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WO2025039248A1 - Matériau d'adsorption sélective pour le traitement des eaux usées contenant du béryllium et son procédé de préparation, et procédé de traitement des eaux usées contenant du béryllium l'utilisant - Google Patents

Matériau d'adsorption sélective pour le traitement des eaux usées contenant du béryllium et son procédé de préparation, et procédé de traitement des eaux usées contenant du béryllium l'utilisant Download PDF

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Publication number
WO2025039248A1
WO2025039248A1 PCT/CN2023/114596 CN2023114596W WO2025039248A1 WO 2025039248 A1 WO2025039248 A1 WO 2025039248A1 CN 2023114596 W CN2023114596 W CN 2023114596W WO 2025039248 A1 WO2025039248 A1 WO 2025039248A1
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WO
WIPO (PCT)
Prior art keywords
adsorption material
containing wastewater
beryllium
treating
selective adsorption
Prior art date
Application number
PCT/CN2023/114596
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English (en)
Chinese (zh)
Inventor
邵立南
杨晓松
孙超
Original Assignee
矿冶科技集团有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 矿冶科技集团有限公司 filed Critical 矿冶科技集团有限公司
Priority to PCT/CN2023/114596 priority Critical patent/WO2025039248A1/fr
Publication of WO2025039248A1 publication Critical patent/WO2025039248A1/fr

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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives

Definitions

  • the present application relates to the field of wastewater treatment, and in particular to a selective adsorption material for treating beryllium-containing wastewater, a preparation method thereof, and a method for treating beryllium-containing wastewater using the selective adsorption material.
  • the purpose of the present application is to provide a selective adsorption material for treating beryllium-containing wastewater, a preparation method thereof, and a method for treating beryllium-containing wastewater using the same, so as to solve the above-mentioned problems.
  • a method for preparing a selective adsorption material for treating beryllium-containing wastewater comprising:
  • the activated carbon is mixed with nitric acid, heated at 50-80°C for 2-3 hours, washed to neutrality, and dried at 80-110°C to obtain modified activated carbon;
  • the modified activated carbon, the loading solution and 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid sulfonic acid succinimide ester sodium salt are mixed, ammonia water is added to adjust the pH value to 9-10, and then a first heat treatment and a second heat treatment are sequentially performed to obtain a primary adsorption material; the temperature of the first heat treatment is 60-80° C. and the time is 45-60 min; the temperature of the second heat treatment is 100-120° C. and the time is 8-10 h;
  • the primary adsorption material is washed and then vacuum dried to obtain the selective adsorption material for treating beryllium-containing wastewater.
  • the particle size of the activated carbon is 20-50 mesh;
  • the mass volume ratio of the activated carbon to the nitric acid is 5g:(10-20)mL.
  • the mass volume ratio of the aluminum chloride, the ethanol, the maleimide and the mercaptoethylamine is 1 g: (60-80) mL: (0.1-0.5) g: (0.01-0.5) g.
  • the sodium salt of 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid sulfosuccinimide ester is prepared in advance as an aqueous solution with a mass fraction of 12-18% for use;
  • the mass volume ratio of the modified activated carbon, the loading solution, and the sodium salt of 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid sulfonic acid succinimide ester is 5g:(50-80)mL:(20-40)mL.
  • the cleaning comprises:
  • the primary adsorption material was repeatedly washed with deionized water and ethanol for 30-45 min.
  • the vacuum drying temperature is 60-80°C.
  • the present application also provides a selective adsorption material for treating beryllium-containing wastewater, which is prepared using the preparation method of the selective adsorption material for treating beryllium-containing wastewater.
  • the material with a particle size of 0.3-0.85 mm accounts for greater than or equal to 98 wt %.
  • the selective adsorption material for treating beryllium-containing wastewater is mixed with the beryllium-containing wastewater and subjected to adsorption treatment.
  • the adsorption treatment is carried out at a pH of 6-10.
  • the present application provides a method for preparing a selective adsorption material for treating wastewater containing beryllium.
  • the activated carbon is first pre-treated with acid to expand the pores, which is conducive to the transfer and diffusion of ions during the adsorption process and the loading of more selective adsorption particles in the pores.
  • After loading aluminum it is treated with ammonia water to form a hydrated oxide with a special aluminum metal-hydroxyl group.
  • the oxygen in the hydroxyl group has unbonded electrons that cooperate with the empty orbit of beryllium to form a coordination bond adsorption, which improves the adsorption selectivity of beryllium; at the same time, it is also loaded with imine and thiol groups, and the selectivity for beryllium is further increased through coordination. Compared with other adsorbents on the market, it has a different separation principle.
  • the adsorption treatment of heavy metals in this application mainly relies on the hydroxyl groups of hydrated aluminum oxide, as well as the adsorption of imine and thiol groups.
  • the selective adsorption material for treating beryllium-containing wastewater provided in the present application has good selectivity, large adsorption capacity, good stability, no need for frequent regeneration, and long service life.
  • the use of the selective adsorption material for treating beryllium-containing wastewater provided in the present application to treat beryllium-containing wastewater can meet the comprehensive wastewater discharge standard (total beryllium ⁇ 0.005 mg/L), with high adsorption efficiency and low treatment cost.
  • FIG1 is a scanning electron microscope photograph of the selective adsorption material for treating beryllium-containing wastewater obtained in Example 1 before and after modification;
  • FIG. 2 is an infrared spectrum of the selective adsorption material for treating beryllium-containing wastewater obtained in Example 1.
  • compositions, processes, methods, articles, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • Parts by mass refers to the basic unit of measurement for expressing the mass ratio of multiple components. 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass of component A is a parts and the mass of component B is b parts, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike the mass parts, the sum of the mass of all components is not limited to 100 parts.
  • a and/or B includes (A and B) and (A or B).
  • a method for preparing a selective adsorption material for treating beryllium-containing wastewater comprising:
  • the activated carbon is mixed with nitric acid, heated at 50-80°C for 2-3 hours, washed to neutrality, and dried at 80-110°C to obtain modified activated carbon;
  • the modified activated carbon, the loading solution and 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid sulfonic acid succinimide ester sodium salt are mixed, ammonia water is added to adjust the pH value to 9-10, and then a first heat treatment and a second heat treatment are sequentially performed to obtain a primary adsorption material; the temperature of the first heat treatment is 60-80° C. and the time is 45-60 min; the temperature of the second heat treatment is 100-120° C. and the time is 8-10 h;
  • the primary adsorption material is washed and then vacuum dried to obtain the selective adsorption material for treating beryllium-containing wastewater.
  • the temperature of the heating treatment may be 50°C, 60°C, 70°C, 80°C or any value between 50°C and 80°C, and the time may be 2h, 2.5h, 3h or any value between 2-3h; the temperature of the constant temperature drying may be 80°C, 90°C, 100°C, 110°C or any value between 80°C and 110°C.
  • the pH value of the solution adjusted by adding ammonia water may be 9, 10 or any value between 9-10; the temperature of the first heat treatment may be 60°C, 70°C, 80°C or any value between 60-80°C, and the time may be 45min, 50min, 55min, 60min or any value between 45-60min; the temperature of the second heat treatment may be 100°C, 110°C, 120°C or any value between 100-120°C, and the time may be 8h, 9h, 10h or any value between 8-10h.
  • the particle size of the activated carbon is 20-50 mesh;
  • the mass volume ratio of the activated carbon to the nitric acid is 5g:(10-20)mL.
  • the particle size of the activated carbon can be 20 mesh, 30 mesh, 40 mesh, 50 mesh or any value between 20-50 mesh;
  • the mass volume ratio of the activated carbon to the nitric acid can be 5g:10mL, 5g:15mL, 5g:20mL or any value between 5g:(10-20)mL.
  • the mass volume ratio of the aluminum chloride, the ethanol, the maleimide and the mercaptoethylamine is 1 g: (60-80) mL: (0.1-0.5) g: (0.01-0.5) g.
  • the mass volume ratio of the aluminum chloride, the ethanol, the maleimide and the mercaptoethylamine can be 1g:60ml:0.1g:0.1g, 1g:60ml:0.1g:0.5g, 1g:60ml:0.5g:0.1g, 1g:60ml:0.5g:0.5g, 1g:80ml:0.1g:0.1g, 1g:80ml:0.1g:0.5g, 1g:80ml:0.5g:0.1g, 1g:80ml:0.5g:0.1g, 1g:80ml:0.5g:0.1g, 1g:80ml:0.5g:0.5g or 1g:(60-80)mL:(0.1-0.5)g:(0.1-0.5)g.
  • the sodium salt of 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid sulfosuccinimide ester is pre-formulated into an aqueous solution with a mass fraction of 12-18% for use;
  • the mass volume ratio of the modified activated carbon, the loading solution, and the sodium salt of 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid sulfonic acid succinimide ester is 5g:(50-80)mL:(20-40)mL.
  • the mass fraction of the sodium salt of 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid sulfonyl succinimide ester pre-formulated can be 12%, 13%, 14%, 15%, 16%, 17%, 18% or any value between 12-18%;
  • the mass volume ratio of the activated carbon, the loading solution and the sodium salt of 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid sulfonyl succinimide ester can be any value between 5g:50mL:20mL, 5g:50mL:40mL, 5g:80mL:20mL, 5g:80mL:40mL or 5g:(50-80)mL:(20-40)mL.
  • the cleaning comprises:
  • the vacuum drying temperature is 60-80°C.
  • the present application also provides a selective adsorption material for treating beryllium-containing wastewater, which is prepared using the preparation method of the selective adsorption material for treating beryllium-containing wastewater.
  • the material with a particle size of 0.3-0.85 mm accounts for greater than or equal to 98 wt %.
  • the present application also provides a method for treating beryllium-containing wastewater using the selective adsorption material for treating beryllium-containing wastewater, comprising:
  • the selective adsorption material for treating beryllium-containing wastewater is mixed with the beryllium-containing wastewater and subjected to adsorption treatment.
  • the adsorption treatment is carried out at a pH of 6-10.
  • the pH of the system can be 6, 7, 8, 9, 10 or any value between 6 and 10.
  • This embodiment provides a selective adsorption material for treating beryllium-containing wastewater, and the preparation method thereof is as follows:
  • the scanning electron microscope photograph of the obtained selective adsorption material for treating beryllium-containing wastewater is shown in Figure 1, wherein the left picture is the scanning electron microscope photograph before modification, and the right picture is the scanning electron microscope photograph after modification.
  • Figure 2 is an infrared spectrum of the selective adsorption material for treating beryllium-containing wastewater obtained in Example 1. As shown in Figure 2, the material has a hydroxyl stretching vibration peak at 3139.23 cm -1 , a thiol vibration peak at 2466.51 cm -1 , an imine vibration peak at 1641.61 cm -1 , and metal-hydroxyl vibration peaks at 1404.37 cm -1 and 634.38 cm-1 .
  • the beryllium-containing wastewater is treated by using the selective adsorption material for treating beryllium-containing wastewater, specifically comprising:
  • This embodiment provides a selective adsorption material for treating beryllium-containing wastewater, and the preparation method thereof is as follows:
  • the beryllium-containing wastewater is treated by using the selective adsorption material for treating beryllium-containing wastewater, specifically comprising:
  • This embodiment provides a selective adsorption material for treating beryllium-containing wastewater, and the preparation method thereof is as follows:
  • the beryllium-containing wastewater is treated by using the selective adsorption material for treating beryllium-containing wastewater, specifically comprising:
  • This comparative example provides a selective adsorption material for treating beryllium-containing wastewater, and its preparation method is as follows:
  • the beryllium-containing wastewater is treated by using the selective adsorption material for treating beryllium-containing wastewater, specifically comprising:
  • This comparative example provides a selective adsorption material for treating beryllium-containing wastewater, and its preparation method is as follows:
  • the beryllium-containing wastewater is treated by using the above-mentioned selective adsorption material for treating beryllium-containing wastewater, specifically comprising:
  • This comparative example provides a selective adsorption material for treating beryllium-containing wastewater, and its preparation method is as follows:
  • the beryllium-containing wastewater is treated by using the selective adsorption material for treating beryllium-containing wastewater, specifically comprising:
  • This comparative example provides a selective adsorption material for treating beryllium-containing wastewater, and its preparation method is as follows:
  • the beryllium-containing wastewater is treated by using the selective adsorption material for treating beryllium-containing wastewater, specifically comprising:
  • This comparative example provides a selective adsorption material for treating beryllium-containing wastewater, and its preparation method is as follows:
  • the beryllium-containing wastewater is treated by using the selective adsorption material for treating beryllium-containing wastewater, specifically comprising:
  • This comparative example provides a selective adsorption material for treating beryllium-containing wastewater, and its preparation method is as follows:

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

La présente demande concerne un matériau d'adsorption sélective pour le traitement des eaux usées contenant du béryllium et son procédé de préparation, et un procédé de traitement des eaux usées contenant du béryllium l'utilisant. Le procédé comprend les étapes suivantes : mélange de charbon actif avec de l'acide nitrique, chauffage du mélange résultant à 50-80°C pendant 2-3 heures, lavage de celui-ci jusqu'à ce que celui-ci soit neutre, et séchage de celui-ci à une température constante de 80 à 110°C, de façon à obtenir du charbon actif modifié ; mélange de chlorure d'aluminium, d'éthanol, de maléimide et de mercaptoéthylamine, de façon à obtenir une solution de charge ; mélange du charbon actif modifié, de la solution de charge et du sulfosuccinimidyl 4-(N-maléimidométhyl)cyclohexane-1-carboxylate de sodium, ajout d'eau ammoniacale pour ajuster la valeur de pH à 9-10, puis réalisation de façon séquentielle d'un premier traitement thermique et d'un second traitement thermique, de façon à obtenir un matériau d'adsorption primaire ; et nettoyage du matériau d'adsorption primaire, puis soumission de celui-ci à un séchage sous vide, de façon à obtenir un matériau d'adsorption sélective pour traiter les eaux usées contenant du béryllium. Le matériau préparé au moyen du procédé fourni par la présente demande permet aux eaux usées traitées de se conformer aux valeurs limites prescrites dans la norme intégrée de rejet des eaux usées en Chine, et présente une efficacité d'adsorption élevée et de faibles coûts de traitement.
PCT/CN2023/114596 2023-08-24 2023-08-24 Matériau d'adsorption sélective pour le traitement des eaux usées contenant du béryllium et son procédé de préparation, et procédé de traitement des eaux usées contenant du béryllium l'utilisant WO2025039248A1 (fr)

Priority Applications (1)

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PCT/CN2023/114596 WO2025039248A1 (fr) 2023-08-24 2023-08-24 Matériau d'adsorption sélective pour le traitement des eaux usées contenant du béryllium et son procédé de préparation, et procédé de traitement des eaux usées contenant du béryllium l'utilisant

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PCT/CN2023/114596 WO2025039248A1 (fr) 2023-08-24 2023-08-24 Matériau d'adsorption sélective pour le traitement des eaux usées contenant du béryllium et son procédé de préparation, et procédé de traitement des eaux usées contenant du béryllium l'utilisant

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008036573A (ja) * 2006-08-09 2008-02-21 National Institute Of Advanced Industrial & Technology アンモニウムイオン選択的吸着剤
US20080314830A1 (en) * 2007-06-22 2008-12-25 I. Kruger Inc. Method of Removing Phosphorus from Wastewater
CN114682220A (zh) * 2022-06-01 2022-07-01 矿冶科技集团有限公司 用于处理含铊、汞废水的选择性吸附材料及其制备方法和使用其处理含铊、汞废水的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008036573A (ja) * 2006-08-09 2008-02-21 National Institute Of Advanced Industrial & Technology アンモニウムイオン選択的吸着剤
US20080314830A1 (en) * 2007-06-22 2008-12-25 I. Kruger Inc. Method of Removing Phosphorus from Wastewater
CN114682220A (zh) * 2022-06-01 2022-07-01 矿冶科技集团有限公司 用于处理含铊、汞废水的选择性吸附材料及其制备方法和使用其处理含铊、汞废水的方法

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