阅读说明：本技术 一种用于工业污水处理的天然吸附剂的制备方法 (Preparation method of natural adsorbent for industrial sewage treatment ) 是由 孙静亚 叶啸天 张富生 陈庆国 于 2019-08-29 设计创作，主要内容包括：本发明涉及吸附剂制备技术领域,公开了一种用于工业污水处理的天然吸附剂的制备方法,步骤为：将花生壳清洗、干燥、粉碎、过筛后得到花生壳粉末；将花生壳粉末加入硝酸溶液中,加热反应后得到氧化后的花生壳粉末；将氧化后的花生壳粉末与氯化亚砜混合,加热回流反应后得到酰氯化的花生壳粉末；将酰氯化的花生壳粉末和乙二胺混合,加热反应后得到表面改性的花生壳粉末；将表面改性的花生壳粉末、甲壳素、膨润土和沸石混合,搅拌均匀得到混合料；将混合料揉成小球状,灼烧后得到所述天然吸附剂。本发明以花生壳作为原料,制得的天然吸附剂来源广、价格低廉、无二次污染,且对重金属离子、三态氮、COD及色素的吸附性能好。(The invention relates to the technical field of adsorbent preparation, and discloses a preparation method of a natural adsorbent for industrial sewage treatment, which comprises the following steps: cleaning peanut shells, drying, crushing and sieving to obtain peanut shell powder; adding the peanut shell powder into a nitric acid solution, and heating for reaction to obtain oxidized peanut shell powder; mixing the oxidized peanut shell powder with thionyl chloride, and heating and refluxing for reaction to obtain acyl chlorinated peanut shell powder; mixing acyl chlorinated peanut shell powder and ethylenediamine, and heating for reaction to obtain surface modified peanut shell powder; mixing the surface-modified peanut shell powder, the chitin, the bentonite and the zeolite, and uniformly stirring to obtain a mixture; kneading the mixture into a small ball shape, and firing to obtain the natural adsorbent. The peanut shell is used as a raw material, and the prepared natural adsorbent has the advantages of wide source, low price, no secondary pollution and good adsorption performance on heavy metal ions, ternary nitrogen, COD (chemical oxygen demand) and pigments.)

1. A preparation method of a natural adsorbent for industrial sewage treatment is characterized by comprising the following steps:

(1) cleaning peanut shells, drying, crushing and sieving to obtain peanut shell powder;

(2) adding peanut shell powder into 5-10mol/L nitric acid solution, heating for reaction, filtering, washing, and drying to obtain oxidized peanut shell powder, wherein the adding ratio of the peanut shell powder to the nitric acid solution is 1g (20 ~ 40 mL);

(3) mixing the oxidized peanut shell powder with thionyl chloride according to the mass ratio of 1 (1.5-3), and heating and refluxing for reaction to obtain acyl chlorinated peanut shell powder;

(4) mixing acyl chlorinated peanut shell powder and ethylenediamine in a mass ratio of 1 (1.5-3), heating for reaction, washing and drying to obtain surface modified peanut shell powder;

(5) mixing the surface modified peanut shell powder, the chitin, the bentonite and the zeolite in a mass ratio of (1-5) to (10-15) to 1:1, and uniformly stirring to obtain a mixture;

(6) kneading the mixture into a pellet shape, burning for 4-6h at 650-750 ℃, and cooling to obtain the natural adsorbent.

2. The method for preparing a natural adsorbent for industrial sewage treatment according to claim 1, wherein the drying temperature in step (1) is 50-80 ℃, and the natural adsorbent is sieved by a sieve of 80-100 meshes.

3. The method for preparing the natural adsorbent for industrial sewage treatment according to claim 1, wherein the heating reaction in the step (2) is carried out at a temperature of 60-80 ℃ for 8-10 h.

4. The method for preparing a natural adsorbent for industrial sewage treatment according to claim 1 or 3, wherein the drying temperature in the step (2) is 90-110 ℃.

5. The method for preparing a natural adsorbent for industrial sewage treatment according to claim 1, wherein the heating reflux reaction temperature in the step (3) is 70-80 ℃ and the reaction time is 3-5 h.

6. The method as claimed in claim 1, wherein the heating in step (4) is carried out at 115-125 deg.C for 9-11 h.

7. The method for preparing a natural adsorbent for industrial sewage treatment according to claim 1 or 6, wherein the drying temperature in the step (4) is 90-110 ℃.

8. The method of claim 1, wherein the mass of the single pellet in the step (6) is 0.6-0.7 g.

Technical Field

The invention relates to the technical field of adsorbent preparation, in particular to a preparation method of a natural adsorbent for industrial sewage treatment.

Background

At present, due to the rapid development of the industrial society, the ecological environment is fatally damaged by industrial production, the deterioration of the ecological environment becomes an important factor restricting the economic development of China, and the living environment of human beings is seriously threatened. Under the influence of industrial development, the discharge of industrial sewage is a typical environmental pollution representative, and the treatment difficulty is high due to high contents of heavy metals, industrial additives, organic solvents and the like in the industrial sewage. Adsorption is an important step in the treatment of industrial wastewater, so the selection of the adsorbent plays a crucial role in the treatment effect of industrial wastewater.

Disclosure of Invention

The invention provides a preparation method of a natural adsorbent for industrial sewage treatment, aiming at overcoming the problems that in the prior art, activated carbon is used as an adsorbent in industrial sewage treatment, the price is higher, the loss during regeneration is larger, the adsorption effect on common pollutants in the industrial sewage such as ammonia nitrogen, heavy metal and the like is limited, and the treatment requirement of the industrial sewage cannot be met.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a natural adsorbent for industrial sewage treatment comprises the following steps:

(1) cleaning peanut shells, drying, crushing and sieving to obtain peanut shell powder;

(2) adding peanut shell powder into 5-10mol/L nitric acid solution, heating for reaction, then carrying out suction filtration, washing and drying to obtain oxidized peanut shell powder, wherein the adding proportion of the peanut shell powder to the nitric acid solution is 1g (20-40 mL);

(3) mixing the oxidized peanut shell powder with thionyl chloride according to the mass ratio of 1 (1.5-3), and heating and refluxing for reaction to obtain acyl chlorinated peanut shell powder;

(4) mixing acyl chlorinated peanut shell powder and ethylenediamine in a mass ratio of 1 (1.5-3), heating for reaction, washing and drying to obtain surface modified peanut shell powder;

(5) mixing the surface modified peanut shell powder, the chitin, the bentonite and the zeolite in a mass ratio of (1-5) to (10-15) to 1:1, and uniformly stirring to obtain a mixture;

(6) kneading the mixture into a pellet shape, burning for 4-6h at 650-750 ℃, and cooling to obtain the natural adsorbent.

Peanut is an annual herbaceous plant of leguminous, is a nut which is widely eaten by people, and has rich yield in China. The peanut shell has affinity to heavy metal ions due to the porosity and the peanut shell fiber, and can remove dye in wastewater. Therefore, the invention adopts the peanut shells as the raw material and modifies the raw material to prepare the natural adsorbent, and has the advantages of wide source, low price, no secondary pollution and the like.

In the steps (1) - (4), oxidizing the peanut shell powder by nitric acid, acylating chlorination by thionyl chloride and amination by ethylenediamine in sequence, wherein the surface of the finally obtained surface-modified peanut shell powder has rich amino groups, can be chelated with heavy metal ions, and improves the adsorption capacity of the heavy metal ions; and the chitosan can be crosslinked with hydroxyl on the surface of the chitin added in the step (5) to form hydrogen bonds, so that the peanut shell powder is fixed and uniformly dispersed in the globular adsorbent.

The main component of the bentonite added in the step (5) is montmorillonite which has a large specific surface area, so that the bentonite has strong adsorption capacity and can adsorb pollutants in sewage; in addition, the bentonite can also play a role in agglomerating other materials together under the condition of adding water, so that the adsorbent keeps a certain shape and is not easy to loosen. Chitin is a natural polymer, is abundant in earth, is mostly taken from shells of shrimps and crabs, and can adsorb and complex heavy metal ions in sewage. The zeolite has a unique lattice structure, so that the zeolite has good adsorption performance on ammonia nitrogen in sewage.

Therefore, the surface modified peanut shell powder, the bentonite, the chitin and the zeolite are mixed and then fired to prepare the globular natural adsorbent, which has good adsorption performance on heavy metal ions, ammonia nitrogen and organic pollutants in industrial sewage, and the adsorbent has good agglomeration performance and is not easy to loosen when in use.

Preferably, the drying temperature in the step (1) is 50-80 ℃, and the mixture is sieved by a sieve with 80-100 meshes. By adopting the drying temperature and the particle size range, the obtained peanut shell powder can be ensured to have good specific surface area and effective components, so that the prepared natural adsorbent has good adsorption performance.

Preferably, the heating reaction temperature in the step (2) is 60-80 ℃, and the reaction time is 8-10 h. In the reaction temperature and time, the surface of the peanut shell powder can be fully oxidized by nitric acid, so that the subsequent reaction modification is facilitated.

Preferably, the drying temperature in step (2) is 90 to 110 ℃. Drying at the temperature can ensure sufficient drying, and meanwhile, effective components in the oxidized peanut shell powder cannot be damaged.

Preferably, the reflux reaction temperature in the step (3) is 70-80 ℃, and the reaction time is 3-5 h. Under the reaction temperature and time, the oxidized peanut shell powder can effectively react with thionyl chloride to obtain acyl chlorinated peanut shell powder for subsequent modification, so that the adsorption performance of the prepared natural adsorbent is ensured.

Preferably, the heating reaction temperature in the step (4) is 115 ℃ and 125 ℃, and the reaction time is 9-11 h. In the reaction temperature and time, the acyl-chlorinated peanut shell powder can fully react with ethylenediamine to aminate the surface, and the surface of the obtained surface-modified peanut shell powder has rich active groups such as amino groups, so that the surface-modified peanut shell powder can effectively adsorb pollutants such as heavy metal ions and dyes in sewage, and the adsorption performance of the adsorbent is improved.

Preferably, the drying temperature in step (4) is 90 to 110 ℃. At this drying temperature, sufficient drying is ensured without destroying the active ingredients in the surface-modified peanut shell powder.

Preferably, the mass of the individual pellets in step (6) is 0.6 to 0.7 g. The natural adsorbent is made into the small balls within the mass range, so that the specific surface area of the adsorbent can meet the adsorption requirement, and the situation that the natural adsorbent is too small in particle size, easy to loosen and not beneficial to recovery can be avoided.

Therefore, the invention has the following beneficial effects:

(1) the natural adsorbent prepared by using peanut shells as raw materials and modifying the peanut shells has the advantages of wide source, low price, no secondary pollution and the like, and can achieve the purpose of treating wastes with processes of wastes against one another;

(2) the peanut shell powder is subjected to nitric acid oxidation, thionyl chloride acyl chlorination and ethylenediamine amination in sequence, so that the finally obtained surface-modified peanut shell powder has rich amino groups on the surface, can be chelated with heavy metal ions, and improves the adsorption capacity of the heavy metal ions; and can form hydrogen bond by the hydroxyl crosslinking on the surface of the chitin, so that the peanut shell powder is fixed and uniformly dispersed in the globular adsorbent;

(3) the surface modified peanut shell powder, bentonite, chitin and zeolite are mixed and then fired to prepare the globular natural adsorbent, which has good adsorption performance on heavy metal ions, ammonia nitrogen and organic pollutants in industrial sewage, and the adsorbent has good agglomeration performance and is not easy to loosen when in use.

Detailed Description

The invention is further described with reference to specific embodiments.