WO2019011150A1 - 一种基于苹果酸和 KMnO4 联合改性牛粪沼渣水热炭的制备方法 - Google Patents

一种基于苹果酸和 KMnO4 联合改性牛粪沼渣水热炭的制备方法 Download PDF

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WO2019011150A1
WO2019011150A1 PCT/CN2018/094122 CN2018094122W WO2019011150A1 WO 2019011150 A1 WO2019011150 A1 WO 2019011150A1 CN 2018094122 W CN2018094122 W CN 2018094122W WO 2019011150 A1 WO2019011150 A1 WO 2019011150A1
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malic acid
cow dung
biogas residue
hydrothermal
kmno
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PCT/CN2018/094122
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French (fr)
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WO2019011150A9 (zh
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靳红梅
朱宁
奚永兰
孙恩惠
杜静
黄红英
叶小梅
郑孟杰
李丹阳
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江苏省农业科学院
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Priority to US16/485,114 priority Critical patent/US11235305B2/en
Priority to EP18832156.6A priority patent/EP3542896B1/en
Publication of WO2019011150A1 publication Critical patent/WO2019011150A1/zh
Publication of WO2019011150A9 publication Critical patent/WO2019011150A9/zh

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    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • 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
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia

Definitions

  • the invention relates to the field of adsorbing materials and water environment pollution control, in particular to a method for preparing a hydrothermal charcoal based on the combined modification of malic acid and KMnO 4 .
  • Biogas project is an effective way to treat manure from large-scale farms, and is especially suitable for aquaculture wastewater treatment.
  • China's biogas project has grown rapidly and has become a “standard” for scale farms.
  • biogas projects generate large amounts of fermentation residues (ie, biogas slurry and biogas residue) while producing biogas, and their production has exceeded 300 million tons per year.
  • the harmless treatment and resource utilization of biogas residue is an important way to make full use of resources and improve the income of biogas projects.
  • the cow dung biogas residue is produced in a large amount and rich in carbon source. It is an ideal raw material for the preparation of functional carbon materials. It can not only turn the biogas residue into treasure, but also prolong the biogas engineering industrial chain and increase the added value of the fermentation product.
  • the reaction temperature is usually above 300 °C, and the moisture content of the material generally does not exceed 10%; while hydrothermal carbonization (HTC) is water (often subcritical) State) is the reaction medium in which the biomass is converted to hydrothermal charcoal at a certain temperature (usually below 300 ° C) and pressure in a closed high pressure reactor.
  • HTC water (often subcritical) State) is the reaction medium in which the biomass is converted to hydrothermal charcoal at a certain temperature (usually below 300 ° C) and pressure in a closed high pressure reactor.
  • HTC is not restricted by the moisture content of raw materials. HTC has mild reaction conditions and simple operation. Dehydration and decarboxylation in the reaction process is accompanied by exothermic heat, which can reduce energy consumption. It is especially suitable for treating high residue (such as more than 85%). Waste, greatly reducing operating costs.
  • the cow dung biogas residue is alkaline (pH 7.3-7.7), and the water content is between 80% and 90%. It is especially suitable as a raw material for HTC.
  • the preparation conditions are similar to those of other hydrothermal carbon preparation methods.
  • the prepared biogas residue hot carbon material can be applied to the fields of anaerobic fermentation, adsorption of harmful substances in waste water, use of returning fields, etc., and has the advantages of increasing the volumetric gas production rate of the anaerobic fermentation system, increasing the removal rate of heavy metals in the water, and reducing the greenhouse gas. The role of emissions.
  • Chinese patent CN107352540 A discloses a hydrothermal method for preparing manganese oxide-loaded activated carbon and a device thereof
  • Chinese patent CN106128782 A discloses a nano-manganese tetraoxide/activated carbon composite material and a preparation method thereof, but these two documents
  • there is no treatment for modifying the activated carbon and there is also a problem of a low surface area. Therefore, on the basis of the original cow manure and slag hydrothermal charcoal, the development of modified carbon materials with high specific surface area, developed pore structure and stable properties has become a technical problem to be solved in the promotion of biogas residue hot coal.
  • the present invention provides a method for preparing a hydrothermal charcoal combined with modified malic acid and KMnO 4 with improved adsorption performance to improve the application value of hydrothermal charcoal in the field of adsorbent materials.
  • the method for preparing the modified cow dung biogas residue hydrothermal carbon comprises the following steps:
  • the digestive product of the cow dung biogas residue taken from the medium temperature complete mixed anaerobic reactor is referred to ( ⁇ , Fu Guangqing, Chang Zhizhou, Ye Xiaomei, Chen Guangyin, Du Jing, pig, cow dung anaerobic Nitrogen form transformation in fermentation and its distribution in biogas slurry and biogas residue, Journal of Agricultural Engineering).
  • step 2) Take the raw material of the cow dung biogas residue obtained in step 1), add 0.5-1.0 mol ⁇ L -1 malic acid solution, according to the solid-liquid ratio (w/v, kg/L) 1:6 to 1:10, fully After mixing evenly, ultrasonic (40KHz, 100W) for 40-90min under the condition of 35 ⁇ 85°C, the reactants are naturally cooled to room temperature (20 ⁇ 25°C), and fully washed with deionized water until the eluate is near. After neutral filtration, naturally air-dried or dried at 55-80 ° C, the malic acid-modified cow dung biogas residue can be obtained;
  • step 3 Take the malic acid modified cow dung biogas residue obtained in step 2), add 0.13 ⁇ 0.25mol ⁇ L -1 KMnO 4 solution to be fully mixed and then in the high temperature and high pressure reactor at a temperature of 180 ⁇ 220 ° C, time The hydrothermal reaction is carried out for 2 to 3 hours at a heating rate of 1 to 5 ° C ⁇ min -1 ; the solid-liquid ratio (w/v, kg/L) of the malic acid modified cow dung biogas residue and the KMnO 4 solution is 1: 5 to 1:10.
  • Step 3 After the reaction is cooled, the reaction product is thoroughly washed with deionized water until the eluate is near neutral, filtered, naturally air-dried or dried at 55-80 ° C to be modified. Sexual cow dung, slag, water, hot charcoal.
  • the method of the invention has the following beneficial effects :
  • the invention utilizes the method of combined modification of malic acid and KMnO 4 to modify the raw material, and to a certain extent, the richness of the C/O functional group in the hydrothermal carbon material can be increased by means of malic acid, and KMnO 4 can make the material.
  • the purpose of reaming and increasing pores is achieved; the specific surface area of the modified hydrothermal carbon is obviously increased, and the pore size distribution is mainly mesoporous.
  • the hydrothermal carbon material obtained by the method of the invention has high adsorption performance to harmful substances such as ammonia nitrogen (NH 4 + -N), and compared with the unmodified cow dung biogas residue hydrothermal carbon, the modified hot coal The highest adsorption amount is 12.14 times that of unmodified hot coal.
  • the invention selects the fermentation by-product - cow dung biogas residue as raw material, which is cheap and easy to obtain and reduces secondary pollution, and makes the waste resource utilization and high value utilization, and improves the application of the cow charcoal residue slag hot coal.
  • the effect and utilization value have promoted the benefits and development of biogas projects.
  • Figure 1 is a scanning electron microscope (SEM) image of modified and unmodified cow dung biogas residue hydrothermal charcoal.
  • (a) is unmodified hydrothermal carbon, and (b) is modified hydrothermal carbon.
  • Figure 2 is a schematic diagram showing the adsorption effect of modified and unmodified cow manure residue hydrothermal charcoal on different initial concentrations of ammonia nitrogen (NH 4 + -N).
  • Figure 3 is a schematic diagram showing the adsorption kinetics of ammonia and nitrogen (NH 4 + -N) on modified and unmodified cow dung biogas residue.
  • Figure 4 is a schematic diagram showing the adsorption effects of modified and unmodified cow dung biogas slag hot coal on different initial concentrations of ammonia nitrogen (NH 4 + -N) in the actual wastewater of pig farms.
  • test group
  • Control group The appropriate amount of cow dung biogas residue powder and deionized water were mixed well according to the solid-liquid ratio (w/v) of 1:8, and then hydrothermal reaction was carried out in a high temperature and high pressure reaction kettle.
  • the hydrothermal reaction temperature was 220 °C.
  • the hydrothermal reaction time is 2h
  • the heating rate is 1 ⁇ 5 ° C ⁇ min -1 ; after the reaction is cooled, it is washed with water until the eluate is near neutral, filtered, dried at 55-80 ° C to obtain unmodified (Control group) of cow dung biogas residue hot coal (Y-HTC).
  • both pore diameters are mainly mesopores, and the specific surface area of G-HTC is significantly improved compared with Y-HTC, which is increased by nearly 179.78%; the C/O content is in Y-HTC and G-HTC. Both ranked first, and the content of C/O in G-HTC was higher than that of Y-HTC.
  • FIG. 1 Scanning electron microscopy (SEM) images of G-HTC and Y-HTC are shown in Fig. 1. It can be seen from Fig. 1 that the unmodified hydrothermal charcoal Y-HTC (Fig. 1a) has a long trench on the surface and a small pore size. The porosity of the surface of the modified hydrothermal carbon G-HTC (Fig. 1b) is obviously improved and is honeycomb-like.
  • step 1) ultrasonic treatment in the temperature range of 35 ⁇ 85 ° C, 40KHz, 100W power ultrasonic treatment 40 ⁇ 90min, can achieve the purpose of the invention
  • the temperature of the hydrothermal reaction is 180 to 220 ° C, the time is 2 to 3 h, and the heating rate is 1 to 5 ° C / min, which can achieve the object of the invention.
  • Example 1 0.3 g of the G-HTC obtained in Example 1 was weighed into a 250 mL Erlenmeyer flask, and 100 mL of different concentrations (20 mg ⁇ L -1 , 50 mg ⁇ L -1 , 100 mg ⁇ L -1 ) of ammonia nitrogen (NH 4 + -N) were added. The solution was repeated three times in each experiment; it was shaken on a constant-temperature shaking shaker (28 ° C, 220 r ⁇ min -1 ) for 3 h, and after the adsorption equilibrium was reached, the supernatant was taken and passed through a 0.45 ⁇ m filter, and determined by an ultraviolet-visible spectrophotometer. The concentration of ammonia nitrogen (NH 4 + -N) in the filtrate, while taking the same procedure as above for the Y-HTC obtained in Example 1, was taken as a comparative example.
  • concentration of ammonia nitrogen (NH 4 + -N) in the filtrate while taking the same procedure as above for the Y-HTC obtained
  • Example 1 0.3 g of the G-HTC obtained in Example 1 was weighed into a 250 mL Erlenmeyer flask, and 100 mL of a solution of 100 mg ⁇ L -1 of ammonia nitrogen (NH 4 + -N) was added and shaken on a constant temperature shaking shaker (28 ° C, 220r ⁇ min -1 ), set different sampling time (0, 15, 30, 60, 90, 120, 150, 180min), and the supernatant was passed through a 0.45 ⁇ m filter, and the filtrate was measured by UV-visible spectrophotometer. The concentration of ammonia nitrogen (NH 4 + -N) in the same time, while taking the same steps as above for Y-HTC as a comparative example.
  • Liquid Liquid, the dilution of the raw solution with water to make the concentration of NH 4 + -N in the wastewater is 20, 50 and 100 mg ⁇ L -1 , respectively, shaking on a constant temperature shaking shaker (28 ° C, 220 r ⁇ min -1 ) for 3 h, taking the supernatant
  • the concentration of NH 4 + -N in the filtrate was measured by a UV-visible spectrophotometer through a 0.45 ⁇ m filter while taking the same procedure as above for Y-HTC as a comparative example.

Abstract

一种基于苹果酸和KMnO4联合改性牛粪沼渣水热炭的制备方法，首先将牛粪沼渣与苹果酸混合，进行超声处理，得到苹果酸改性牛粪沼渣；再与KMnO4在高温高压反应釜中进行水热反应，即得到联合改性牛粪沼渣水热炭材料。

Description

一种基于苹果酸和KMnO 4联合改性牛粪沼渣水热炭的制备方法 技术领域
本发明涉及吸附材料以及水环境污染治理领域，特别涉及一种基于苹果酸和KMnO 4联合改性牛粪沼渣水热炭的制备方法。
背景技术
沼气工程是规模养殖场粪污处理的有效途径，特别适合于养殖污水处理。近年来，我国沼气工程快速增长，几乎成为规模养殖场的“标配”。然而，沼气工程在产生沼气的同时，会产生大量发酵残余物(即沼液和沼渣)，其产生量已经超过3亿吨/年。对于沼渣进行无害化处理及资源化，是充分利用资源、提高沼气工程收益的重要途径。牛粪沼渣产生量大、富含碳源，是制备功能碳材料的理想原料，不仅可以将沼渣变废为宝，而且能延长沼气工程产业链，提高发酵产物附加值。
目前，应用较多的生物炭采用的多为热解炭化所得，其反应温度通常在300℃以上，且物料含水率一般不超过10％；而水热炭化(HTC)以水(常处于亚临界状态)为反应介质，在密闭的高压反应釜中以一定温度(通常在300℃以下)和压强将其中的生物质转化为水热炭。HTC不受原料含水率的制约，HTC反应条件温和、操作简单，反应过程中的脱水脱羧伴随着放热，可降低能耗，特别适合处理沼渣这类含水率高(通常在85％以上)的废弃物，大大降低了运行成本。牛粪沼渣偏碱性(pH值7.3～7.7)，含水率在80％～90％之间，特别适合作为HTC的原料，制备条件与其他水热炭制备方法相近。所制备的沼渣水热炭材料可应用于厌氧发酵、废水中有害物质吸附、还田利用等领域，具有提高厌氧发酵系统的容积产气率、增加水中重金属的去除率、降低温室气体排放的作用。
目前，以牛粪沼渣为原料制备水热炭的研究尚未见报道，但从已有的利用牛粪为原料制备的生物炭特性来看，比表面积普遍较低(Ke Wu，Ying Gao，Guangkuo Zhu，Jinjiao Zhu，Qiaoxia Yuan，Yingquan Chen，Mingzhi Cai，LiangFeng，Characterization of dairy manure hydrochar and aqueous phase products generated by hydrothermal carbonization at different temperatures，Journal of Analytical and Applied Pyrolysis)。这影响了其对污染物的吸附作用。
中国专利CN107352540 A公开了一种水热法制备负载锰氧化物活性炭的方 法及其装置，中国专利CN106128782 A公开了一种纳米四氧化三锰/活性炭复合材料及其制备方法，但这两篇文献同样未对活性炭采取改性的处理措施，同样存在表面积较低的问题。因此，在原有牛粪沼渣水热炭的基础上，开发出具有比表面积高、孔结构发达且性质稳定的改性炭材料，已成为推广沼渣水热炭的技术亟待解决的技术难题。
发明内容
针对上述问题，本发明提供一种吸附性能良好的苹果酸和KMnO 4联合改性牛粪沼渣水热炭的制备方法，以提高牛粪沼渣水热炭在吸附材料领域的应用价值。
具体而言，本发明提供的改性牛粪沼渣水热炭的制备方法，包括如下步骤：
1)将自然风干或烘干(烘箱温度为60～70℃)至含水率为7％～10％的牛粪沼渣研磨后过20目筛，得到牛粪沼渣原料；
本申请中，牛粪沼渣取自中温完全混合式厌氧反应器(CSTR)的消化产物参见(靳红梅，付广青，常志州，叶小梅，陈广银，杜静，猪、牛粪厌氧发酵中氮素形态转化及其在沼液和沼渣中的分布，农业工程学报)。
2)取步骤1)中得到的牛粪沼渣原料，加入0.5～1.0mol·L -1苹果酸溶液，按照固液比(w/v，kg/L)1：6～1：10，充分混合均匀后，35～85℃条件下超声(40KHz，100W)40～90min，待反应物自然冷却至室温(20～25℃)，用去离子水对其进行充分水洗，直至洗出液为近中性后过滤，自然风干或在55～80℃条件下烘干，即可得到苹果酸改性牛粪沼渣；
3)取步骤2)中得到的苹果酸改性牛粪沼渣，加入0.13～0.25mol·L -1KMnO 4溶液待充分混合均匀后于高温高压反应釜中，在温度180～220℃，时间为2～3h，升温速率1～5℃·min -1条件下进行水热反应；苹果酸改性牛粪沼渣和KMnO 4溶液的固液比(w/v，kg/L)为1:5～1:10。
4)步骤3)反应结束冷却后，再用去离子水对反应产物进行充分水洗，直至洗出液为近中性，过滤，自然风干或在55～80℃条件下烘干，即可得到改性牛粪沼渣水热炭。
与现有水热炭制备方法相比，本发明方法具有以下有益效果 ：
1)本发明利用苹果酸和KMnO 4联合改性的方法对原料进行改性，在一定程度上，可以借助苹果酸增加水热炭材料中含C/O官能团的丰富度，KMnO 4可使 材料达到扩孔、增孔的目的；改性水热炭比表面积明显增大，孔径分布以介孔为主。
2)本发明方法获得的水热炭材料对氨氮(NH 4 +-N)等有害物质具有高吸附性能，与未改性的牛粪沼渣水热炭相比，改性后水热炭的吸附量最高是未改性水热炭的12.14倍。
3)本发明选取发酵副产物—牛粪沼渣为原料，其廉价易得且减少二次污染，而且使此类废弃物资源化、高值化利用，提高牛粪沼渣水热炭的应用效果和利用价值，促进了沼气工程的效益和发展。
附图说明
图1为改性及未改性牛粪沼渣水热炭的扫描电子显微镜(SEM)图。
图中：(a)为未改性水热炭，(b)为改性水热炭。
图2为改性及未改性牛粪沼渣水热炭对不同初始浓度氨氮(NH 4 +-N)的吸附效果示意图。
图3为改性及未改性牛粪沼渣水热炭对氨氮(NH 4 +-N)的吸附动力学效果示意图。
图4为改性和未改性牛粪沼渣水热炭对猪场实际废水中不同初始浓度氨氮(NH 4 +-N)的吸附效果示意图。
具体实施方式
以下的实施例将对本发明进行更为全面的描述，但其中涉及到的具体参数是为了充分展示本发明的特征及优点，因此本领域的技术人员可在不违背本发明内涵的条件下做更为宽泛的推广及应用。
实施例中牛粪沼渣来源参见文献“靳红梅，付广青，常志州，叶小梅，陈广银，杜静，猪、牛粪厌氧发酵中氮素形态转化及其在沼液和沼渣中的分布，农业工程学报”，自然风干或在60～70℃条件下烘干至含水率为7％～10％，并研磨后过20目筛后获得。
实施例1基于苹果酸和KMnO4联合改性牛粪沼渣水热炭的制备
实验组：
1)取适量牛粪沼渣，加入0.5mol·L -1苹果酸溶液，按照固液比(w/v，kg/L)1：10(具体实施中，牛粪沼渣和苹果酸的固液比可以在1:6～1:10范围内选择) 混合均匀后，50℃条件下进行超声60min(40KHz，100W)；得到的固液混合物过滤、水洗至洗出液为中性、55～80℃条件下烘干，即可得到苹果酸改性牛粪沼渣；
2)将步骤1)中得到的苹果酸改性牛粪沼渣与0.1367mol·L -1KMnO 4(具体实施中，其浓度范围为0.13～0.25mol/L)按照固液比(w/v,kg/L)为1：8(具体实施中，苹果酸改性牛粪沼渣和KMnO 4溶液的固液比可以在1:5～1:10范围内选择)充分混合均匀后于高温高压反应釜中进行水热反应，水热反应的温度为220℃，水热反应的时间为2h，升温速率为1～5℃·min -1；反应结束冷却后进行水洗至洗出液为近中性，过滤，55～80℃烘干即可得到苹果酸和KMnO 4联合改性的牛粪沼渣水热炭(G-HTC)；
对照组：取适量牛粪沼渣粉末与去离子水按照固液比(w/v)为1：8充分混合后，于高温高压反应釜中进行水热反应，水热反应的温度为220℃，水热反应的时间为2h，升温速率为1～5℃·min -1；反应结束冷却后进行水洗至洗出液为近中性，过滤，55～80℃烘干即可得到未改性(对照组)的牛粪沼渣水热炭(Y-HTC)。
G-HTC和Y-HTC的元素组成和比表面积如表1所示：测定方法参见文献“Hongmei Jin,Sergio Capareda,Zhizhou Chang,Jun Gao,Yueding Xu,Jianying Zhang.Biochar pyrolytically produced from municipal solid wastes for aqueous As(V)removal:Adsorption property and its improvement with KOH activation.Bioresource Technology”。
表1 牛粪沼渣水热炭比表面积及元素组成
Figure PCTCN2018094122-appb-000001
由表1可见，两者孔径均以介孔为主，且G-HTC的比表面积与Y-HTC相比显著提高，提高了近179.78％；C/O含量在Y-HTC和G-HTC中均居首位，且G-HTC中C/O的含量均高于Y-HTC。
G-HTC和Y-HTC的扫描电子显微镜(SEM)图如图1所示，由图1可见，未改性的水热炭Y-HTC(图1a)表面呈长条沟渠，孔径较少，而改性水热炭G-HTC(图1b)表面的孔隙度明显得到改善，且呈蜂窝状。
在具体实施过程中，步骤1)超声处理在温度范围35～85℃，40KHz，100W功率超声处理40～90min，均可实现发明之目的；
水热反应的温度为180～220℃，时间为2～3h，升温速率为1～5℃/min，均可实现发明之目的。
实施例2
称取0.3g实施例1获得的G-HTC于250mL锥形瓶中，并加入100mL不同浓度(20mg·L -1、50mg·L -1、100mg·L -1)氨氮(NH 4 +-N)溶液，每个实验做三次重复；于恒温震荡摇床上震荡(28℃，220r·min -1)3h，达到吸附平衡后取上清液并过0.45μm滤膜，采用紫外可见分光光度计测定滤液中的氨氮(NH 4 +-N)浓度，同时对于实施例1获得的Y-HTC采取上述同样的步骤以作为对比例。
实验结果如图2所示，可见，G-HTC和Y-HTC对氨氮(NH 4 +-N)的吸附效果均随氨氮初始浓度的增加而升高，且氨氮(NH 4 +-N)浓度为100mg·L -1时，G-HTC对其吸附量可达9.83mg·g -1，而Y-HTC仅0.81mg·g -1，表明改性的牛粪沼渣水热炭对氨氮(NH 4 +-N)有较好的吸附性能。
实施例3
称取0.3g实施例1获得的G-HTC于250mL锥形瓶中，并加入100mL浓度为100mg·L -1的氨氮(NH 4 +-N)溶液，于恒温震荡摇床上震荡(28℃，220r·min -1)，设定不同的取样时间(0、15、30、60、90、120、150、180min)，并将上清液过0.45μm滤膜，采用紫外可见分光光度计测定滤液中的氨氮(NH 4 +-N)浓度，同时对于Y-HTC采取上述同样的步骤以作为对比例。
检测结果如图3所示，可见，G-HTC对氨氮(NH 4 +-N)的最大吸附量是Y-HTC的12.21倍，两者均在60min内达到吸附饱和。
实施例4
称取0.3g实施例1获得的G-HTC放于250mL锥形瓶中，并加入100mL猪场废水(取自猪场沉淀池，原液NH 4 +-N浓度约为200mg·L -1)稀释液，即将原液加水稀释后使得废水中NH 4 +-N浓度分别为20、50和100mg·L -1，于恒温震 荡摇床上震荡(28℃，220r·min -1)3h，取上清液过0.45μm滤膜，采用紫外可见分光光度计测定滤液中的NH 4 +-N浓度，同时对于Y-HTC采取上述同样的步骤以作为对比例。
检测结果如图4所示，可见，G-HTC对氨氮(NH 4 +-N)的最大吸附量是Y-HTC的9.51倍。
本技术领域技术人员可以理解的是，除非另外定义，这里使用的所有术语(包括技术术语和科学术语)具有与本发明所属领域中的普通技术人员的一般理解相同的意义。还应该理解的是，诸如通用字典中定义的那些术语应该被理解为具有与现有技术的上下文中的意义一致的意义，并且除非像这里一样定义，不会用理想化或过于正式的含义来解释。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (6)

  1. 一种基于苹果酸和KMnO 4联合改性牛粪沼渣水热炭的制备方法，其特征在于，包括以下步骤：
    1)将牛粪沼渣与苹果酸溶液混合均匀后超声处理，得到苹果酸改性牛粪沼渣；
    2)向步骤1)获得的苹果酸改性牛粪沼渣中加入KMnO 4溶液，混合均匀后进行水热反应，即得到所述牛粪沼渣水热炭；
    所述水热反应的反应釜填充度为60％～80％。
  2. 根据权利要求1所述一种基于苹果酸和KMnO 4联合改性牛粪沼渣水热炭的制备方法，其特征在于，步骤1)所述牛粪沼渣含水率为7％～10％，并过20目筛。
  3. 根据权利要求1所述一种基于苹果酸和KMnO 4联合改性牛粪沼渣水热炭的制备方法，其特征在于，所述超声处理是指：35～85℃温度下，40KHz，100W超声处理40～90min。
  4. 根据权利要求1所述一种基于苹果酸和KMnO 4联合改性牛粪沼渣水热炭的制备方法，其特征在于，所述苹果酸溶液浓度为0.5～1.0mol·L -1，牛粪沼渣和苹果酸的固液比为1:6～1:10。
  5. 根据权利要求1所述一种基于苹果酸和KMnO 4联合改性牛粪沼渣水热炭的制备方法，其特征在于，所述KMnO 4溶液的浓度为0.13～0.25mol·L -1，苹果酸改性牛粪沼渣和KMnO 4溶液的固液比为1:5～1:10。
  6. 根据权利要求1所述一种基于苹果酸和KMnO 4联合改性牛粪沼渣水热炭的制备方法，其特征在于，所述水热反应的温度为180～220℃，时间为2～3h，升温速率为1～5℃·min -1。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112973658A (zh) * 2021-03-09 2021-06-18 天津大学 牛粪沼渣炭催化剂及利用其的抗生素的降解方法
CN113680315A (zh) * 2021-07-06 2021-11-23 同济大学 一种负载锰镧氧化物的水热碳微球复合材料及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111847938B (zh) * 2020-07-06 2022-08-05 上海大学 利用沼渣水热炭生产环保型陶粒的方法
CN112250270A (zh) * 2020-09-10 2021-01-22 浙江科技学院 一种沼液在厌氧发酵中高值回用的方法
CN113683151B (zh) * 2021-08-31 2023-03-21 中国水产科学研究院黑龙江水产研究所 养殖水净化的磁性水热炭的制备方法
CN115536022B (zh) * 2022-10-26 2024-01-16 天津科技大学 一种基于山竹壳的生物质多孔炭材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105800588A (zh) * 2016-03-22 2016-07-27 中国科学院上海高等研究院 用于重金属离子吸附的微藻基生物炭材料的制备方法
CN106128782A (zh) 2016-07-25 2016-11-16 云南大学 一种纳米四氧化三锰/活性炭复合材料及其制备方法
CN107352540A (zh) 2017-08-29 2017-11-17 中国科学院城市环境研究所 一种水热法制备负载锰氧化物活性炭的方法及其装置
CN107469768A (zh) * 2017-08-25 2017-12-15 华南农业大学 一种畜禽粪沼渣生物炭/锰氧化物复合材料及其制备方法
CN107903909A (zh) * 2017-11-15 2018-04-13 河南永泽环境科技有限公司 一种土壤修复剂及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100509141C (zh) * 2004-06-24 2009-07-08 中国海洋大学 一种药剂活化法制备活性炭基材料so2吸附剂的方法
CN102815699B (zh) * 2012-08-30 2015-04-08 上海烟草集团有限责任公司 一种多孔生物质材料及其制备和应用
CN104226243A (zh) * 2013-06-18 2014-12-24 中国石油天然气股份有限公司 一种浒苔基新型炭材料的制备方法
CN104492382A (zh) * 2013-12-06 2015-04-08 东华理工大学 一种用于修复含铀废水的羧基化水热生物质炭的制备方法
US9938152B2 (en) * 2014-07-25 2018-04-10 Farad Power, Inc. Method of making activated nano-porous carbon

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105800588A (zh) * 2016-03-22 2016-07-27 中国科学院上海高等研究院 用于重金属离子吸附的微藻基生物炭材料的制备方法
CN106128782A (zh) 2016-07-25 2016-11-16 云南大学 一种纳米四氧化三锰/活性炭复合材料及其制备方法
CN107469768A (zh) * 2017-08-25 2017-12-15 华南农业大学 一种畜禽粪沼渣生物炭/锰氧化物复合材料及其制备方法
CN107352540A (zh) 2017-08-29 2017-11-17 中国科学院城市环境研究所 一种水热法制备负载锰氧化物活性炭的方法及其装置
CN107903909A (zh) * 2017-11-15 2018-04-13 河南永泽环境科技有限公司 一种土壤修复剂及其制备方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
HONGMEI JINGUANGQING FUZHIZHOU CHANGXIAOMEI YEGUANGYIN CHENJING DU: "Form Transformation of Nitrogen in Anaerobic Fermentation of Pig Manure and Cow Dung and Distribution of Nitrogen in Biogas Slurry and Biogas Residue", JOURNAL OF AGRICULTURAL ENGINEERING
HONGMEI JINSERGIO CAPAREDAZHIZHOU CHANGJUN GAOYUEDING XUJIANYING ZHANG: "Biochar Pyrolytically Produced from Municipal Solid Wastes for Aqueous As (V) Removal: Adsorption Property and Its Improvement with KOH Activation", BIORESOURCE TECHNOLOGY
See also references of EP3542896A4
ZHAO, TINGLING ET AL.: "Hydrothermal Synthesis of Diary Manure Hydrochar in the Medium of KMn04 Solution and its Adsorption Properties for Pb(II", ENVIRONMENTAL CHEMISTRY, vol. 35, no. 12, 1 December 2016 (2016-12-01), pages 2535 - 2542, XP055615146 *
ZHENG, YANGQING ET AL.: "Preparation of Biochars from Biogas Residue and Asorption of Ammonia-nitrogen in Biogas Slurry", HUA GONG XUE BAO = CIESC JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING, CHINA , vol. 65, no. 5, 31 May 2014 (2014-05-31), pages 1856 - 1861, XP009515773, ISSN: 0438-1157 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112973658A (zh) * 2021-03-09 2021-06-18 天津大学 牛粪沼渣炭催化剂及利用其的抗生素的降解方法
CN113680315A (zh) * 2021-07-06 2021-11-23 同济大学 一种负载锰镧氧化物的水热碳微球复合材料及其制备方法和应用

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