WO2020098390A1 - Method for preparing cellulose microsphere adsorbent - Google Patents

Method for preparing cellulose microsphere adsorbent Download PDF

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WO2020098390A1
WO2020098390A1 PCT/CN2019/107742 CN2019107742W WO2020098390A1 WO 2020098390 A1 WO2020098390 A1 WO 2020098390A1 CN 2019107742 W CN2019107742 W CN 2019107742W WO 2020098390 A1 WO2020098390 A1 WO 2020098390A1
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cellulose
solution
reaction
add
cotton straw
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管敏富
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管敏富
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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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—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 form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • 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
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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 relates to the field of chemical industry and environmental protection, in particular to a preparation method of cellulose microsphere adsorbent.
  • Cellulose is the oldest and richest natural polymer on the planet, and the most precious natural renewable resource for human beings. Cellulose has the advantages of reproducibility, biodegradability, good biocompatibility and non-toxicity. Modification of cellulose, introduction of some functional groups, preparation of adsorbents with a certain form, can be widely used in wastewater treatment. China's printing and dyeing textile industry discharges a large amount of dye wastewater every year, causing serious pollution to the environment. The composition of dye wastewater is complex, the color is deep, and the amount of discharge is large. It is extremely difficult to treat and recycle. In addition, many production wastewaters contain heavy metal ions. These wastewaters have a great adverse impact on the environment, water resources and human health. The preparation of effective wastewater treatment substances is the focus of research.
  • the purpose of the present invention is to provide a method for preparing cellulose microsphere adsorbent in order to solve the problems mentioned in the background and the deficiencies of the prior art.
  • the invention provides a method for preparing a cellulose microsphere adsorbent, which includes the following steps:
  • Step 1 Wash cotton straw, mechanically crush it after drying, add a mixed solution of xylene and ethanol to the cotton straw powder, put it in a boiling water bath to react, take out and wash, suction filter, add hydrochloric acid solution, 90 °C Water bath treatment for 1.5h, then add deionized water to the water bath for 3h, filter with suction, dry for use;
  • Step 2 Add solution A to the cotton straw powder pretreated in step 1 for reaction, suction filtration, and after drying, add solution B to the obtained powder for reaction. After the reaction, wash with distilled water until neutral and dry. Get cotton straw cellulose;
  • Step 3 Configure the cotton straw cellulose prepared in Step 2 as an aqueous solution for use;
  • Step 4 Add castor oil and Tween 80 to the flask, turn on the stirring device and heating device, stir for 20min, then add cotton straw cellulose aqueous solution, continue the reaction for 30min, add epichlorohydrin to react for 9h;
  • Step 5 The reaction system was allowed to stand overnight, the surface oil phase was removed, the cellulose microspheres were washed with ethyl acetate and ethanol respectively, and the cellulose microsphere adsorbent was obtained after drying.
  • the volume ratio of xylene and ethanol in the mixed solution in step one is 3: 2.
  • the solution A in the second step is formed by mixing hydrogen peroxide and sodium hydroxide in deionized water.
  • the solution B is formed by mixing trichloroacetic acid and nitric acid dissolved deionized water.
  • the concentration of the cotton straw aqueous solution in step 3 is 8-16 wt%.
  • the rotation speed of the stirring device in step 4 is 540-660 rad / min, and the reaction temperature is 50-80 ° C.
  • the present invention controls the mass fraction of cellulose, and the cellulose molecules can be well dispersed in the solution to perform a sufficient cross-linking reaction, and the prepared cellulose microspheres have a moderate particle size and a large adsorption capacity.
  • the stirring speed of the controlled reaction is 540-660 rad / min, and the reaction temperature is 50-80 ° C, which can make the cross-linking reaction between epichlorohydrin and cellulose molecules sufficient, and the formed microspheres have a Large total surface area, good adsorption performance.
  • Step 1 Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 °C water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 °C, 200r / min water bath reaction for 3h, suction filtration, dried at 60 °C for use;
  • Step 2 Add solution A to the cotton straw powder pretreated in step 1, the material-liquid ratio is 1:20 (g / mL), solution A is 0.6mL hydrogen peroxide and 3g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 90 °C for 4h, filtering with suction, drying at 60 °C, adding solution B to the obtained powder, the material-liquid ratio is 1:25 (g / mL), solution B is 0.8g trichloro Acetic acid and 6mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 60 °C for 3h, washed with distilled water until neutral, and dried at 60 °C to obtain cotton straw cellulose;
  • Step 3 Configure the cotton straw cellulose prepared in Step 2 as a 16wt% aqueous solution for use;
  • Step 4 Add 60mL castor oil and 0.25g Tween 80 to the flask, adjust the rotation speed to 540rad / min, increase the temperature to 80 ° C, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, continue the reaction for 30min, add 1.45mL ring Oxychloropropane, reaction 9h;
  • Step 5 Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 °C to obtain cellulose Microsphere adsorbent.
  • Step 1 Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 °C water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 °C, 200r / min water bath reaction for 3h, suction filtration, dried at 60 °C for use;
  • Step two Add solution A to the cotton straw powder pretreated in step one, the material-liquid ratio is 1:20 (g / mL), solution A is 0.2mL hydrogen peroxide and 8g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 60 °C for 4h, filtering with suction, drying at 60 °C, adding solution B to the powder obtained, the material-liquid ratio is 1:25 (g / mL), solution B is 1.2g trichloro Acetic acid and 2mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 80 °C for 1h, washed with distilled water until neutral, and dried at 60 °C to obtain cotton straw cellulose;
  • Step 3 Configure the cotton straw cellulose prepared in Step 2 as an 8wt% aqueous solution for use;
  • Step 4 Add 80 mL of castor oil and 0.05 g of Tween 80 to the flask, adjust the rotation speed to 660 rad / min, increase the temperature to 50 ° C, stir for 20 min, then add 10 mL of cotton straw cellulose aqueous solution, continue the reaction for 30 min, add 2.25 mL of ring Oxychloropropane, reaction 9h;
  • Step 5 Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 °C to obtain cellulose Microsphere adsorbent.
  • Step 1 Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 °C water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 °C, 200r / min water bath reaction for 3h, suction filtration, dried at 60 °C for use;
  • Step two Add solution A to the cotton straw powder pretreated in step one, the material-liquid ratio is 1:20 (g / mL), solution A is 0.5mL hydrogen peroxide and 4g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 80 °C for 4h, filtering with suction, drying at 60 °C, adding solution B to the powder obtained, the material-liquid ratio is 1:25 (g / mL), solution B is 0.9g trichloromethane Acetic acid and 5mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 65 °C for 2.5h, washed with distilled water to neutral, and dried at 60 °C to obtain cotton straw cellulose;
  • Step 3 Configure the cotton straw cellulose prepared in Step 2 as a 14wt% aqueous solution for use;
  • Step 4 Add 65mL castor oil and 0.2g Tween 80 to the flask, adjust the rotation speed to 570rad / min, increase the temperature to 70 ° C, stir for 20min, then add 10mL cotton straw aqueous cellulose solution, continue the reaction for 30min, add 1.65mL ring Oxychloropropane, reaction 9h;
  • Step 5 Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 °C to obtain cellulose Microsphere adsorbent.
  • Step 1 Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 °C water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 °C, 200r / min water bath reaction for 3h, suction filtration, dried at 60 °C for use;
  • Step two Add solution A to the cotton straw powder pretreated in step one, the material-liquid ratio is 1:20 (g / mL), solution A is 0.3mL hydrogen peroxide and 7g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 70 °C for 4h, filtering with suction, and drying at 60 °C, adding solution B to the obtained powder, the material-liquid ratio is 1:25 (g / mL), solution B is 1.1g trichloro Acetic acid and 3mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 75 °C for 1.5h, washed with distilled water until neutral, and dried at 60 °C to obtain cotton straw cellulose;
  • Step 3 Configure the cotton straw cellulose prepared in Step 2 as a 10wt% aqueous solution for use;
  • Step 4 Add 75mL castor oil and 0.1g Tween 80 to the flask, adjust the rotation speed to 630rad / min, increase the temperature to 60 °C, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, and continue the reaction for 30min, add 2.05mL ring Oxychloropropane, reaction 9h;
  • Step 5 Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 °C to obtain cellulose Microsphere adsorbent.
  • Step 1 Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 °C water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 °C, 200r / min water bath reaction for 3h, suction filtration, dried at 60 °C for use;
  • Step two Add solution A to the cotton straw powder pretreated in step one, the material-liquid ratio is 1:20 (g / mL), solution A is 0.4mL hydrogen peroxide and 5.5g sodium hydroxide dissolved in 100mL It is mixed with deionized water, reacted at 75 °C for 4h, filtered with suction, and dried at 60 °C. Solution B is added to the obtained powder.
  • the material-liquid ratio is 1:25 (g / mL).
  • Solution B is 1g of trichloromethane Acetic acid and 4mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 70 °C for 2h, washed with distilled water until neutral, and dried at 60 °C to obtain cotton straw cellulose;
  • Step 3 Configure the cotton straw cellulose prepared in Step 2 as a 12wt% aqueous solution for use;
  • Step 4 Add 70mL castor oil and 0.15g Tween 80 to the flask, adjust the rotation speed to 600rad / min, increase the temperature to 65 °C, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, continue the reaction for 30min, add 1.85mL ring Oxychloropropane, reaction 9h;
  • Step 5 Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 °C to obtain cellulose Microsphere adsorbent.
  • Example 1 The difference between this comparative example and Example 1 is that the concentration of the cotton straw aqueous solution in step 3 is 5 wt%.
  • Step 1 Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 °C water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 °C, 200r / min water bath reaction for 3h, suction filtration, dried at 60 °C for use;
  • Step 2 Add solution A to the cotton straw powder pretreated in step 1, the material-liquid ratio is 1:20 (g / mL), solution A is 0.6mL hydrogen peroxide and 3g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 90 °C for 4h, filtering with suction, drying at 60 °C, adding solution B to the obtained powder, the material-liquid ratio is 1:25 (g / mL), solution B is 0.8g trichloro Acetic acid and 6mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 60 °C for 3h, washed with distilled water until neutral, and dried at 60 °C to obtain cotton straw cellulose;
  • Step 3 Configure the cotton straw cellulose prepared in Step 2 as a 5wt% aqueous solution for use;
  • Step 4 Add 60mL castor oil and 0.25g Tween 80 to the flask, adjust the rotation speed to 540rad / min, increase the temperature to 80 ° C, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, continue the reaction for 30min, add 1.45mL ring Oxychloropropane, reaction 9h;
  • Step 5 Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 °C to obtain cellulose Microsphere adsorbent.
  • Step 1 Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 °C water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 °C, 200r / min water bath reaction for 3h, suction filtration, dried at 60 °C for use;
  • Step 2 Add solution A to the cotton straw powder pretreated in step 1, the material-liquid ratio is 1:20 (g / mL), solution A is 0.6mL hydrogen peroxide and 3g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 90 °C for 4h, filtering with suction, drying at 60 °C, adding solution B to the obtained powder, the material-liquid ratio is 1:25 (g / mL), solution B is 0.8g trichloro Acetic acid and 6mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 60 °C for 3h, washed with distilled water until neutral, and dried at 60 °C to obtain cotton straw cellulose;
  • Step 3 Configure the cotton straw cellulose prepared in Step 2 as a 16wt% aqueous solution for use;
  • Step 4 Add 60mL of castor oil and 0.25g of Tween 80 to the flask, adjust the speed to 400rad / min, heat to 80 ° C, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, continue the reaction for 30min, add 1.45mL Oxychloropropane, reaction 9h;
  • Step 5 Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 °C to obtain cellulose Microsphere adsorbent.
  • cellulose microsphere adsorbent was added to 100mL of 5 ⁇ g / mL active blue M solution, 100mL0.08g / mL Cr 6+ solution and 100mL 0.08g / mL Cu 2+ solution for adsorption, measured by spectrophotometry The absorption value of the filtrate after adsorption, the adsorption rate is calculated, the test results are shown in the table below:
  • the cellulose microsphere adsorbent prepared by the present invention has a very good adsorption effect on dye wastewater, the adsorption rate of reactive blue M reaches 92.66-98.74%, and the metal ions Cr 6+ and Cu 2 in wastewater + Also has a good adsorption effect, the adsorption rate of Cr 6+ reaches 82.55-88.37%, and the adsorption rate of Cu 2+ reaches 88.76-93.46%.
  • the cellulose microsphere adsorbent prepared in Example 5 achieves the best treatment effect, so Example 5 is the optimal solution of the present invention.
  • Comparative Example 1 the concentration of the cotton straw aqueous cellulose solution is 5 wt%, the mass fraction is too low, and the cross-linking reaction between the cellulose molecules cannot be performed well, resulting in the formation of microspheres with a too small particle size and poor adsorption performance.
  • the stirring speed in Comparative Example 2 is 400 rad / min. The stirring speed is too low, which is not conducive to the dispersion of the aqueous phase in the reaction system, the droplets cannot be well dispersed, the total surface area of the formed microspheres is small, and the adsorption performance is poor.

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Abstract

A method for preparing a cellulose microsphere adsorbent, comprising the following steps: cleaning, drying and crushing cotton straw, adding a mixture of xylene and ethanol, performing a reaction in a boiling water bath, performing washing and suction filtration, adding a hydrochloric acid solution for treatment, adding deionized water for a reaction in a water bath, performing suction filtration, and drying the product for use; adding a solution A to the pre-treated cotton straw powder for a reaction, performing suction filtration and drying, then adding a solution B for a reaction, washing and drying the resultant to obtain cotton straw cellulose, and formulating the cotton straw cellulose into an aqueous solution for use; adding castor oil and Tween 80 into a flask, stirring for 20 min, adding the aqueous solution of the cotton straw cellulose to continue the reaction, and then adding epichlorohydrin for reaction; and removing the oil phase in the reaction system, and cleaning and drying the product to obtain a cellulose microsphere adsorbent. The obtained cellulose microsphere adsorbent has a good adsorption effect on active blue M and metal ions Cr6+ and Cu2+ in wastewater, and has broad application prospects.

Description

一种纤维素微球吸附剂的制备方法Method for preparing cellulose microsphere adsorbent 技术领域Technical field
本发明涉及化工与环保领域，尤其是涉及一种纤维素微球吸附剂的制备方法。The invention relates to the field of chemical industry and environmental protection, in particular to a preparation method of cellulose microsphere adsorbent.
背景技术Background technique
纤维素是地球上最古老、最丰富的天然高分子，是取之不尽用之不竭的人类最宝贵的天然可再生资源。纤维素具有可再生性、可生物降解性、生物相容性好、无毒等优点。对纤维素进行改性，引入一些功能性基团，制备得到具有一定形态的吸附剂，可以在废水处理方面得到广泛的利用。我国印染纺织工业每年都要排放大量的染料废水，对环境造成了严重污染。染料废水的成分复杂，色度深，排放量大，处理和回收的难度极大。此外许多生产废水中含有重金属离子，这些废水排放后对环境、水资源、人类健康都造成了极大的不利影响，制备有效的废水处理物质是研究的重点。Cellulose is the oldest and richest natural polymer on the planet, and the most precious natural renewable resource for human beings. Cellulose has the advantages of reproducibility, biodegradability, good biocompatibility and non-toxicity. Modification of cellulose, introduction of some functional groups, preparation of adsorbents with a certain form, can be widely used in wastewater treatment. China's printing and dyeing textile industry discharges a large amount of dye wastewater every year, causing serious pollution to the environment. The composition of dye wastewater is complex, the color is deep, and the amount of discharge is large. It is extremely difficult to treat and recycle. In addition, many production wastewaters contain heavy metal ions. These wastewaters have a great adverse impact on the environment, water resources and human health. The preparation of effective wastewater treatment substances is the focus of research.
发明内容Summary of the invention
要解决的技术问题：Technical problems to be solved:
本发明的目的是为了解决背景技术中提到的问题以及现有技术的不足，提供一种纤维素微球吸附剂的制备方法。The purpose of the present invention is to provide a method for preparing cellulose microsphere adsorbent in order to solve the problems mentioned in the background and the deficiencies of the prior art.
技术方案：Technical solutions:
本发明提供了一种纤维素微球吸附剂的制备方法，包括以下步骤：The invention provides a method for preparing a cellulose microsphere adsorbent, which includes the following steps:
步骤一、将棉花秸杆洗净，烘干后机械粉碎，向棉花秸杆粉末中加入二甲苯和乙醇的混合液，置于沸水浴中反应，取出洗涤，抽滤，加入盐酸溶液，90℃水浴处理1.5h，再加入去离子水水浴反应3h，抽滤，干燥后备用；Step 1: Wash cotton straw, mechanically crush it after drying, add a mixed solution of xylene and ethanol to the cotton straw powder, put it in a boiling water bath to react, take out and wash, suction filter, add hydrochloric acid solution, 90 ℃ Water bath treatment for 1.5h, then add deionized water to the water bath for 3h, filter with suction, dry for use;
步骤二、向步骤一中预处理后的棉花秸杆粉末中加入溶液A进行反应，抽滤，干燥后，向得到的粉末中加入溶液B进行反应，反应后用蒸馏水洗涤至中性，烘干得到棉花秸杆纤维素；Step 2: Add solution A to the cotton straw powder pretreated in step 1 for reaction, suction filtration, and after drying, add solution B to the obtained powder for reaction. After the reaction, wash with distilled water until neutral and dry. Get cotton straw cellulose;
步骤三、将步骤二中制备得到的棉花秸秆纤维素配置成水溶液备用；Step 3: Configure the cotton straw cellulose prepared in Step 2 as an aqueous solution for use;
步骤四、在烧瓶中加入蓖麻油和吐温80，开启搅拌装置和升温装置，搅拌20min，然后加入棉花秸秆纤维素水溶液，继续反应30min后，加入环氧氯丙烷反应9h；Step 4: Add castor oil and Tween 80 to the flask, turn on the stirring device and heating device, stir for 20min, then add cotton straw cellulose aqueous solution, continue the reaction for 30min, add epichlorohydrin to react for 9h;
步骤五、将反应后的体系静置一夜，去除表面油相，将纤维素微球分别用乙酸乙 酯和乙醇清洗，烘干后即得纤维素微球吸附剂。Step 5. The reaction system was allowed to stand overnight, the surface oil phase was removed, the cellulose microspheres were washed with ethyl acetate and ethanol respectively, and the cellulose microsphere adsorbent was obtained after drying.
优选的，步骤一混合液中的二甲苯和乙醇的体积比为3∶2。Preferably, the volume ratio of xylene and ethanol in the mixed solution in step one is 3: 2.
优选的，步骤二中溶液A为过氧化氢和氢氧化钠溶于去离子水中混合而成。Preferably, the solution A in the second step is formed by mixing hydrogen peroxide and sodium hydroxide in deionized water.
优选的，步骤二中溶液B为三氯乙酸和硝酸溶去离子水混合而成。Preferably, in the second step, the solution B is formed by mixing trichloroacetic acid and nitric acid dissolved deionized water.
优选的，步骤三中棉花秸秆纤维素水溶液的浓度为8-16wt％。Preferably, the concentration of the cotton straw aqueous solution in step 3 is 8-16 wt%.
优选的，步骤四中搅拌装置的转速为540-660rad/min，反应温度为50-80℃。Preferably, the rotation speed of the stirring device in step 4 is 540-660 rad / min, and the reaction temperature is 50-80 ° C.
有益效果：Beneficial effect:
(1)本发明控制纤维素的质量分数，纤维素分子之间能够很好的分散在溶液中，进行充分地交联反应，制备的纤维素微球粒径适中、吸附量较大大。(1) The present invention controls the mass fraction of cellulose, and the cellulose molecules can be well dispersed in the solution to perform a sufficient cross-linking reaction, and the prepared cellulose microspheres have a moderate particle size and a large adsorption capacity.
(2)本发明中控制反应的搅拌速度为540-660rad/min，反应温度为50-80℃，能够使环氧氯丙烷与纤维素分子之间充分交联反应，并且形成的微球具有较大的总表面积，吸附性能较好。(2) In the present invention, the stirring speed of the controlled reaction is 540-660 rad / min, and the reaction temperature is 50-80 ° C, which can make the cross-linking reaction between epichlorohydrin and cellulose molecules sufficient, and the formed microspheres have a Large total surface area, good adsorption performance.
具体实施方式detailed description
下面的实施例可使本专业技术人员更全面地理解本发明，但不以任何方式限制本发明。The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
实施例1Example 1
步骤一、将棉花秸杆用蒸馏水冲洗干净，烘干后机械粉碎至50目，向棉花秸杆粉末中加入二甲苯和乙醇的混合液，料液比为1∶10(g/mL)，其中二甲苯和乙醇的体积比为3∶2，置于沸水浴中反应6h，取出用乙醇洗涤3次，抽滤，加入0.1mol/L盐酸溶液，料液比为1∶12(g/mL)，90℃水浴处理1.5h，再加入去离子水，料液比为1∶20(g/mL)，85℃，200r/min水浴反应3h，抽滤，60℃干燥后备用；Step 1: Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 ℃ water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 ℃, 200r / min water bath reaction for 3h, suction filtration, dried at 60 ℃ for use;
步骤二、向步骤一中预处理后的棉花秸杆粉末中加入溶液A，料液比为1∶20(g/mL)，溶液A为0.6mL过氧化氢和3g氢氧化钠溶于100mL去离子水中混合而成，在90℃下反应4h，抽滤，60℃干燥后，向得到的粉末中加入溶液B，料液比为1∶25(g/mL)，溶液B为0.8g三氯乙酸和6mL硝酸溶于100mL去离子水混合而成，在60℃下处理3h，蒸馏水洗涤至中性，60℃烘干后得到棉花秸杆纤维素；Step 2: Add solution A to the cotton straw powder pretreated in step 1, the material-liquid ratio is 1:20 (g / mL), solution A is 0.6mL hydrogen peroxide and 3g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 90 ℃ for 4h, filtering with suction, drying at 60 ℃, adding solution B to the obtained powder, the material-liquid ratio is 1:25 (g / mL), solution B is 0.8g trichloro Acetic acid and 6mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 60 ℃ for 3h, washed with distilled water until neutral, and dried at 60 ℃ to obtain cotton straw cellulose;
步骤三、将步骤二中制备得到的棉花秸秆纤维素配置成16wt％的水溶液备用；Step 3: Configure the cotton straw cellulose prepared in Step 2 as a 16wt% aqueous solution for use;
步骤四、在烧瓶中加入60mL蓖麻油和0.25g吐温80，调整转速为540rad/min，升温至80℃，搅拌20min，然后加入10mL棉花秸秆纤维素水溶液，继续反应30min后，加入1.45mL环氧氯丙烷，反应9h；Step 4: Add 60mL castor oil and 0.25g Tween 80 to the flask, adjust the rotation speed to 540rad / min, increase the temperature to 80 ° C, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, continue the reaction for 30min, add 1.45mL ring Oxychloropropane, reaction 9h;
步骤五、将反应后的体系静置一夜，去除表面油相，将纤维素微球用乙酸乙酯溶液清洗3次，再用乙醇溶液清洗6次，在80℃烘箱中烘干即得纤维素微球吸附剂。Step 5: Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 ℃ to obtain cellulose Microsphere adsorbent.
实施例2Example 2
步骤一、将棉花秸杆用蒸馏水冲洗干净，烘干后机械粉碎至50目，向棉花秸杆粉末中加入二甲苯和乙醇的混合液，料液比为1∶10(g/mL)，其中二甲苯和乙醇的体积比为3∶2，置于沸水浴中反应6h，取出用乙醇洗涤3次，抽滤，加入0.1mol/L盐酸溶液，料液比为1∶12(g/mL)，90℃水浴处理1.5h，再加入去离子水，料液比为1∶20(g/mL)，85℃，200r/min水浴反应3h，抽滤，60℃干燥后备用；Step 1: Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 ℃ water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 ℃, 200r / min water bath reaction for 3h, suction filtration, dried at 60 ℃ for use;
步骤二、向步骤一中预处理后的棉花秸杆粉末中加入溶液A，料液比为1∶20(g/mL)，溶液A为0.2mL过氧化氢和8g氢氧化钠溶于100mL去离子水中混合而成，在60℃下反应4h，抽滤，60℃干燥后，向得到的粉末中加入溶液B，料液比为1∶25(g/mL)，溶液B为1.2g三氯乙酸和2mL硝酸溶于100mL去离子水混合而成，在80℃下处理1h，蒸馏水洗涤至中性，60℃烘干后得到棉花秸杆纤维素；Step two: Add solution A to the cotton straw powder pretreated in step one, the material-liquid ratio is 1:20 (g / mL), solution A is 0.2mL hydrogen peroxide and 8g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 60 ℃ for 4h, filtering with suction, drying at 60 ℃, adding solution B to the powder obtained, the material-liquid ratio is 1:25 (g / mL), solution B is 1.2g trichloro Acetic acid and 2mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 80 ℃ for 1h, washed with distilled water until neutral, and dried at 60 ℃ to obtain cotton straw cellulose;
步骤三、将步骤二中制备得到的棉花秸秆纤维素配置成8wt％的水溶液备用；Step 3: Configure the cotton straw cellulose prepared in Step 2 as an 8wt% aqueous solution for use;
步骤四、在烧瓶中加入80mL蓖麻油和0.05g吐温80，调整转速为660rad/min，升温至50℃，搅拌20min，然后加入10mL棉花秸秆纤维素水溶液，继续反应30min后，加入2.25mL环氧氯丙烷，反应9h；Step 4: Add 80 mL of castor oil and 0.05 g of Tween 80 to the flask, adjust the rotation speed to 660 rad / min, increase the temperature to 50 ° C, stir for 20 min, then add 10 mL of cotton straw cellulose aqueous solution, continue the reaction for 30 min, add 2.25 mL of ring Oxychloropropane, reaction 9h;
步骤五、将反应后的体系静置一夜，去除表面油相，将纤维素微球用乙酸乙酯溶液清洗3次，再用乙醇溶液清洗6次，在80℃烘箱中烘干即得纤维素微球吸附剂。Step 5: Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 ℃ to obtain cellulose Microsphere adsorbent.
实施例3Example 3
步骤一、将棉花秸杆用蒸馏水冲洗干净，烘干后机械粉碎至50目，向棉花秸杆粉末中加入二甲苯和乙醇的混合液，料液比为1∶10(g/mL)，其中二甲苯和乙醇的体积比为3∶2，置于沸水浴中反应6h，取出用乙醇洗涤3次，抽滤，加入0.1mol/L盐酸溶液，料液比为1∶12(g/mL)，90℃水浴处理1.5h，再加入去离子水，料液比为1∶20(g/mL)，85℃，200r/min水浴反应3h，抽滤，60℃干燥后备用；Step 1: Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 ℃ water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 ℃, 200r / min water bath reaction for 3h, suction filtration, dried at 60 ℃ for use;
步骤二、向步骤一中预处理后的棉花秸杆粉末中加入溶液A，料液比为1∶20(g/mL)，溶液A为0.5mL过氧化氢和4g氢氧化钠溶于100mL去离子水中混合而成，在80℃下反应4h，抽滤，60℃干燥后，向得到的粉末中加入溶液B，料液比为1∶25(g/mL)，溶液B为0.9g三氯乙酸和5mL硝酸溶于100mL去离子水混合而成，在65℃下处理2.5h，蒸馏水洗涤至中性，60℃烘干后得到棉花秸杆纤维素；Step two: Add solution A to the cotton straw powder pretreated in step one, the material-liquid ratio is 1:20 (g / mL), solution A is 0.5mL hydrogen peroxide and 4g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 80 ℃ for 4h, filtering with suction, drying at 60 ℃, adding solution B to the powder obtained, the material-liquid ratio is 1:25 (g / mL), solution B is 0.9g trichloromethane Acetic acid and 5mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 65 ℃ for 2.5h, washed with distilled water to neutral, and dried at 60 ℃ to obtain cotton straw cellulose;
步骤三、将步骤二中制备得到的棉花秸秆纤维素配置成14wt％的水溶液备用；Step 3: Configure the cotton straw cellulose prepared in Step 2 as a 14wt% aqueous solution for use;
步骤四、在烧瓶中加入65mL蓖麻油和0.2g吐温80，调整转速为570rad/min，升温至70℃，搅拌20min，然后加入10mL棉花秸秆纤维素水溶液，继续反应30min后，加入1.65mL环氧氯丙烷，反应9h；Step 4: Add 65mL castor oil and 0.2g Tween 80 to the flask, adjust the rotation speed to 570rad / min, increase the temperature to 70 ° C, stir for 20min, then add 10mL cotton straw aqueous cellulose solution, continue the reaction for 30min, add 1.65mL ring Oxychloropropane, reaction 9h;
步骤五、将反应后的体系静置一夜，去除表面油相，将纤维素微球用乙酸乙酯溶液清洗3次，再用乙醇溶液清洗6次，在80℃烘箱中烘干即得纤维素微球吸附剂。Step 5: Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 ℃ to obtain cellulose Microsphere adsorbent.
实施例4Example 4
步骤一、将棉花秸杆用蒸馏水冲洗干净，烘干后机械粉碎至50目，向棉花秸杆粉末中加入二甲苯和乙醇的混合液，料液比为1∶10(g/mL)，其中二甲苯和乙醇的体积比为3∶2，置于沸水浴中反应6h，取出用乙醇洗涤3次，抽滤，加入0.1mol/L盐酸溶液，料液比为1∶12(g/mL)，90℃水浴处理1.5h，再加入去离子水，料液比为1∶20(g/mL)，85℃，200r/min水浴反应3h，抽滤，60℃干燥后备用；Step 1: Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 ℃ water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 ℃, 200r / min water bath reaction for 3h, suction filtration, dried at 60 ℃ for use;
步骤二、向步骤一中预处理后的棉花秸杆粉末中加入溶液A，料液比为1∶20(g/mL)，溶液A为0.3mL过氧化氢和7g氢氧化钠溶于100mL去离子水中混合而成，在70℃下反应4h，抽滤，60℃干燥后，向得到的粉末中加入溶液B， 料液比为1∶25(g/mL)，溶液B为1.1g三氯乙酸和3mL硝酸溶于100mL去离子水混合而成，在75℃下处理1.5h，蒸馏水洗涤至中性，60℃烘干后得到棉花秸杆纤维素；Step two: Add solution A to the cotton straw powder pretreated in step one, the material-liquid ratio is 1:20 (g / mL), solution A is 0.3mL hydrogen peroxide and 7g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 70 ℃ for 4h, filtering with suction, and drying at 60 ℃, adding solution B to the obtained powder, the material-liquid ratio is 1:25 (g / mL), solution B is 1.1g trichloro Acetic acid and 3mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 75 ℃ for 1.5h, washed with distilled water until neutral, and dried at 60 ℃ to obtain cotton straw cellulose;
步骤三、将步骤二中制备得到的棉花秸秆纤维素配置成10wt％的水溶液备用；Step 3: Configure the cotton straw cellulose prepared in Step 2 as a 10wt% aqueous solution for use;
步骤四、在烧瓶中加入75mL蓖麻油和0.1g吐温80，调整转速为630rad/min，升温至60℃，搅拌20min，然后加入10mL棉花秸秆纤维素水溶液，继续反应30min后，加入2.05mL环氧氯丙烷，反应9h；Step 4: Add 75mL castor oil and 0.1g Tween 80 to the flask, adjust the rotation speed to 630rad / min, increase the temperature to 60 ℃, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, and continue the reaction for 30min, add 2.05mL ring Oxychloropropane, reaction 9h;
步骤五、将反应后的体系静置一夜，去除表面油相，将纤维素微球用乙酸乙酯溶液清洗3次，再用乙醇溶液清洗6次，在80℃烘箱中烘干即得纤维素微球吸附剂。Step 5: Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 ℃ to obtain cellulose Microsphere adsorbent.
实施例5Example 5
步骤一、将棉花秸杆用蒸馏水冲洗干净，烘干后机械粉碎至50目，向棉花秸杆粉末中加入二甲苯和乙醇的混合液，料液比为1∶10(g/mL)，其中二甲苯和乙醇的体积比为3∶2，置于沸水浴中反应6h，取出用乙醇洗涤3次，抽滤，加入0.1mol/L盐酸溶液，料液比为1∶12(g/mL)，90℃水浴处理1.5h，再加入去离子水，料液比为1∶20(g/mL)，85℃，200r/min水浴反应3h，抽滤，60℃干燥后备用；Step 1: Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 ℃ water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 ℃, 200r / min water bath reaction for 3h, suction filtration, dried at 60 ℃ for use;
步骤二、向步骤一中预处理后的棉花秸杆粉末中加入溶液A，料液比为1∶20(g/mL)，溶液A为0.4mL过氧化氢和5.5g氢氧化钠溶于100mL去离子水中混合而成，在75℃下反应4h，抽滤，60℃干燥后，向得到的粉末中加入溶液B，料液比为1∶25(g/mL)，溶液B为1g三氯乙酸和4mL硝酸溶于100mL去离子水混合而成，在70℃下处理2h，蒸馏水洗涤至中性，60℃烘干后得到棉花秸杆纤维素；Step two: Add solution A to the cotton straw powder pretreated in step one, the material-liquid ratio is 1:20 (g / mL), solution A is 0.4mL hydrogen peroxide and 5.5g sodium hydroxide dissolved in 100mL It is mixed with deionized water, reacted at 75 ℃ for 4h, filtered with suction, and dried at 60 ℃. Solution B is added to the obtained powder. The material-liquid ratio is 1:25 (g / mL). Solution B is 1g of trichloromethane Acetic acid and 4mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 70 ℃ for 2h, washed with distilled water until neutral, and dried at 60 ℃ to obtain cotton straw cellulose;
步骤三、将步骤二中制备得到的棉花秸秆纤维素配置成12wt％的水溶液备用；Step 3: Configure the cotton straw cellulose prepared in Step 2 as a 12wt% aqueous solution for use;
步骤四、在烧瓶中加入70mL蓖麻油和0.15g吐温80，调整转速为600rad/min，升温至65℃，搅拌20min，然后加入10mL棉花秸秆纤维素水溶液，继续反应30min后，加入1.85mL环氧氯丙烷，反应9h；Step 4: Add 70mL castor oil and 0.15g Tween 80 to the flask, adjust the rotation speed to 600rad / min, increase the temperature to 65 ℃, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, continue the reaction for 30min, add 1.85mL ring Oxychloropropane, reaction 9h;
步骤五、将反应后的体系静置一夜，去除表面油相，将纤维素微球用乙酸乙酯溶液清洗3次，再用乙醇溶液清洗6次，在80℃烘箱中烘干即得纤维素微球吸附 剂。Step 5: Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 ℃ to obtain cellulose Microsphere adsorbent.
对比例1Comparative Example 1
本对比例与实施例1的区别在于步骤三中棉花秸秆纤维素水溶液的浓度为5wt％。The difference between this comparative example and Example 1 is that the concentration of the cotton straw aqueous solution in step 3 is 5 wt%.
具体地说是：Specifically:
步骤一、将棉花秸杆用蒸馏水冲洗干净，烘干后机械粉碎至50目，向棉花秸杆粉末中加入二甲苯和乙醇的混合液，料液比为1∶10(g/mL)，其中二甲苯和乙醇的体积比为3∶2，置于沸水浴中反应6h，取出用乙醇洗涤3次，抽滤，加入0.1mol/L盐酸溶液，料液比为1∶12(g/mL)，90℃水浴处理1.5h，再加入去离子水，料液比为1∶20(g/mL)，85℃，200r/min水浴反应3h，抽滤，60℃干燥后备用；Step 1: Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 ℃ water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 ℃, 200r / min water bath reaction for 3h, suction filtration, dried at 60 ℃ for use;
步骤二、向步骤一中预处理后的棉花秸杆粉末中加入溶液A，料液比为1∶20(g/mL)，溶液A为0.6mL过氧化氢和3g氢氧化钠溶于100mL去离子水中混合而成，在90℃下反应4h，抽滤，60℃干燥后，向得到的粉末中加入溶液B，料液比为1∶25(g/mL)，溶液B为0.8g三氯乙酸和6mL硝酸溶于100mL去离子水混合而成，在60℃下处理3h，蒸馏水洗涤至中性，60℃烘干后得到棉花秸杆纤维素；Step 2: Add solution A to the cotton straw powder pretreated in step 1, the material-liquid ratio is 1:20 (g / mL), solution A is 0.6mL hydrogen peroxide and 3g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 90 ℃ for 4h, filtering with suction, drying at 60 ℃, adding solution B to the obtained powder, the material-liquid ratio is 1:25 (g / mL), solution B is 0.8g trichloro Acetic acid and 6mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 60 ℃ for 3h, washed with distilled water until neutral, and dried at 60 ℃ to obtain cotton straw cellulose;
步骤三、将步骤二中制备得到的棉花秸秆纤维素配置成5wt％的水溶液备用；Step 3: Configure the cotton straw cellulose prepared in Step 2 as a 5wt% aqueous solution for use;
步骤四、在烧瓶中加入60mL蓖麻油和0.25g吐温80，调整转速为540rad/min，升温至80℃，搅拌20min，然后加入10mL棉花秸秆纤维素水溶液，继续反应30min后，加入1.45mL环氧氯丙烷，反应9h；Step 4: Add 60mL castor oil and 0.25g Tween 80 to the flask, adjust the rotation speed to 540rad / min, increase the temperature to 80 ° C, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, continue the reaction for 30min, add 1.45mL ring Oxychloropropane, reaction 9h;
步骤五、将反应后的体系静置一夜，去除表面油相，将纤维素微球用乙酸乙酯溶液清洗3次，再用乙醇溶液清洗6次，在80℃烘箱中烘干即得纤维素微球吸附剂。Step 5: Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 ℃ to obtain cellulose Microsphere adsorbent.
对比例2Comparative Example 2
本对比例与实施例1的区别在于步骤四中搅拌速度为400rad/min。具体地说是：The difference between this comparative example and Example 1 is that the stirring speed in step 4 is 400 rad / min. Specifically:
步骤一、将棉花秸杆用蒸馏水冲洗干净，烘干后机械粉碎至50目，向棉花秸杆粉末中加入二甲苯和乙醇的混合液，料液比为1∶10(g/mL)，其中二甲苯和乙 醇的体积比为3∶2，置于沸水浴中反应6h，取出用乙醇洗涤3次，抽滤，加入0.1mol/L盐酸溶液，料液比为1∶12(g/mL)，90℃水浴处理1.5h，再加入去离子水，料液比为1∶20(g/mL)，85℃，200r/min水浴反应3h，抽滤，60℃干燥后备用；Step 1: Rinse the cotton straw with distilled water, dry and mechanically pulverize it to 50 mesh, add a mixed liquid of xylene and ethanol to the cotton straw powder, the material-liquid ratio is 1:10 (g / mL), where The volume ratio of xylene and ethanol is 3: 2, placed in a boiling water bath to react for 6h, taken out and washed with ethanol 3 times, filtered with suction, added 0.1mol / L hydrochloric acid solution, the material-liquid ratio is 1:12 (g / mL) At 90 ℃ water bath for 1.5h, then add deionized water, the material-liquid ratio is 1:20 (g / mL), 85 ℃, 200r / min water bath reaction for 3h, suction filtration, dried at 60 ℃ for use;
步骤二、向步骤一中预处理后的棉花秸杆粉末中加入溶液A，料液比为1∶20(g/mL)，溶液A为0.6mL过氧化氢和3g氢氧化钠溶于100mL去离子水中混合而成，在90℃下反应4h，抽滤，60℃干燥后，向得到的粉末中加入溶液B，料液比为1∶25(g/mL)，溶液B为0.8g三氯乙酸和6mL硝酸溶于100mL去离子水混合而成，在60℃下处理3h，蒸馏水洗涤至中性，60℃烘干后得到棉花秸杆纤维素；Step 2: Add solution A to the cotton straw powder pretreated in step 1, the material-liquid ratio is 1:20 (g / mL), solution A is 0.6mL hydrogen peroxide and 3g sodium hydroxide dissolved in 100mL It is made up by mixing in ionic water, reacting at 90 ℃ for 4h, filtering with suction, drying at 60 ℃, adding solution B to the obtained powder, the material-liquid ratio is 1:25 (g / mL), solution B is 0.8g trichloro Acetic acid and 6mL nitric acid are dissolved in 100mL deionized water and mixed, treated at 60 ℃ for 3h, washed with distilled water until neutral, and dried at 60 ℃ to obtain cotton straw cellulose;
步骤三、将步骤二中制备得到的棉花秸秆纤维素配置成16wt％的水溶液备用；Step 3: Configure the cotton straw cellulose prepared in Step 2 as a 16wt% aqueous solution for use;
步骤四、在烧瓶中加入60mL蓖麻油和0.25g吐温80，调整转速为400rad/min，升温至80℃，搅拌20min，然后加入10mL棉花秸秆纤维素水溶液，继续反应30min后，加入1.45mL环氧氯丙烷，反应9h；Step 4: Add 60mL of castor oil and 0.25g of Tween 80 to the flask, adjust the speed to 400rad / min, heat to 80 ° C, stir for 20min, then add 10mL of cotton straw cellulose aqueous solution, continue the reaction for 30min, add 1.45mL Oxychloropropane, reaction 9h;
步骤五、将反应后的体系静置一夜，去除表面油相，将纤维素微球用乙酸乙酯溶液清洗3次，再用乙醇溶液清洗6次，在80℃烘箱中烘干即得纤维素微球吸附剂。Step 5: Allow the reaction system to stand overnight, remove the surface oil phase, wash the cellulose microspheres with ethyl acetate solution 3 times, then with ethanol solution 6 times, and dry in an oven at 80 ℃ to obtain cellulose Microsphere adsorbent.
将实施例1-5和对比例1-2中制备得到的吸附剂进行性能测试。The performance of the adsorbents prepared in Examples 1-5 and Comparative Examples 1-2 was tested.
将0.3g纤维素微球吸附剂分别加入100mL的5μg/mL的活性蓝M溶液、100mL0.08g/mL Cr 6+溶液和100mL 0.08g/mL Cu 2+溶液中进行吸附，采用分光光度法测定吸附后滤液的吸光值，计算出吸附率，测试结果见下表： 0.3g cellulose microsphere adsorbent was added to 100mL of 5μg / mL active blue M solution, 100mL0.08g / mL Cr 6+ solution and 100mL 0.08g / mL Cu 2+ solution for adsorption, measured by spectrophotometry The absorption value of the filtrate after adsorption, the adsorption rate is calculated, the test results are shown in the table below:
 A 活性蓝M吸附率/％Reactive blue M adsorption rate /% Cr 6+吸附率/％ Cr 6+ adsorption rate /% Cu 2+吸附率/％ Cu 2+ adsorption rate /%
实施例1Example 1 92.6692.66 82.5582.55 88.7688.76
实施例2Example 2 93.2893.28 84.1784.17 90.3290.32
实施例3Example 3 95.4195.41 84.8984.89 90.8890.88
实施例4Example 4 97.2697.26 86.2486.24 92.5792.57
实施例5Example 5 98.7498.74 88.3788.37 93.4693.46
对比例1Comparative Example 1 74.1374.13 61.4361.43 68.9568.95
对比例2Comparative Example 2 85.1885.18 65.2765.27 76.4276.42
由测试结果可知，本发明制备得到的纤维素微球吸附剂对染料废水具有很好的吸附效果，对活性蓝M吸附率达到92.66-98.74％，对废水中的金属离子Cr 6+和Cu 2+也具有较好的吸附效果，对Cr 6+吸附率达到82.55-88.37％，对Cu 2+吸附率达到88.76-93.46％。实施例5中制备的纤维素微球吸附剂达到了最好的处理效果，因此实施例5是本发明的最优方案。对比例1中棉花秸秆纤维素水溶液的浓度为5wt％，质量分数太低，纤维素分子之间不能很好的进行交联反应，造成形成的微球粒径过小，吸附性能较差。对比例2中搅拌速度为400rad/min，搅拌速度过低，不利于反应体系中的水相分散，液滴得不到很好的分散，形成的微球总表面积较小，吸附性能欠佳。 It can be seen from the test results that the cellulose microsphere adsorbent prepared by the present invention has a very good adsorption effect on dye wastewater, the adsorption rate of reactive blue M reaches 92.66-98.74%, and the metal ions Cr 6+ and Cu 2 in wastewater + Also has a good adsorption effect, the adsorption rate of Cr 6+ reaches 82.55-88.37%, and the adsorption rate of Cu 2+ reaches 88.76-93.46%. The cellulose microsphere adsorbent prepared in Example 5 achieves the best treatment effect, so Example 5 is the optimal solution of the present invention. In Comparative Example 1, the concentration of the cotton straw aqueous cellulose solution is 5 wt%, the mass fraction is too low, and the cross-linking reaction between the cellulose molecules cannot be performed well, resulting in the formation of microspheres with a too small particle size and poor adsorption performance. The stirring speed in Comparative Example 2 is 400 rad / min. The stirring speed is too low, which is not conducive to the dispersion of the aqueous phase in the reaction system, the droplets cannot be well dispersed, the total surface area of the formed microspheres is small, and the adsorption performance is poor.

Claims (6)

  1. 一种纤维素微球吸附剂的制备方法，其特征在于，包括以下步骤：A method for preparing cellulose microsphere adsorbent, characterized in that it includes the following steps:
    步骤一、将棉花秸杆洗净，烘干后机械粉碎，向棉花秸杆粉末中加入二甲苯和乙醇的混合液，置于沸水浴中反应，取出洗涤，抽滤，加入盐酸溶液，90℃水浴处理1.5h，再加入去离子水水浴反应3h，抽滤，干燥后备用；Step 1: Wash cotton straw, mechanically crush it after drying, add a mixed solution of xylene and ethanol to the cotton straw powder, put it in a boiling water bath to react, take out and wash, suction filter, add hydrochloric acid solution, 90 ℃ Water bath treatment for 1.5h, then add deionized water to the water bath for 3h, filter with suction, dry for use;
    步骤二、向步骤一中预处理后的棉花秸杆粉末中加入溶液A进行反应，抽滤，干燥后，向得到的粉末中加入溶液B进行反应，反应后用蒸馏水洗涤至中性，烘干得到棉花秸杆纤维素；Step 2: Add solution A to the cotton straw powder pretreated in step 1 for reaction, suction filtration, and after drying, add solution B to the obtained powder for reaction. After the reaction, wash with distilled water until neutral and dry. Get cotton straw cellulose;
    步骤三、将步骤二中制备得到的棉花秸秆纤维素配置成水溶液备用；Step 3: Configure the cotton straw cellulose prepared in Step 2 as an aqueous solution for use;
    步骤四、在烧瓶中加入蓖麻油和吐温80，开启搅拌装置和升温装置，搅拌20min，然后加入棉花秸秆纤维素水溶液，继续反应30min后，加入环氧氯丙烷反应9h；Step 4: Add castor oil and Tween 80 to the flask, turn on the stirring device and heating device, stir for 20min, then add cotton straw cellulose aqueous solution, continue the reaction for 30min, add epichlorohydrin to react for 9h;
    步骤五、将反应后的体系静置一夜，去除表面油相，将纤维素微球分别用乙酸乙酯和乙醇清洗，烘干后即得纤维素微球吸附剂。Step 5: The system after the reaction was allowed to stand overnight, the surface oil phase was removed, the cellulose microspheres were washed with ethyl acetate and ethanol, and the cellulose microsphere adsorbent was obtained after drying.
  2. 根据权利要求1所述的一种纤维素微球吸附剂的制备方法，其特征在于，步骤一混合液中的二甲苯和乙醇的体积比为3∶2。The method for preparing a cellulose microsphere adsorbent according to claim 1, wherein the volume ratio of xylene and ethanol in the mixed solution in step one is 3: 2.
  3. 根据权利要求1所述的一种纤维素微球吸附剂的制备方法，其特征在于，步骤二中溶液A为过氧化氢和氢氧化钠溶于去离子水中混合而成。The method for preparing a cellulose microsphere adsorbent according to claim 1, wherein the solution A in step 2 is a mixture of hydrogen peroxide and sodium hydroxide dissolved in deionized water.
  4. 根据权利要求1所述的一种纤维素微球吸附剂的制备方法，其特征在于，步骤二中溶液B为三氯乙酸和硝酸溶去离子水混合而成。The method for preparing a cellulose microsphere adsorbent according to claim 1, wherein the solution B in step 2 is a mixture of trichloroacetic acid and nitric acid dissolved deionized water.
  5. 根据权利要求1所述的一种纤维素微球吸附剂的制备方法，其特征在于，步骤三中棉花秸秆纤维素水溶液的浓度为8-16wt％。The method for preparing a cellulose microsphere adsorbent according to claim 1, wherein the concentration of the cotton straw aqueous cellulose solution in step 3 is 8-16 wt%.
  6. 根据权利要求1所述的一种纤维素微球吸附剂的制备方法，其特征在于，步骤四中搅拌装置的转速为540-660rad/min，反应温度为50-80℃。The method for preparing a cellulose microsphere adsorbent according to claim 1, wherein the rotation speed of the stirring device in step 4 is 540-660 rad / min, and the reaction temperature is 50-80 ° C.
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