CN108325503B - An Amine-Activated Carbon Composite Reagent for Removing Anionic Pollutants - Google Patents

An Amine-Activated Carbon Composite Reagent for Removing Anionic Pollutants Download PDF

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CN108325503B
CN108325503B CN201810154020.2A CN201810154020A CN108325503B CN 108325503 B CN108325503 B CN 108325503B CN 201810154020 A CN201810154020 A CN 201810154020A CN 108325503 B CN108325503 B CN 108325503B
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冯成洪
田晨浩
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Beijing Normal University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/20Solid 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
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

本发明公开了一种去除阴离子型污染物的胺基‑活性炭复合药剂,其制备方法如下:活性炭的环氧化物化学改良、改良活性炭的胺基化改性和产物物理分离与干化。该复合药剂充分利用了环氧化物的选择性改性能力与胺基定向偶联能力,具有成本低、正电荷密度大和季铵盐类结构等优势特征,对水中阴离子型污染物尤其是大中分子的无机络合物和有机污染物有较好的去除效果。

Figure 201810154020

The invention discloses an amine-activated carbon composite agent for removing anionic pollutants. The preparation method is as follows: epoxide chemical modification of activated carbon, amination modification of modified activated carbon, and physical separation and drying of products. The compound agent makes full use of the selective modification ability of epoxides and the directional coupling ability of amine groups, and has the advantages of low cost, high positive charge density and quaternary ammonium salt structure. Molecular inorganic complexes and organic pollutants have a better removal effect.

Figure 201810154020

Description

Amino-activated carbon composite medicament for removing anionic pollutants
Technical Field
The invention relates to the field of adsorption, and particularly relates to an amino-activated carbon composite medicament.
Background
Anionic pollutants mainly comprising cyanide, dye, nitride, nitrite, chloride, sulfide, fluoride, surfactant and the like are widely existed in industries such as mineral washing processing, electroplating, organic chemistry and the like, and have long-term potential harm to the environment and huge ecological risk. With the rapid development of economy, the anion pollution in the environment shows an increasingly serious trend, and the anion pollution of different degrees appears in underground water and surface water, so that the situation is very severe.
Adsorption and ion exchange have been considered as one of the most effective techniques for the removal of anionic contaminants from water. Compared with the ion exchange technology which has the defects of large generation amount of regenerated waste liquid, poor organic pollution resistance, long period and large salt consumption, the adsorption technology is considered as the anion pollutant removal technology with the most development potential in an efficient, economical and flexible operation mode. The key of the technology is the complexity of the research and development process and the synthesis process of the high-efficiency adsorbing material. The powdered activated carbon has the characteristics of higher specific surface area, chemical and mechanical stability, ion exchange capacity and the like, so the powdered activated carbon is generally considered to be a better adsorption material and can become a high-efficiency and low-cost material for removing anionic pollutants with great development prospect after being modified.
In previous researches, document 1 "Zhengjing Jingwei, Linjianwei, Zhanyanhui, Fangqiao, Yangjuan, Wanghong, Cetylpyridinium chloride modified activated carbon has an adsorption effect on nitrate in water [ J ]. environmental science, 2013, (11): 4325-; document 2 "Zhengxi, Linjianwei, Zhan-kuan, Yangjuan, Fangqiao. lanthanum and cationic surfactant jointly modify the adsorption of activated carbon on phosphate and nitrate in water [ J ]. environmental chemistry 2015, (05): 939-. Document 3 "Dai X, Breuer P L, Jeffrey M i.e. contrast of activated carbon and ion-exchange resins in a recovery scrubber from cyanamide solutions [ J ]. Hydrometallurgy,2010,101(1): 48-57" indicates that both activated carbon and resin have an adsorption effect on copper cyanide compounds and silver cyanide compounds, and that the adsorption of activated carbon has the advantage of being easier to elute than the adsorption of resin. The research proves that the capability of the activated carbon for adsorbing anionic pollutants after alkali modification can be obviously improved, mainly due to the fact that the density and the number of cationic groups on the surface of the activated carbon are obviously improved.
Based on the above, there is an urgent need to develop a medicament which has low cost and simple process, and can effectively remove inorganic complex and organic pollutants of large and medium molecules, so as to meet the market demand.
Disclosure of Invention
The invention aims to provide an amino-activated carbon (AmMAC) efficient composite agent for removing anionic pollutants in water, which takes cheap coal-based activated carbon as an original framework material and is modified by diethylamine, so that the AmMAC efficient composite agent has a good removal effect on the anionic pollutants in water, particularly inorganic complexes and organic pollutants of large and medium molecules.
An amido-active carbon composite medicament for removing anionic pollutants is prepared by the following process steps:
(1) preparation of improved activated carbon homogenate
Mixing the coal-based activated carbon powder with epoxy chloropropane and N, N-dimethylformamide, and continuously stirring the mixed solution in a constant-temperature water bath magnetic stirrer at the temperature of 40 ℃ to prepare an improved activated carbon homogenate activated by epoxy chloropropane; wherein, the raw material mixing proportion is that 100-150mmol of epichlorohydrin and 60-75mmol of N, N-dimethylformamide are added into each gram of coal-based activated carbon powder;
(2) preparation of amino modified activated carbon
Under the condition of constant temperature and uniform stirring, slowly dripping diethylamine into the improved activated carbon homogenate, wherein the addition amount of the diethylamine is 80-120mmol per gram of coal-based activated carbon powder, and preparing the amino-modified activated carbon homogenate;
(3) separation and drying
And (3) carrying out solid-liquid separation on the prepared amino modified activated carbon homogenate by using a sand core suction filtration device, intercepting solid particles on a filter membrane, drying the filter membrane covered with the modified material in an electric heating blast box, taking out and grinding to obtain a finished product.
Preferably, 125mmol of epichlorohydrin and 65mmol of N, N-dimethylformamide are added to each gram of coal-based activated carbon powder in the step (1).
Preferably, in the step (1), 100-150 mesh coal-based activated carbon powder is selected as a raw material.
Preferably, in step (1), the stirring speed is 120rpm, and the mixture is continuously stirred for 2 h.
Preferably, the adding amount of the diethylamine in the step (2) is 100mmol per gram of the coal-based activated carbon powder.
Preferably, in step (2), the titration rate is 0.15ml/min, the temperature is controlled at 40 ℃, the stirring speed is 120rpm, and the mixture is continuously stirred for 2 h.
Preferably, in the step (3), the drying temperature is 65 ℃, the drying time is 2 hours, and the grinding fineness is 100 meshes.
Compared with the traditional activated carbon adsorption, the medicament fully utilizes the selective modification capability of the epichlorohydrin and the directional coupling capability of the diethylamine, the modified activated carbon has a stable structure, a large number of positive charge groups and an obvious quaternary ammonium salt structure are carried on the surface, and the medicament has a good removal effect on anionic pollutants in a water body, particularly inorganic complexes and organic pollutants of large and medium molecules, and has the following advantages:
1. the preparation process is simple, the active carbon does not need to be subjected to pre-oxidation treatment, the cost is low, and the industrial production is easy to realize.
2. The invention carries out the reaction at the low temperature of 40 ℃, reduces the energy consumption,
3. the agent has a quaternary ammonium salt structure, and the removal amount of anionic pollutants (taking Congo red as an example) of the modified agent is improved by 3 times compared with that of unmodified activated carbon.
4. The medicament fully utilizes the performances of stable carbon structure skeleton, high-efficiency directional coupling capability of amido, high-density positive charges on the surface and the like, has the characteristics of high reaction speed, large capacity and high efficiency, can reach balance after reacting for 45 minutes, can reach 95 percent of the maximum removal rate within 5 minutes, and can reach 670mg/L of Congo red removal under the condition of pH 4.
Drawings
FIG. 1 is a scanning electron microscope image of an amino modified activated carbon composite medicament;
FIG. 2 is a comparison of kinetics of Congo red adsorption removal of an amino-modified activated carbon composite medicament and unmodified activated carbon;
FIG. 3 is a comparison of adsorption isotherms of various proportions of amino-modified activated carbon composite reagents and unmodified activated carbon against Congo red;
FIG. 4 shows the adsorption capacity of the amino-modified activated carbon composite reagent to Congo red at different pH values.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
10g of raw material coal-based activated carbon powder with 100 meshes is mixed with 100mL of epoxy chloropropane and 50mL of N, N-dimethylformamide, and the mixture is shaken to ensure that the powdered activated carbon is not bonded and is uniformly dispersed in the mixed solution. The mixed solution was transferred to a constant temperature water bath magnetic stirrer, the temperature was controlled at 40 ℃ and the stirring speed was 120rpm, and the mixed solution was continuously stirred for 2 hours. Then, 100mL of diethylamine was slowly dropped into the activated carbon homogenate with uniform stirring at a rate of 0.15mL/min, a temperature of 40 ℃ and a stirring rate of 120rpm, and the mixture was continuously stirred for 2 hours. And (4) carrying out suction filtration on the turbid liquid by using a sand core suction filtration device, and intercepting the modified material particles on the filter membrane. And (3) placing the filter membrane covered with the modified material in an electric heating blast box, drying for 2h at 65 ℃, taking out, grinding to 100 meshes, and completing the separation and drying of the amine-based activated carbon to prepare 100-mesh amine-based modified activated carbon powder with a quaternary ammonium salt structure and used for efficiently removing anionic pollutants in water. FIG. 1 shows the appearance of an amino-modified activated carbon composite medicament.
Example 2
In the case of a typical anionic pollutant Congo red, a 1000mL glass beaker is used, 100mg/L of Congo red dye solution is added, and 500mg of the amino modified activated carbon agent in example 1 is added. The supernatant was filtered by stirring with a mechanical stirrer at 60rpm and at 0,1, 5, 10, 15, 20, 25, 30, 45, 60, 75, 90, 120, 180 minutes, respectively, and the residual absorbance was measured at 508nm wavelength using an ultraviolet-visible spectrophotometer and congo red dye reaction removal kinetics were calculated from a standard curve. The above process was repeated using unmodified activated carbon as the agent. The calculation results are shown in fig. 2.
Example 3
In the case of a typical anionic pollutant, Congo red, 0.1g of the amine-modified activated carbon agent of example 1 was added to each of 6 1000mL glass beakers, followed by 1, 2.5, 5, 10, 25, and 50mg/L of Congo red dye solution. A mechanical stirrer was used, and the rotation speed was set to 60 rpm. And (3) filtering the sample by using a 0.45-micron filter membrane, measuring the absorbance of the Congo red in the filtrate at the wavelength of 508nm by using an ultraviolet-visible spectrophotometer, and calculating the removal efficiency of the Congo red according to a standard curve. The above process was repeated using unmodified activated carbon as the agent.
Example 4
Taking a typical anionic pollutant Congo red as a case, a 1000mL glass beaker is used, 100mg/L of Congo red dye solution is added, 100mg of the amino modified activated carbon agent in example 1 is added, the pH value of the solution is adjusted, and the adsorption capacity of the agent on Congo red under different pH values of the solution is detected, which is shown in FIG. 4. As can be seen from FIG. 4, the amino modified activated carbon has a good removal effect on wastewater in different acid and alkali environments, particularly in strongly alkaline wastewater, and the removal efficiency can reach more than 200mg/g at most.
The amino modified activated carbon medicament can not only remove inorganic anion pollutants, but also has better removal effect on organic anion pollutants, has the maximum effective adsorption capacity up to 313mg/L, and has better removal effect on different acid-base environment wastewater.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (2)

1.一种去除阴离子型污染物的胺基-活性炭复合药剂,其特征在于,采用如下工艺步骤制备而成:1. an amine group-activated carbon composite medicament for removing anionic pollutants, is characterized in that, adopts following processing steps to prepare from: (1)改良活性炭匀浆的制备(1) Preparation of modified activated carbon homogenate 选择100-150目的煤基活性炭粉末做为原料与环氧氯丙烷和N,N-二甲基甲酰胺混合,在40℃的恒温水浴磁力搅拌器中连续搅拌混合液,搅拌速度为120rpm,连续搅拌混合液2h,制备环氧氯丙烷活化的改良活性炭匀浆;其中,原料混合比例为每克煤基活性炭粉末添加125mmol的环氧氯丙烷和65mmol的N,N-二甲基甲酰胺;Select 100-150 mesh coal-based activated carbon powder as the raw material to mix with epichlorohydrin and N,N-dimethylformamide, and continuously stir the mixture in a constant temperature water bath magnetic stirrer at 40°C, with a stirring speed of 120rpm, continuously The mixture was stirred for 2 hours to prepare an improved activated carbon homogenate activated by epichlorohydrin; wherein, the mixing ratio of the raw materials was to add 125 mmol of epichlorohydrin and 65 mmol of N,N-dimethylformamide per gram of coal-based activated carbon powder; (2)胺基改性活性炭的制备(2) Preparation of amine-modified activated carbon 在40℃恒温匀速搅拌条件下将二乙胺缓慢滴入改良活性炭匀浆中,二乙胺的加入量为每克煤基活性炭粉末加入100mmol,制得胺基改性的活性炭匀浆;滴定速度为0.15mL /min,搅拌速度为120rpm,连续搅拌混合液2h;Diethylamine was slowly dripped into the modified activated carbon homogenate under the condition of constant stirring at a constant speed of 40 °C. The amount of diethylamine added was 100 mmol per gram of coal-based activated carbon powder to obtain an amine-based modified activated carbon homogenate; titration speed is 0.15mL/min, the stirring speed is 120rpm, and the mixture is continuously stirred for 2h; (3)分离及干化(3) Separation and drying 利用砂芯抽滤装置将已制得的胺基改性的活性炭匀浆液进行固液分离,截流固体颗粒于滤膜上,将覆盖有改性材料的滤膜置于电热鼓风箱中进行干燥,取出后研磨,得成品。The obtained amine-modified activated carbon homogenate was separated from solid and liquid by means of a sand core suction filtration device, the solid particles were intercepted on the filter membrane, and the filter membrane covered with the modified material was placed in an electric heating blast box for drying. Take out and grind to get the finished product. 2.根据权利要求1所述的复合药剂,其特征在于,步骤(3)中,干燥温度为65℃,干燥时间为2h,研磨细度为100目。2 . The compound medicine according to claim 1 , wherein, in step (3), the drying temperature is 65° C., the drying time is 2 h, and the grinding fineness is 100 meshes. 3 .
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