WO2020220194A1 - Preparation method for iron-aluminum composite bone char fluoride removal agent and prepared fluoride removal agent - Google Patents
Preparation method for iron-aluminum composite bone char fluoride removal agent and prepared fluoride removal agent Download PDFInfo
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- WO2020220194A1 WO2020220194A1 PCT/CN2019/084978 CN2019084978W WO2020220194A1 WO 2020220194 A1 WO2020220194 A1 WO 2020220194A1 CN 2019084978 W CN2019084978 W CN 2019084978W WO 2020220194 A1 WO2020220194 A1 WO 2020220194A1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
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- the invention belongs to the technical field of fluorine removal from groundwater, and specifically relates to a preparation method of an iron-aluminum composite bone char fluoride removal agent and the prepared fluoride removal agent.
- the national drinking water standard stipulates that the maximum concentration of fluorine in drinking water must be less than 1.0mg/L. If you drink groundwater with excessive fluoride ion concentration for a long time, it is easy to cause dental fluorosis and skeletal fluorosis. It can be seen that long-term use of groundwater with excessive fluorine will seriously affect human health. Therefore, removing fluorine in drinking water is of great significance.
- the technologies for removing fluorine in groundwater include adsorption, membrane separation, ion exchange, electrodialysis, flocculation, etc.
- membrane separation technology can effectively remove fluorine, but the equipment investment and operating costs are too high, and the management is complicated, making it difficult to In practice, especially large-scale promotion and application in rural areas.
- Ion exchange can remove fluorine, but when there are coexisting ions such as NO 3- , SO 4 3- , PO 4 3- , and Cl -in the local sewage, the removal effect of fluorine will be reduced.
- Flocculation can also effectively remove fluorine, but a large amount of flocculant is required, which increases the treatment cost of the medicament.
- the adsorption method is to remove fluorine through the adsorption of fluorine by the adsorbent.
- the adsorption method has the advantages of convenient operation and management, no need to add chemicals, and is widely used.
- Patent literature discloses a method for preparing bone charcoal fluoride removal agent loaded with aluminum ions.
- the adsorption capacity of the bone charcoal fluoride removal agent obtained by this method has been improved, but the increase is small, only 60% higher than ordinary bone charcoal . Therefore, a bone charcoal defluoride agent with higher adsorption capacity is needed.
- the present invention provides a method for preparing an iron-aluminum composite bone charcoal fluoride removal agent and the prepared iron-aluminum composite bone charcoal fluoride removal agent.
- the preparation method of the iron-aluminum composite bone char fluoride remover of the present invention includes the following steps:
- step (2) The bone charcoal obtained in step (1) is cooled, ground, sieved, washed with water, and dried to obtain bone charcoal particles;
- step (3) The bone carbon particles obtained in step (2) are immersed in a Fe 2 (SO 4 ) 3 solution with a mass percentage concentration of 2-8% according to a solid-liquid ratio of 1:2.5-1:10 for 0.3-0.7h, and washed with water After drying, the solid-to-liquid ratio of 1:3-1:8 is immersed in Al 2 (SO 4 ) 3 solution with a mass percentage concentration of 3-10% for 0.5-1.5 hours, washed with water and dried to obtain Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 composite bone charcoal fluoride removal agent.
- animal bones are animal bones, preferably bovine bones.
- the mesh size of the sieved mesh is 10-80 mesh, and the particle size corresponding to the sieved particles is 0.2-2 mm.
- deionized water is used for the water washing, and the water washing until the pH becomes neutral.
- the drying is performed using an oven, and the drying temperature is 100°C.
- the present invention also provides an iron-aluminum composite bone charcoal fluoride removal agent, which is prepared by using the preparation method of the iron-aluminum composite bone charcoal fluoride removal agent.
- the present invention loads aluminum ions and iron ions on bone char, so that the fluorine adsorption capacity of bone charcoal fluoride remover is 8.5 times that of bone charcoal without aluminum iron ions, and the fluorine removal ability is significantly enhanced;
- the three regeneration efficiencies are 94.5%, 90.4% and 86.5%, respectively, and the recyclability is high.
- Fig. 1 is a diagram of the adsorption equilibrium between the iron-aluminum composite bone charcoal fluoride remover and other bovine bone charcoal in Example 1 of the present invention.
- Bone charcoal particles are obtained by drying in an oven (Shanghai Jinghong, DHG-9030A 9070A, electric heating constant temperature blast drying oven, the same below) at 100°C.
- the Langmuir equation is used to simulate the adsorption process of different bovine bone charcoal to fluorine, and the maximum adsorption capacity (adsorption capacity) of different bovine bone charcoal to fluorine is shown in Table 1. From Table 1, it can be seen that Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1, 2 , 3, Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 has the largest adsorption capacity, and the three are higher than unmodified bovine bone charcoal and Fe 2 (SO 4 ) 3 modified bovine bone charcoal and Al 2 (SO 4 ) 3 modified bovine bone charcoal adsorption capacity.
- the adsorption capacity of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 for fluorine is 45.5 mg ⁇ g -1 , which is 8.5 times that of unmodified bovine bone charcoal.
- the adsorption of unmodified bovine bone charcoal and Fe 2 (SO 4 ) 3 -bovine bone charcoal basically reaches equilibrium after 8 hours, while Al 2 (SO 4 ) 3 -bovine bone charcoal and Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) It takes longer for 3 -bovine bone charcoal 1 to reach adsorption equilibrium, which also means that the adsorption capacity will be larger.
- Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 The adsorption capacity is the largest.
- the regeneration method is as follows: After saturated adsorption, 5g of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 is soaked in 150 ml of NaOH solution with a mass percentage concentration of 1% for 9 hours, then filter paper (double Delineate filter paper, General Electric Biotechnology Co., Ltd.) filter, put Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 on the filter paper into a 100 ml flask, and add 20 ml of deionized water, then Use 0.05 mol ⁇ L -1 hydrochloric acid to adjust the solution to a neutral pH.
- Regenerate according to the above regeneration method in which 100ml of NaOH solution with mass percentage concentration of 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5% is used for regeneration. After regeneration, Al 2 with different concentrations of NaOH regenerated is obtained (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -Bovine Bone Charcoal 1, and then the adsorption capacity after regeneration was measured, and the results are shown in Table 2 below.
- the primary regeneration Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 is regenerated after saturated adsorption to obtain secondary regeneration Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1, in the same way, obtain three regenerated Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1, and then measure the adsorption capacity after the second and third regeneration, The results obtained are shown in Table 4.
- the adsorption capacity of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 is 12.50 mg ⁇ g -1 , which can reach the original adsorption capacity
- the adsorption capacity after the second and third regeneration can still reach 90.42% and 86.54% of the original adsorption capacity.
- the experimental results show that Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3- Bovine bone charcoal has good reproducibility and is a kind of fluoride removal material that can be practically applied.
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Abstract
A preparation method for an iron-aluminum composite bone char fluoride removal agent, comprising the following steps: (1) washing the surface of animal bones and carbonizing the animal bones at 400°C to 450°C for 1.5 h to 2 h to obtain bone char; (2) after cooling the bone char obtained in step (1), grinding, sieving, washing with water, and drying the bone char to obtain bone char particles; and (3) soaking the bone char particles obtained in step (2) in an Fe 2(SO 4) 3 solution with a mass percentage concentration of 2% to 8% at a solid-to-liquid ratio of 1:2.5 to 1:10 for 0.3 h to 0.7 h, washing with water and drying the bone char particles, then soaking the same in an Al 2(SO 4) 3 solution with a mass percentage concentration of 3% to 10% at a solid-to-liquid ratio of 1:3 to 1:8 for 0.5 h to 1.5 h, and washing with water and drying the bone char particles to obtain an Al 2(SO 4) 3-Fe 2(SO 4) 3 composite bone char fluoride removal agent. Further disclosed is an iron-aluminum composite bone char fluoride removal agent prepared by the above method.
Description
本发明属于地下水除氟技术领域，具体涉及一种铁铝复合骨炭除氟剂的制备方法及制得的除氟剂。The invention belongs to the technical field of fluorine removal from groundwater, and specifically relates to a preparation method of an iron-aluminum composite bone char fluoride removal agent and the prepared fluoride removal agent.
国家饮用水标准(GB5749-2006)中规定饮用水中氟最大浓度必须低于1.0mg/L，如果长期饮用氟离子浓度超标的地下水，容易导致氟斑牙和氟骨症。由此可见，长期引用氟超标的地下水，将严重影响人体健康，为此，去除饮用水中的氟具有重要的意义。The national drinking water standard (GB5749-2006) stipulates that the maximum concentration of fluorine in drinking water must be less than 1.0mg/L. If you drink groundwater with excessive fluoride ion concentration for a long time, it is easy to cause dental fluorosis and skeletal fluorosis. It can be seen that long-term use of groundwater with excessive fluorine will seriously affect human health. Therefore, removing fluorine in drinking water is of great significance.
目前去除地下水中氟的技术有吸附法、膜分离、离子交换、电渗析、絮凝等，其中，膜分离技术能有效地去除氟，但设备投资和运行成本均过高，且管理复杂，难以在实践中，特别是农村大规模的推广应用。离子交换能够去除氟，但当地下水中伴有其他阴离子如NO
3-、SO
4
3-、PO
4
3-、Cl
-等共存离子时，将降低氟的去除效果。絮凝也能有效地去除氟，但需要大量的絮凝剂，从而增加了药剂的处理费用，另外絮凝处理产生的沉淀还需过滤处理，这也增加了该工艺的处理单元和费用。吸附方法是通过吸附剂对氟的吸附作用而去除氟，吸附法具有运行管理方便，无需投加药剂等优点，而被广泛应用。
At present, the technologies for removing fluorine in groundwater include adsorption, membrane separation, ion exchange, electrodialysis, flocculation, etc. Among them, membrane separation technology can effectively remove fluorine, but the equipment investment and operating costs are too high, and the management is complicated, making it difficult to In practice, especially large-scale promotion and application in rural areas. Ion exchange can remove fluorine, but when there are coexisting ions such as NO 3- , SO 4 3- , PO 4 3- , and Cl -in the local sewage, the removal effect of fluorine will be reduced. Flocculation can also effectively remove fluorine, but a large amount of flocculant is required, which increases the treatment cost of the medicament. In addition, the sediment produced by the flocculation treatment needs to be filtered, which also increases the processing unit and cost of the process. The adsorption method is to remove fluorine through the adsorption of fluorine by the adsorbent. The adsorption method has the advantages of convenient operation and management, no need to add chemicals, and is widely used.
专利文献(公开号为CN101596446A)中公开了负载铝离子的骨炭除氟剂的制备方法，该方法得到的骨炭除氟剂吸附容量得到了提高，但提高幅度小，仅比一般骨炭高60％以上。因而需要吸附容量更高的骨炭除氟剂。Patent literature (publication number CN101596446A) discloses a method for preparing bone charcoal fluoride removal agent loaded with aluminum ions. The adsorption capacity of the bone charcoal fluoride removal agent obtained by this method has been improved, but the increase is small, only 60% higher than ordinary bone charcoal . Therefore, a bone charcoal defluoride agent with higher adsorption capacity is needed.
发明内容Summary of the invention
本发明为了解决以往骨炭除氟剂吸附容量小的问题，而提供一种铁铝复合骨炭除氟剂的制备方法和制得的铁铝复合骨炭除氟剂。In order to solve the problem of small adsorption capacity of the previous bone charcoal fluoride removal agent, the present invention provides a method for preparing an iron-aluminum composite bone charcoal fluoride removal agent and the prepared iron-aluminum composite bone charcoal fluoride removal agent.
本发明所述铁铝复合骨炭除氟剂的制备方法，包括如下步骤：The preparation method of the iron-aluminum composite bone char fluoride remover of the present invention includes the following steps:
(1)将畜骨表面洗净，在400-450℃炭化1.5-2h而得骨炭；(1) Wash the surface of animal bones and carbonize at 400-450℃ for 1.5-2h to obtain bone charcoal;
(2)将步骤(1)中获得的骨炭冷却后研磨过筛，水洗后烘干得到骨炭粒；(2) The bone charcoal obtained in step (1) is cooled, ground, sieved, washed with water, and dried to obtain bone charcoal particles;
(3)将步骤(2)中获得的骨炭粒按固液比1:2.5-1:10在质量百分比浓度为2-8％的Fe
2(SO
4)
3溶液中浸泡0.3-0.7h，水洗后烘干，然后按1:3-1:8的固液比在质量百分比浓度为3-10％的Al
2(SO
4)
3溶液中浸泡0.5-1.5h，水洗后烘干，得到Al
2(SO
4)
3-Fe
2(SO
4)
3复合骨炭除氟剂。
(3) The bone carbon particles obtained in step (2) are immersed in a Fe 2 (SO 4 ) 3 solution with a mass percentage concentration of 2-8% according to a solid-liquid ratio of 1:2.5-1:10 for 0.3-0.7h, and washed with water After drying, the solid-to-liquid ratio of 1:3-1:8 is immersed in Al 2 (SO 4 ) 3 solution with a mass percentage concentration of 3-10% for 0.5-1.5 hours, washed with water and dried to obtain Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 composite bone charcoal fluoride removal agent.
进一步地，所述畜骨为兽骨，优选牛骨。Further, the animal bones are animal bones, preferably bovine bones.
进一步地，过筛的筛网的目数为10-80目，过筛的粒子对应的粒径为0.2～2mm。Further, the mesh size of the sieved mesh is 10-80 mesh, and the particle size corresponding to the sieved particles is 0.2-2 mm.
进一步地，所述步骤(2)、步骤(3)中，水洗使用去离子水，水洗至pH显中性。Further, in the steps (2) and (3), deionized water is used for the water washing, and the water washing until the pH becomes neutral.
进一步地，所述步骤(2)、步骤(3)中，烘干使用烘箱进行，烘干的温度为100℃。Further, in the steps (2) and (3), the drying is performed using an oven, and the drying temperature is 100°C.
本发明还提供一种铁铝复合骨炭除氟剂，其使用所述铁铝复合骨炭除氟剂的制备方法制得。The present invention also provides an iron-aluminum composite bone charcoal fluoride removal agent, which is prepared by using the preparation method of the iron-aluminum composite bone charcoal fluoride removal agent.
有益效果：本发明通过在骨炭上负载铝离子和铁离子，使得骨炭除氟剂对氟的吸附容量是一般未负载铝铁离子的骨炭的8.5倍，除氟能力显著增强；一次、二次、三次再生效率分别为94.5％、90.4％和86.5％，循环使用性高。Beneficial effects: The present invention loads aluminum ions and iron ions on bone char, so that the fluorine adsorption capacity of bone charcoal fluoride remover is 8.5 times that of bone charcoal without aluminum iron ions, and the fluorine removal ability is significantly enhanced; The three regeneration efficiencies are 94.5%, 90.4% and 86.5%, respectively, and the recyclability is high.
图1为本发明实施例1的铁铝复合骨炭除氟剂与其他牛骨炭的吸附平衡图。Fig. 1 is a diagram of the adsorption equilibrium between the iron-aluminum composite bone charcoal fluoride remover and other bovine bone charcoal in Example 1 of the present invention.
下面通过实施例对本发明技术方案进行详细说明，但是本发明的保护范围不局限于所述实施例。The technical solutions of the present invention will be described in detail below through embodiments, but the protection scope of the present invention is not limited to the embodiments.
实施例1Example 1
将洗净的牛骨900g放入马弗炉(箱式电阻炉SX-5-12，天津泰斯特有限公司)中，在450℃炭化2h而得骨炭。将骨炭冷却至室温后，使用研磨机(天津泰斯特，FW100研磨机)磨碎通过目数为80目(粒径约0.2mm)的筛网，再用去离子水清洗至水澄清，在100℃的烘箱(上海精宏，DHG-9030A 9070A，电热恒温鼓风干燥箱，以下相同)中烘干得到骨炭粒(未改性骨炭)。Put 900 g of the washed beef bones into a muffle furnace (box-type resistance furnace SX-5-12, Tianjin Test Co., Ltd.) and carbonize at 450°C for 2 hours to obtain bone charcoal. After cooling the bone charcoal to room temperature, use a grinder (Tianjin Tester, FW100 grinder) to grind through a sieve of 80 mesh (particle size about 0.2mm), and then rinse with deionized water until the water is clear. Bone charcoal particles (unmodified bone charcoal) are obtained by drying in an oven (Shanghai Jinghong, DHG-9030A 9070A, electric heating constant temperature blast drying oven, the same below) at 100°C.
将骨炭粒(未改性骨炭)50g加入250ml质量百分比浓度为4％的Fe
2(SO
4)
3溶液中浸泡0.5h，用去离子水洗至pH显中性，在100℃的烘箱中烘干得到Fe
2(SO
4)
3改性牛骨炭。然后将Fe
2(SO
4)
3改性牛骨炭50g加入250ml质量百分比浓度为8％的Al
2(SO
4)
3溶液中浸泡1h，用去离子水洗至pH显中性，在100℃烘箱中烘干，得到Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1。
Add 50g of bone charcoal particles (unmodified bone charcoal) into 250ml Fe 2 (SO 4 ) 3 solution with a concentration of 4% by mass for 0.5h, wash with deionized water until the pH is neutral, and dry in an oven at 100°C The Fe 2 (SO 4 ) 3 modified bovine bone charcoal is obtained. Then add 50g of Fe 2 (SO 4 ) 3 modified bovine bone charcoal to 250ml of Al 2 (SO 4 ) 3 solution with a mass percentage concentration of 8% and soak for 1 hour, wash with deionized water until the pH becomes neutral, and in an oven at 100℃ After drying, Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 is obtained.
实施例2Example 2
将洗净的牛骨900g放入马弗炉中，在450℃炭化2h而得骨炭。将骨炭冷却后，使用研磨机磨碎通过目数为80目(粒径约0.2mm)的筛网，再用去离子水清洗至水澄清，在100℃烘箱中烘干得到骨炭粒(未改性骨炭)。Put 900g of washed beef bones into a muffle furnace and carbonize at 450°C for 2 hours to obtain bone charcoal. After cooling the bone charcoal, use a grinder to grind through a sieve of 80 mesh (particle size about 0.2mm), then wash with deionized water until the water is clear, and dry it in an oven at 100℃ to obtain bone charcoal particles (unchanged) Sex bone char).
将骨炭粒(未改性骨炭)50g加入150ml质量百分比浓度为8％的Fe
2(SO
4)
3溶液中浸泡0.3h，用去离子水洗至pH显中性，在100℃烘箱中烘干得到Fe
2(SO
4)
3改性牛骨炭。然后将Fe
2(SO
4)
3改性牛骨炭50g加入200ml质量百分比浓度为10％的Al
2(SO
4)
3溶液中浸泡 0.5h，用去离子水洗至pH显中性，在100℃烘箱中烘干，得到Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭2。
Add 50g of bone charcoal particles (unmodified bone charcoal) into 150ml Fe 2 (SO 4 ) 3 solution with a mass percentage concentration of 8%, soak for 0.3h, wash with deionized water until the pH becomes neutral, and dry in an oven at 100°C. Fe 2 (SO 4 ) 3 modified bovine bone charcoal. Then add 50g of Fe 2 (SO 4 ) 3 modified bovine bone charcoal to 200ml of Al 2 (SO 4 ) 3 with a concentration of 10% by mass, soak for 0.5h, wash with deionized water until the pH becomes neutral, and oven at 100℃ Dry in the middle to obtain Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 2.
实施例3Example 3
将洗净的牛骨900g放入马弗炉中，在450℃炭化2h而得骨炭。将骨炭冷却后，使用研磨机磨碎通过目数为10目(粒径约2mm)的筛网，再用去离子水清洗至水澄清，在100℃烘箱中烘干得到骨炭粒(未改性骨炭)。Put 900g of washed beef bones into a muffle furnace and carbonize at 450°C for 2h to obtain bone charcoal. After cooling the bone charcoal, use a grinder to grind through a 10 mesh (particle size about 2mm) screen, then wash with deionized water until the water is clear, and dry it in an oven at 100°C to obtain bone charcoal particles (unmodified) Bone char).
将骨炭粒(未改性骨炭)50g加入450ml质量百分比浓度为2％的Fe
2(SO
4)
3溶液中浸泡0.7h，用去离子水洗至pH显中性，在100℃烘箱中烘干得到Fe
2(SO
4)
3改性牛骨炭。然后将Fe
2(SO
4)
3改性牛骨炭50g加入350ml质量百分比浓度为3％的Al
2(SO
4)
3溶液中浸泡1.5h，用去离子水洗至pH显中性，在100℃烘箱中烘干，得到Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭3。
Add 50g of bone charcoal particles (unmodified bone charcoal) into 450ml Fe 2 (SO 4 ) 3 solution with a concentration of 2% by mass, soak for 0.7h, wash with deionized water until the pH is neutral, and dry in an oven at 100°C. Fe 2 (SO 4 ) 3 modified bovine bone charcoal. Then add 50g of Fe 2 (SO 4 ) 3 modified bovine bone charcoal to 350ml of Al 2 (SO 4 ) 3 solution with a mass percentage concentration of 3% and soak for 1.5h, wash with deionized water until the pH becomes neutral, and oven at 100℃ Dry in the middle to obtain Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 3.
对比例1Comparative example 1
将牛骨900g放入马弗炉中，在450℃炭化2h而得骨炭。将骨炭冷却后，使用研磨机磨碎通过目数为80目(粒径约0.2mm)的筛网，再用去离子水清洗至水澄清，在100℃烘箱中烘干得到骨炭粒(未改性骨炭)。Put 900g of beef bones into a muffle furnace and carbonize at 450°C for 2h to obtain bone charcoal. After cooling the bone charcoal, use a grinder to grind through a sieve of 80 mesh (particle size about 0.2mm), then wash with deionized water until the water is clear, and dry it in an oven at 100℃ to obtain bone charcoal particles (unchanged) Sex bone char).
对比例2Comparative example 2
将上述骨炭粒(未改性骨炭)50g加入250ml质量百分比浓度为4％的Fe
2(SO
4)
3溶液中浸泡0.5h，用去离子水洗至pH显中性，在100℃烘箱中烘干得到Fe
2(SO
4)
3改性牛骨炭。
Add 50g of the above bone charcoal particles (unmodified bone charcoal) into 250ml Fe 2 (SO 4 ) 3 solution with a concentration of 4% by mass, soak for 0.5h, wash with deionized water until the pH becomes neutral, and dry in an oven at 100°C The Fe 2 (SO 4 ) 3 modified bovine bone charcoal is obtained.
对比例3Comparative example 3
将上述骨炭粒(未改性骨炭)50g加入250mL质量百分比浓度为8％的Al
2(SO
4)
3溶液中浸泡1h，用去离子水洗至pH显中性，在100℃烘箱中烘干，得到Al
2(SO
4)
3改性牛骨炭。
Add 50g of the above-mentioned bone charcoal particles (unmodified bone charcoal) to 250mL of Al 2 (SO 4 ) 3 solution with a mass percentage concentration of 8%, soak for 1 hour, wash with deionized water until the pH becomes neutral, and dry in an oven at 100°C. The Al 2 (SO 4 ) 3 modified bovine bone charcoal is obtained.
吸附容量测定Determination of adsorption capacity
取未改性牛骨炭0.5g、Fe
2(SO
4)
3改性牛骨炭0.5g、Al
2(SO
4)
3改性牛骨炭0.5g和0.5g的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1、2、3，分别浸泡在初始浓度为60mg/L、120mg/L、180mg/L、240mg/L、300mg/L的氟化钠溶液40mL中，在24h后测定溶液浓度，并计算吸附量。通过Langmuir方程模拟不同牛骨炭对氟的吸附过程，得到不同牛骨炭对氟的最大吸附量(吸附容量)如表1所示，由表1可知，Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1、2、3中，Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1的吸附容量最大，且三者均高于未改性牛骨炭、Fe
2(SO
4)
3改性牛骨炭和Al
2(SO
4)
3改性牛骨炭的吸附容量。其中Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1对氟的吸附容量为45.5mg·g
-1，是未改性牛骨炭的8.5倍。
Take 0.5 g of unmodified bovine bone charcoal, 0.5 g of Fe 2 (SO 4 ) 3 modified bovine bone charcoal, 0.5 g of Al 2 (SO 4 ) 3 modified bovine bone charcoal, and 0.5 g of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -Bovine bone charcoal 1, 2, 3, soaked in 40mL of sodium fluoride solution with initial concentration of 60mg/L, 120mg/L, 180mg/L, 240mg/L, 300mg/L respectively, after 24h Determine the concentration of the solution and calculate the adsorption capacity. The Langmuir equation is used to simulate the adsorption process of different bovine bone charcoal to fluorine, and the maximum adsorption capacity (adsorption capacity) of different bovine bone charcoal to fluorine is shown in Table 1. From Table 1, it can be seen that Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1, 2 , 3, Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 has the largest adsorption capacity, and the three are higher than unmodified bovine bone charcoal and Fe 2 (SO 4 ) 3 modified bovine bone charcoal and Al 2 (SO 4 ) 3 modified bovine bone charcoal adsorption capacity. The adsorption capacity of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 for fluorine is 45.5 mg·g -1 , which is 8.5 times that of unmodified bovine bone charcoal.
表1不同牛骨炭对氟的吸附容量Table 1 Adsorption capacity of different bovine bone charcoal to fluorine
| 种类species | 吸附容量mg·g -1 Adsorption capacity mg·g -1 |
| 未改性牛骨炭Unmodified beef bone charcoal | 5.35.3 |
| Fe 2(SO 4) 3-牛骨炭 Fe 2 (SO 4 ) 3 -Bovine Bone Charcoal | 13.313.3 |
| Al 2(SO 4) 3-牛骨炭 Al 2 (SO 4 ) 3 -beef bone charcoal | 34.534.5 |
|
Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1
Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 - |
45.545.5 |
| Al 2(SO 4) 3-Fe 2(SO 4) 3-牛骨炭2 Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -Bovine Bone Charcoal 2 | 43.743.7 |
| Al 2(SO 4) 3-Fe 2(SO 4) 3-牛骨炭3 Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -Bovine Bone Charcoal 3 | 42.842.8 |
吸附平衡Adsorption equilibrium
取未改性牛骨炭0.5g、Fe
2(SO
4)
3改性牛骨炭0.5g、Al
2(SO
4)
3改性牛骨炭0.5g和0.5g的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1，分别浸泡在初始浓度为17mg/L的氟化钠溶液中，测定吸附容量趋于稳定所需要的时间。结果如图1所示。根据图1可知，4种牛骨炭对氟的吸附容量逐渐增大，10h后吸附逐渐趋于平衡。其中未改性牛骨炭和Fe
2(SO
4)
3-牛骨炭吸附8h左右就基本达到平衡状态，而Al
2(SO
4)
3-牛骨炭和Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1达到吸附平衡的时间较长，这也意味着吸附容量会更大，在达到吸附平衡时，Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1的吸附容量最大。
Take 0.5 g of unmodified bovine bone charcoal, 0.5 g of Fe 2 (SO 4 ) 3 modified bovine bone charcoal, 0.5 g of Al 2 (SO 4 ) 3 modified bovine bone charcoal, and 0.5 g of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -Bovine bone charcoal 1, respectively immersed in a sodium fluoride solution with an initial concentration of 17 mg/L, and measured the time required for the adsorption capacity to stabilize. The result is shown in Figure 1. According to Figure 1, the adsorption capacity of the four bovine bone charcoals for fluorine gradually increased, and the adsorption gradually tended to equilibrium after 10 hours. Among them, the adsorption of unmodified bovine bone charcoal and Fe 2 (SO 4 ) 3 -bovine bone charcoal basically reaches equilibrium after 8 hours, while Al 2 (SO 4 ) 3 -bovine bone charcoal and Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) It takes longer for 3 -bovine bone charcoal 1 to reach adsorption equilibrium, which also means that the adsorption capacity will be larger. When the adsorption equilibrium is reached, Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 The adsorption capacity is the largest.
Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1的再生
Regeneration of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -Bovine Bone Charcoal 1
再生方法如下：将5g的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1在饱和吸附后在150ml质量百分比浓度为1％的NaOH溶液中浸泡9h后，用滤纸(双圈定性滤纸，通用电气生物科技有限公司)过滤，将滤纸上的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1放入100ml烧瓶中，并加入20ml去离子水，然后用0.05mol·L
-1盐酸调节溶液至pH显中性。将Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1在中性溶液中浸泡0.5h后过滤，放入烧杯中用去离子水清洗，然后在100℃烘箱中烘干后，得到再生的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1。
The regeneration method is as follows: After saturated adsorption, 5g of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 is soaked in 150 ml of NaOH solution with a mass percentage concentration of 1% for 9 hours, then filter paper (double Delineate filter paper, General Electric Biotechnology Co., Ltd.) filter, put Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 on the filter paper into a 100 ml flask, and add 20 ml of deionized water, then Use 0.05 mol·L -1 hydrochloric acid to adjust the solution to a neutral pH. Soak the Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 in a neutral solution for 0.5h, then filter, put it in a beaker and wash with deionized water, and then dry it in an oven at 100°C , The regenerated Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 is obtained.
再生效率测定Regeneration efficiency measurement
按上述再生方法进行再生，其中取质量百分比浓度为0.5％、1％、1.5％、2％、3％、4％、5％的NaOH溶液100ml进行再生，再生后得到不同浓度NaOH再生的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1，然后测定再生后的吸附容量，将结果表示于下表2。
Regenerate according to the above regeneration method, in which 100ml of NaOH solution with mass percentage concentration of 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5% is used for regeneration. After regeneration, Al 2 with different concentrations of NaOH regenerated is obtained (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -Bovine Bone Charcoal 1, and then the adsorption capacity after regeneration was measured, and the results are shown in Table 2 below.
表2经不同浓度NaOH再生的再生效率Table 2 Regeneration efficiency of different concentrations of NaOH regeneration
由表2可知，在1％～5％浓度的范围内NaOH溶液对再生骨炭吸附氟的量影响比较小，且再生效率均为94.5％以上。It can be seen from Table 2 that in the concentration range of 1% to 5%, the NaOH solution has a relatively small influence on the amount of fluorine absorbed by the regenerated bone char, and the regeneration efficiency is all above 94.5%.
固液比对骨炭再生效率的影响The effect of solid-liquid ratio on bone char regeneration efficiency
按上述再生方法进行再生，其中取5g的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1按固液比为1:20、1:30、1:40、1:50在质量百分比浓度为1％的NaOH溶液中进行再生，再生后得到不同固液比条件下的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1，然后测定再生后的吸附容量，将结果表示于下表3。
Regenerate according to the above regeneration method, in which 5g of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 is taken according to the solid-liquid ratio of 1:20, 1:30, 1:40, 1:50 Regenerate in a NaOH solution with a concentration of 1% by mass. After regeneration, Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -Bovine bone charcoal 1 is obtained under different solid-liquid ratio conditions, and then the adsorption after regeneration is measured Capacity, the results are shown in Table 3 below.
表3固液比对骨炭再生效率的影响Table 3 The effect of solid-liquid ratio on bone char regeneration efficiency
由表3可知，随着再生液用量的增加，再生后Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1的再生效率呈上升趋势。考虑实际应用中的经济因素，优选Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1与NaOH溶液的固液比为1∶30。
It can be seen from Table 3 that with the increase in the amount of regeneration solution, the regeneration efficiency of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 shows an upward trend after regeneration. Considering economic factors in practical applications, it is preferable that the solid-liquid ratio of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 to NaOH solution is 1:30.
二次、三次再生效率的测定Measurement of secondary and tertiary regeneration efficiency
按照上述再生方法，将一次再生的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1在饱和吸附后进行再生，得到二次再生的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1，按照同样的方式得到三次再生的Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1，然后测定二次、三次再生后的吸附容量，所得结果如表4所示。
According to the above regeneration method, the primary regeneration Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 is regenerated after saturated adsorption to obtain secondary regeneration Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1, in the same way, obtain three regenerated Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1, and then measure the adsorption capacity after the second and third regeneration, The results obtained are shown in Table 4.
表4三次再生的再生效率Table 4 Regeneration efficiency of three regenerations
如表4所示，Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭1在最佳再生条件下，再生后的吸附容量为12.50mg·g
-1，可达到原先吸附容量的95.10％，且经过第二次和第三次再生后的吸附容量仍然能够达到原先吸附容量的90.42％和86.54％，实验结果表明Al
2(SO
4)
3-Fe
2(SO
4)
3-牛骨炭具有良好的可再生性，是一种可以实际应用的除氟材料。
As shown in Table 4, under the optimal regeneration conditions, the adsorption capacity of Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 -bovine bone charcoal 1 is 12.50 mg·g -1 , which can reach the original adsorption capacity The adsorption capacity after the second and third regeneration can still reach 90.42% and 86.54% of the original adsorption capacity. The experimental results show that Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3- Bovine bone charcoal has good reproducibility and is a kind of fluoride removal material that can be practically applied.
如上所述，尽管参照特定的优选实施例已经表示和表述了本发明，但其不得解释为对本发明自身的限制。在不脱离所附权利要求定义的本发明的精神和范围前提下，可对其在形式上和细节上做出各种变化。As mentioned above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the present invention itself. Various changes in form and details can be made without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (6)
- 一种铁铝复合骨炭除氟剂的制备方法，其特征在于，包括如下步骤：A preparation method of iron-aluminum composite bone charcoal fluoride removing agent, which is characterized in that it comprises the following steps:(1)将畜骨表面洗净，在400-450℃炭化1.5-2h而得骨炭；(1) Wash the surface of animal bones and carbonize at 400-450℃ for 1.5-2h to obtain bone charcoal;(2)将步骤(1)中获得的骨炭冷却后研磨过筛，水洗后烘干得到骨炭粒；(2) The bone charcoal obtained in step (1) is cooled, ground, sieved, washed with water, and dried to obtain bone charcoal particles;(3)将步骤(2)中获得的骨炭粒按固液比1:2.5-1:10在质量百分比浓度为2-8％的Fe 2(SO 4) 3溶液中浸泡0.3-0.7h，水洗后烘干，然后按1:3-1:8的固液比在质量百分比浓度为3-10％的Al 2(SO 4) 3溶液中浸泡0.5-1.5h，水洗后烘干，得到Al 2(SO 4) 3-Fe 2(SO 4) 3复合骨炭除氟剂。 (3) The bone carbon particles obtained in step (2) are immersed in a Fe 2 (SO 4 ) 3 solution with a mass percentage concentration of 2-8% according to a solid-liquid ratio of 1:2.5-1:10 for 0.3-0.7h, and washed with water After drying, the solid-to-liquid ratio of 1:3-1:8 is immersed in Al 2 (SO 4 ) 3 solution with a mass percentage concentration of 3-10% for 0.5-1.5 hours, washed with water and dried to obtain Al 2 (SO 4 ) 3 -Fe 2 (SO 4 ) 3 composite bone charcoal fluoride removal agent.
- 根据权利要求1所述的铁铝复合骨炭除氟剂的制备方法，其特征在于，步骤(1)中，所述畜骨为兽骨。The method for preparing the iron-aluminum composite bone charcoal defluorinating agent according to claim 1, wherein in step (1), the animal bone is animal bone.
- 根据权利要求1所述的铁铝复合骨炭除氟剂的制备方法，其特征在于，步骤(2)中，过筛的筛网的目数为10-80目。The method for preparing the iron-aluminum composite bone charcoal defluorinating agent according to claim 1, characterized in that, in step (2), the mesh number of the screen meshed is 10-80 mesh.
- 根据权利要求1所述的铁铝复合骨炭除氟剂的制备方法，其特征在于，所述步骤(2)、步骤(3)中，水洗使用去离子水，水洗至pH显中性。The method for preparing the iron-aluminum composite bone charcoal defluoridation agent according to claim 1, characterized in that, in the steps (2) and (3), deionized water is used for washing with water, and the pH is washed with water until the pH becomes neutral.
- 根据权利要求1所述的铁铝复合骨炭除氟剂的制备方法，其特征在于，所述步骤(2)、步骤(3)中，烘干使用烘箱进行，烘干的温度为100℃。The method for preparing the iron-aluminum composite bone char fluoride removal agent according to claim 1, characterized in that, in the steps (2) and (3), the drying is performed using an oven, and the drying temperature is 100°C.
- 一种铁铝复合骨炭除氟剂，其特征在于，使用权利要求1至5中任一项所述的铁铝复合骨炭除氟剂的制备方法制得。An iron-aluminum composite bone-char fluoride removal agent characterized in that it is prepared by using the iron-aluminum composite bone-char fluoride removal agent described in any one of claims 1 to 5.
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