g.
配制浓度为1000mg/L的氯化钴溶液。分别称取0.1g本实施例制得的3种辐照麦秆多 孔吸附材料，加入20mL1000mg/L的氯化钴溶液，水平震荡2小时(200转/分钟)。如图15，上清液的原子吸收光谱显示，辐照麦秆多孔吸附材料对氯化钴的去除量至少可达167.4mg/g，远高于原料稻草对氯化钴的去除量8.7mg/g。A cobalt chloride solution was prepared at a concentration of 1000 mg / L. Weigh 0.1g of the three kinds of irradiated wheat straw porous adsorbents prepared in this example, add 20mL of 1000mg / L cobalt chloride solution, and shake horizontally for 2 hours (200 rpm). As shown in Fig. 15, the atomic absorption spectrum of the supernatant shows that the removal amount of cobalt chloride by the irradiated wheat straw porous adsorption material can reach at least 167.4 mg / g, which is much higher than the removal amount of raw material straw by 8.7 mg / g.
配制浓度为1000mg/L的氯化锰溶液。分别称取0.1g本实施例制得的3种辐照麦秆多孔吸附材料，加入20mL1000mg/L的氯化锰溶液，水平震荡2小时(200转/分钟)。如图16，上清液的原子吸收光谱显示，辐照麦秆多孔吸附材料对氯化锰的去除量至少可达181.9mg/g，远高于原料稻草对氯化锰的去除量12.2mg/g。Prepare a manganese chloride solution with a concentration of 1000 mg / L. Weigh 0.1g of the three types of irradiated wheat straw porous adsorption materials prepared in this example, add 20mL of a 1000mg / L manganese chloride solution, and shake horizontally for 2 hours (200 rpm). As shown in Figure 16, the atomic absorption spectrum of the supernatant shows that the removal of manganese chloride by the irradiated wheat straw porous adsorbent can reach at least 181.9 mg / g, which is much higher than the removal of manganese chloride by raw straw 12.2 mg / g.

Claims (10)

  1. 一种生物质多孔吸附材料，其特征在于它是由以下方法制得：空气中辐照生物质材料，辐照剂量不低于10kGy；将经过辐照处理的生物质材料分散于氢氧化钠和尿素混合水溶液或氢氧化钠和硫脲混合水溶液中，-12℃～0℃下冰冻30分钟～10小时，冷冻后常温搅拌5～30分钟，过滤，得到生物质溶胶；生物质溶胶经凝胶化得到生物质凝胶，水洗至中性，得到多孔生物质吸附材料。A biomass porous adsorption material, which is characterized in that it is prepared by the following methods: irradiating biomass material in the air with an irradiation dose of not less than 10 kGy; dispersing the biomass material after the irradiation treatment in sodium hydroxide and In a urea mixed aqueous solution or a sodium hydroxide and thiourea mixed aqueous solution, freeze at -12 ° C to 0 ° C for 30 minutes to 10 hours, stir at room temperature for 5 to 30 minutes, and filter to obtain a biomass sol; the biomass sol is gelled Biomass gel is obtained by washing with water to neutrality to obtain a porous biomass adsorption material.
  2. 根据权利要求1所述的生物质多孔吸附材料，其特征在于所述的生物质材料为棉花、稻草、麦秆。The porous porous adsorbent material according to claim 1, wherein the biomass material is cotton, straw, or wheat straw.
  3. 根据权利要求1所述的生物质多孔吸附材料，其特征在于辐照射线为放射性核素 60Co或 137Cs衰变时放射出的γ射线。 The porous porous adsorption material according to claim 1, wherein the radiation ray is a gamma ray emitted when the radionuclide 60 Co or 137 Cs decays.
  4. 根据权利要求1所述的生物质多孔吸附材料，其特征在于所述的经过辐照处理的生物质材料与氢氧化钠和尿素混合水溶液或氢氧化钠和硫脲混合水溶液的质量比为5～10:90～95；The porous porous adsorbent material according to claim 1, wherein the mass ratio of the irradiated biomass material and a mixed aqueous solution of sodium hydroxide and urea or a mixed aqueous solution of sodium hydroxide and thiourea is 5 to 10: 90 ～ 95;
    所述的氢氧化钠和尿素混合水溶液中氢氧化钠、尿素与水的质量比为3～10:5～15:75～92；The mass ratio of sodium hydroxide, urea and water in the mixed aqueous solution of sodium hydroxide and urea is 3 to 10: 5 to 15:75 to 92;
    所述的氢氧化钠和硫脲混合水溶液中氢氧化钠、硫脲与水的质量比为3～10:5～15:75～92。The mass ratio of sodium hydroxide, thiourea to water in the mixed aqueous solution of sodium hydroxide and thiourea is 3 to 10: 5 to 15:75 to 92.
  5. 根据权利要求4所述的生物质多孔吸附材料，其特征在于所述的经过辐照处理的生物质材料与氢氧化钠和尿素混合水溶液或氢氧化钠和硫脲混合水溶液的质量比为5:95；The porous porous adsorption material according to claim 4, characterized in that the mass ratio of the irradiated biomass material and a mixed aqueous solution of sodium hydroxide and urea or a mixed aqueous solution of sodium hydroxide and thiourea is 5: 95;
    所述的氢氧化钠和尿素混合水溶液中氢氧化钠、尿素与水的质量比为3～8:10～15:77～87；The mass ratio of sodium hydroxide, urea and water in the mixed aqueous solution of sodium hydroxide and urea is 3-8: 10-15: 77-87;
    所述的氢氧化钠和硫脲混合水溶液中氢氧化钠、硫脲与水的质量比为3～8:10～15:77～87。The mass ratio of sodium hydroxide, thiourea and water in the mixed aqueous solution of sodium hydroxide and thiourea is 3-8: 10-15: 77-87.
  6. 权利要求1所述的生物质多孔吸附材料的制备方法，其特征在于包括以下步骤：The method for preparing a porous porous adsorbent material according to claim 1, comprising the following steps:
    步骤(1)、空气中辐照生物质材料，辐照剂量不低于10kGy；其中，所述的生物质材料为棉花、稻草、麦秆；Step (1): The biomass material is irradiated in the air, and the radiation dose is not less than 10 kGy; wherein the biomass material is cotton, straw, and wheat straw;
    步骤(2)、将经过辐照处理的生物质材料分散于氢氧化钠和尿素混合水溶液或氢氧化钠和硫脲混合水溶液中，-12℃～0℃下冰冻30分钟～10小时，冷冻后常温搅拌5～30分钟，过滤，得到生物质溶胶；Step (2) Disperse the irradiated biomass material in a mixed aqueous solution of sodium hydroxide and urea or a mixed aqueous solution of sodium hydroxide and thiourea, and freeze at -12 ° C to 0 ° C for 30 minutes to 10 hours. After freezing, Stir for 5-30 minutes at room temperature and filter to obtain a biomass sol;
    步骤(3)、生物质溶胶经凝胶化得到生物质凝胶，水洗至中性，得到多孔生物质吸附材料。In step (3), the biomass sol is gelled to obtain a biomass gel, and then washed to neutrality to obtain a porous biomass adsorption material.
  7. 根据权利要求6所述的生物质多孔吸附材料的制备方法，其特征在于步骤(1)中，辐照射线为放射性核素 60Co或 137Cs衰变时放射出的γ射线。 The method for preparing a porous porous adsorbent according to claim 6, wherein in step (1), the radiation ray is gamma rays emitted when the radionuclide 60 Co or 137 Cs decays.
  8. 根据权利要求6所述的生物质多孔吸附材料的制备方法，其特征在于步骤(2)中，所述的经过辐照处理的生物质材料与氢氧化钠和尿素混合水溶液或氢氧化钠和硫脲混合水溶液的质量比为5～10:90～95；The method for preparing a porous porous adsorbent material according to claim 6, characterized in that in step (2), the radiation-treated biomass material is mixed with an aqueous solution of sodium hydroxide and urea or sodium hydroxide and sulfur The mass ratio of the urea mixed aqueous solution is 5 to 10: 90 to 95;
    所述的氢氧化钠和尿素混合水溶液中氢氧化钠、尿素与水的质量比为3～10:5～15:75～92；The mass ratio of sodium hydroxide, urea and water in the mixed aqueous solution of sodium hydroxide and urea is 3 to 10: 5 to 15:75 to 92;
    所述的氢氧化钠和硫脲混合水溶液中氢氧化钠、硫脲与水的质量比为3～10:5～15:75～92。The mass ratio of sodium hydroxide, thiourea to water in the mixed aqueous solution of sodium hydroxide and thiourea is 3 to 10: 5 to 15:75 to 92.
  9. 权利要求1所述的生物质多孔吸附材料在防治色度污水中的应用。The application of the porous porous adsorbent material according to claim 1 in the prevention and treatment of chromatic waste water.
  10. 根据权利要求1所述的应用，所述的色度污水中含有铜离子、铁离子、钴离子、锰离子、甲基橙、酸性黑、酸性红、酸性蓝、亚甲基蓝、甲基绿、焦糖色素、胭脂红、日落黄、亮蓝中的至少一种。The application according to claim 1, wherein the chromaticity sewage contains copper ions, iron ions, cobalt ions, manganese ions, methyl orange, acid black, acid red, acid blue, methylene blue, methyl green, and caramel At least one of pigment, carmine, sunset yellow, and bright blue.
PCT/CN2019/104754 2018-09-10 2019-09-06 Porous biomass adsorbing material, and preparation method and application thereof WO2020052502A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2020103640A AU2020103640A4 (en) 2018-09-10 2020-11-24 Porous Biomass Adsorbing Material, And Application Thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811052940.XA CN109126730B (en) 2018-09-10 2018-09-10 Biomass porous adsorption material and preparation method and application thereof
CN201811052940.X 2018-09-10

Related Child Applications (1)

Application Number Title Priority Date Filing Date
AU2020103640A Division AU2020103640A4 (en) 2018-09-10 2020-11-24 Porous Biomass Adsorbing Material, And Application Thereof

Publications (1)

Publication Number Publication Date
WO2020052502A1 true WO2020052502A1 (en) 2020-03-19

Family

ID=64824412

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/104754 WO2020052502A1 (en) 2018-09-10 2019-09-06 Porous biomass adsorbing material, and preparation method and application thereof

Country Status (2)

Country Link
CN (1) CN109126730B (en)
WO (1) WO2020052502A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109126730B (en) * 2018-09-10 2021-05-18 江苏省农业科学院 Biomass porous adsorption material and preparation method and application thereof
CN109482149A (en) * 2019-01-10 2019-03-19 海南省辐射环境监测站 A kind of novel VOCs adsorbent material and its absorption to VOCs
CN109731435B (en) * 2019-01-17 2021-10-29 江苏省农业科学院 Application of cellulose-based formaldehyde adsorbent in adsorption of formaldehyde
CN112108122B (en) * 2020-08-18 2023-03-10 江苏省农业科学院 Preparation method of burdock root residue porous adsorptive food raw material
CN115845799A (en) * 2022-11-17 2023-03-28 同济大学 Preparation method of low-temperature-alkali-hydrothermal biochar

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5019291B2 (en) * 2007-10-25 2012-09-05 国立大学法人群馬大学 Metal loading method on woody biomass, silver ion water production method, sodium ion water production method
CN102784621A (en) * 2012-08-29 2012-11-21 西南科技大学 Method for preparing biomass adsorption material based on modified rice husks
CN102921380A (en) * 2012-11-16 2013-02-13 重庆大学 Modification method for improving absorption performance of biomass carbon
CN103027194A (en) * 2013-01-09 2013-04-10 湖北祥源新材科技有限公司 Straw feed and irradiation processing method thereof
CN104785212A (en) * 2014-01-21 2015-07-22 中国科学院过程工程研究所 Biomass adsorbent, and preparation method and applications thereof
CN106390928A (en) * 2016-10-12 2017-02-15 昆明理工大学 Preparation method of active carbon based on cellulose aerogel, and applications thereof
CN109126730A (en) * 2018-09-10 2019-01-04 江苏省农业科学院 A kind of biomass porous adsorbent material and the preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102443180A (en) * 2011-09-15 2012-05-09 复旦大学 Method for preparing cellulose composite aerogel
CN103881148A (en) * 2014-02-23 2014-06-25 江苏省农业科学院 Preparation method for radiated corn starch-based biodegradation particles

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5019291B2 (en) * 2007-10-25 2012-09-05 国立大学法人群馬大学 Metal loading method on woody biomass, silver ion water production method, sodium ion water production method
CN102784621A (en) * 2012-08-29 2012-11-21 西南科技大学 Method for preparing biomass adsorption material based on modified rice husks
CN102921380A (en) * 2012-11-16 2013-02-13 重庆大学 Modification method for improving absorption performance of biomass carbon
CN103027194A (en) * 2013-01-09 2013-04-10 湖北祥源新材科技有限公司 Straw feed and irradiation processing method thereof
CN104785212A (en) * 2014-01-21 2015-07-22 中国科学院过程工程研究所 Biomass adsorbent, and preparation method and applications thereof
CN106390928A (en) * 2016-10-12 2017-02-15 昆明理工大学 Preparation method of active carbon based on cellulose aerogel, and applications thereof
CN109126730A (en) * 2018-09-10 2019-01-04 江苏省农业科学院 A kind of biomass porous adsorbent material and the preparation method and application thereof

Also Published As

Publication number Publication date
CN109126730B (en) 2021-05-18
CN109126730A (en) 2019-01-04

Similar Documents

Publication Publication Date Title
WO2020052502A1 (en) Porous biomass adsorbing material, and preparation method and application thereof
Sardar et al. Remediation of dyes from industrial wastewater using low-cost adsorbents
Wong et al. Potential and challenges of enzyme incorporated nanotechnology in dye wastewater treatment: A review
Gupta Application of low-cost adsorbents for dye removal–a review
Katheresan et al. Efficiency of various recent wastewater dye removal methods: A review
O’mahony et al. Reactive dye biosorption by Rhizopus arrhizus biomass
Ali et al. Biosorption of crystal violet from water on leaf biomass of Calotropis procera
Khalaf Biosorption of reactive dye from textile wastewater by non-viable biomass of Aspergillus niger and Spirogyra sp.
CN109265611B (en) Functionalized cellulose-based porous material and preparation method and application thereof
Ghaneian et al. Application of eggshell as a natural sorbent for the removal of reactive red 123 dye from synthetic textile wastewater
CN109999752B (en) Preparation method and application of multifunctional material for efficiently adsorbing and degrading organic pollutants
Jayarajan et al. Use of low cost nano-porous materials of pomelo fruit peel wastes in removal of textile dye
CN107321333A (en) A kind of preparation method for the hydrogel microsphere for adsorbing dye ions
Muhammad et al. Crystal violet removal from aqueous solution using corn stalk biosorbent
CN110756163A (en) Nano CoFe2O4Carbon fiber felt composite material and preparation method and application thereof
CN109999909A (en) Chitosan/diatomite/graphene oxide composite material and its preparation method and application
Ashraf et al. Methods for the treatment of wastewaters containing dyes and pigments
Ayed et al. Magnetic Fe3O4-natural iron ore/calcium alginate beads as heterogeneous catalyst for Novacron blue dye degradation in water by (photo) Fenton process
Prasanna A novel adsorption process for the removal of salt and dye from saline textile industrial wastewater using a three-stage reactor with surface modified adsorbents
AU2020103640A4 (en) Porous Biomass Adsorbing Material, And Application Thereof
McKay et al. Dye removal using biochars
Meko Adsorption of reactive dyes from textile wastewater using corn stalk activated carbon
Dhami et al. Adsorptive Removal of Malachite Green Dye from Aqueous Solution Using Chemically Modified Charred and Xanthated Wheat Bran
Huang et al. High-efficient biosorption of dye wastewater onto aerobic granular sludge and photocatalytic regeneration of biosorbent by acid TiO 2 hydrosol
Tran et al. Combination of photocatalytic degradation and adsorption in dye removal by TiO2-chitosan-glycerol beads under natural sunlight

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19860514

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19860514

Country of ref document: EP

Kind code of ref document: A1