WO2019119477A1 - 一种聚合氯化锆铝无机高效絮凝剂的制备方法 - Google Patents

一种聚合氯化锆铝无机高效絮凝剂的制备方法 Download PDF

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WO2019119477A1
WO2019119477A1 PCT/CN2017/118445 CN2017118445W WO2019119477A1 WO 2019119477 A1 WO2019119477 A1 WO 2019119477A1 CN 2017118445 W CN2017118445 W CN 2017118445W WO 2019119477 A1 WO2019119477 A1 WO 2019119477A1
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raw water
zirconium
aluminum
solution
flocculant
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PCT/CN2017/118445
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French (fr)
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李星
苏兆阳
杨艳玲
杜鹏
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北京工业大学
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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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium

Definitions

  • the invention belongs to the field of water treatment, and particularly relates to a preparation method of a polymeric zirconium chloride aluminum inorganic high-efficiency flocculant.
  • Coagulation is an important unit in the water treatment process.
  • the removal effect of pollutants directly determines the operating load of the subsequent process and the final effluent quality.
  • Aluminium salt flocculants have played an important role in engineering applications for the past 100 years. However, its removal effect on organic matter is limited, especially the removal effect of small molecular organic matter is not good. In order to improve the removal effect of organic matter, it is a common method to increase the dosage of the aluminum salt flocculant. This operation will increase the residual aluminum content in the water. Drinking high-aluminum water for a long time is not conducive to human health and will increase the risk of heart and brain diseases. Therefore, the development of new flocculants to improve the removal of organic matter (especially small molecular organic matter) is a hot issue in current research.
  • Inorganic low molecular weight zirconium salt flocculant can achieve efficient removal of organic matter, especially compared to aluminum salt flocculant to significantly improve the removal of small molecules of organic matter.
  • inorganic low molecular weight zirconium salt flocculants have poor adaptability to changes in pH of raw water and, therefore, have not been used in engineering.
  • the preparation of a high-efficiency zirconium salt flocculant capable of adapting to the change of pH value of raw water and having a high removal rate of organic matter is a technical problem that researchers in the field of water treatment need to further develop and utilize zirconium salt flocculant.
  • the inventors of the present invention have proposed a method for preparing a polymeric zirconium chloride aluminum inorganic high-efficiency flocculant to overcome the organic pollution of the inorganic low molecular weight zirconium salt flocculant in a lower or higher pH raw water. The disadvantage of poor material removal.
  • the object of the present invention is to provide a polymer zirconium salt flocculant suitable for the wide pH range of raw water for the problem that the inorganic low molecular zirconium salt has poor effect on removing organic pollutants in lower or higher pH raw water.
  • the preparation method particularly relates to a preparation method of a polymeric zirconium chloride aluminum inorganic high-efficiency flocculant.
  • the technical principle of the invention consists in pre-hydrolysis of Zr and Al ions at the same time, the molecular weight of the pre-hydrolyzed product is significantly increased and the molecular chain is longer, and the morphological stability after the addition is strongly affected by the change of the pH value of the raw water.
  • the pre-hydrolyzed product of polyaluminium zirconium chloride is used to realize the efficient removal of organic matter by utilizing the synergistic effect of net trapping and adsorption bridging.
  • the present invention provides a polymeric zirconium chloride aluminum inorganic high-efficiency flocculant which can be obtained by the following method:
  • step (3) adding sodium hydroxide solution dropwise to the compounding liquid in the step (2), adjusting the alkalinity B to 0.5 to 2.0, and continuously stirring at 500 to 600 rpm at room temperature of 20 to 25 ° C until the solution is present. After the color is transparent, it is allowed to stand for 10 to 12 hours to obtain a polyaluminum zirconium chloride solution.
  • the molar ratio of Zr/Al in the step (2) is selected from the range of 3 to 5:1 when the organic matter content of the raw water is TOC ⁇ 7 mg/L; when the organic content of the raw water is TOC ⁇ 7 mg/L, It should be selected from the range of 2 to 3:1.
  • the degree of alkalization (B) in the step (3) refers to a molar ratio of [OH]/[Zr+Al]; when the content of the organic matter in the raw water is TOC ⁇ 7 mg/L, it should be selected from 0.5 to 1.5. Range; when the organic content of raw water TOC ⁇ 7mg/L, it should be selected from the range of 1.5 to 2.0.
  • a river water in Beijing was used as the raw water for the test.
  • the raw water turbidity was 21.8 NTU
  • the TOC was 12.3 mg/L
  • the pH was 7.3
  • the water temperature was 13.8 °C.
  • the flocculating agent prepared by the method of the present invention is subjected to a coagulation test on the above river water.
  • the pH of the raw water was adjusted to 5.5 using hydrochloric acid having a mass concentration of 30%.
  • the test was carried out by adding a flocculant at the beginning of the coagulation test, while stirring rapidly at 500 rpm for 1 min, then slowly stirring for 15 min at 50 rpm, and finally measuring the water quality after sinking for 15 min.
  • the molar ratio of Zr/Al should be selected from the range of 3 ⁇ 5:1; the degree of alkalinity B means that the molar ratio of [OH]/[Zr+Al] should be selected from 0.5 ⁇ 1.5 range, the specific preparation process is as follows:
  • the dosage of polyaluminium zirconium chloride is based on the mole of Zr + Al.
  • the polyaluminum zirconium aluminum flocculant prepared by the invention method of the present invention can effectively remove the turbidity and organic matter in the raw water with a pH value of 5.5, and the residual aluminum content of the effluent, compared with the use of aluminum chloride alone as a flocculating agent. Significantly lower.
  • the high efficiency of coagulation of the polymeric zirconium chloride aluminum flocculant prepared by the new method proposed in the present case in the raw water with lower pH value was proved.
  • the water in a park in Beijing was used as test water.
  • the raw water turbidity was 5.8 NTU
  • the TOC was 4.3 mg/L
  • the pH was 7.7
  • the water temperature was 12.5 °C.
  • the flocculating agent prepared by the method of the present invention is subjected to a coagulation test on the above river water.
  • the pH of the raw water was adjusted to 8.5 using a NaOH solution having a mass concentration of 0.5 mol/L.
  • the test was carried out by adding a flocculant at the beginning of the coagulation test, while stirring rapidly at 500 rpm for 1 min, then slowly stirring for 15 min at 50 rpm, and finally measuring the water quality after sinking for 15 min.
  • the molar ratio of Zr/Al should be selected from the range of 2 to 3:1; the degree of alkalization B means that the molar ratio of [OH]/[Zr+Al] should be selected from 1.5 ⁇
  • the scope of 2.0, the specific preparation process is as follows:
  • the dosage of polyaluminium zirconium chloride is based on the mole of Zr + Al.
  • the method of the invention of the present invention can be used to prepare a polyaluminum zirconium aluminum flocculant, which can remove turbidity and organic matter in raw water with a pH of 8.5, and residual in water after sinking, compared with aluminum chloride alone as a flocculating agent.
  • the aluminum content is significantly reduced, which fully proves that the polymeric zirconium aluminum flocculant prepared by the new method proposed in this case can exert the coagulation efficiency in the raw water with higher pH value.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

一种聚合氯化锆铝无机高效絮凝剂的制备方法属于给水处理技术领域。本发明针对无机低分子锆盐絮凝剂适应原水pH值变化能力较差的问题，通过同时对铝盐和锆盐进行预水解，共聚后生成的铝盐水解产物可拓宽适用的原水pH值范围宽，锆盐水解产物尺寸大强化了网捕卷扫作用可对水中有机污染物高效去除。本发明特别适用于pH值非中性的高有机物含量的原水强化混凝处理。

Description

一种聚合氯化锆铝无机高效絮凝剂的制备方法 技术领域
本发明属给水处理领域，特别涉及一种聚合氯化锆铝无机高效絮凝剂的制备方法。
背景技术
混凝是给水处理工艺中的重要单元，其对污染物的去除效果直接决定着后续工艺的运行负荷及最终出水水质。有研究表明，混凝单元对有机物的去除效果与后续加氯消毒步骤中生成的消毒副产物的多少呈正比关系。即有机物去除效果佳，消毒副产物的生成量少。这些消毒副产物已被证实可致癌，其形成应予以最大限度地限制。为此，如何提高混凝单元对有机物的去除效能受到业内的广泛关注，并成为综合优化混凝效果的重要目标之一。
铝盐絮凝剂在过去的近百年的工程应用中发挥了重要作用。而其对有机物的去除效果有限，尤其是对小分子有机物的去除效果不佳。为了提高有机物的去除效果，增加铝盐絮凝剂的投加量是常用手段。而这一操作会使得出水中的残余铝含量增加，长期饮用高铝含量的水不利于人体健康，并会增加患心脑疾病的风险。为此，研制新型絮凝剂以提高有机物(特别是小分子有机物)的去除效果是当前研究的热点问题。无机低分子锆盐絮凝剂可实现对有机物的高效去除，特别是相比于铝盐絮凝剂对小分子有机物的去除效果有显著提升。然而，无机低分子锆盐絮凝剂对原水pH值变化适应能力较差，因而，始终未能在工程中使用。
为此，制备出能够适应原水pH值变化并具备对有机物较高去除率的高效锆盐絮凝剂是水处理领域研究人员进一步开发利用锆盐絮凝剂的需要攻克的技术难题。为此，本案发明人针对该问题，提出了一种聚合氯化锆铝无机高效絮凝剂的制备方法，以克服无机低分子锆盐絮凝剂在较低或较高的pH值原水中对有机污染物去除效果差的缺点。
发明内容
本发明的目的是针对无机低分子锆盐在较低或较高的pH值原水中对有机污染物去除效果差的问题，提供一种适用于较宽原水pH值范围的高分子锆盐絮凝剂的制备方法，特别涉及一种聚合氯化锆铝无机高效絮凝剂的制备方法。
本发明的技术原理在于：同时对Zr和Al离子进行预水解，生成的预水解产物分子量显著增加且分子链较长，其在投加后的形态稳定性强受原水pH值变化的影响较小，主要以聚合氯化锆铝的预水解产物发挥网捕卷扫和吸附架桥的协同作用实现对有机物的高效去除。
为实现上述目的，本发明提供的一种聚合氯化锆铝无机高效絮凝剂，可以通过如下方法得到：
其制备步骤如下：
(1)称取原料，配制溶液；
(2)将四氯化锆溶液与氯化铝溶液按照Zr/Al摩尔比为2～5：1进行复配并充分混合；
(3)将氢氧化钠溶液逐滴加入到步骤(2)中的复配混合液中，调节碱化度B为0.5～2.0，室温20～25℃下以500～600rpm持续搅拌至溶液呈无色透明后，静置熟化10～12小时，得到聚合氯化锆铝溶液。
所述方法中，步骤(2)中Zr/Al摩尔比，当原水中有机物含量TOC≥7mg/L时，应选自3～5：1范围；当原水中有机物含量TOC＜7mg/L时，应选自2～3：1范围。
所述方法中，步骤(3)中碱化度(B)，是指[OH]/[Zr+Al]的摩尔比值；当原水中有机物含量TOC≥7mg/L时，应选自0.5～1.5范围；当原水中有机物含量TOC＜7mg/L时，应选自1.5～2.0范围。
本发明的技术优势、可取得如下预期的技术效果：
(1)在较宽原水pH值范围内，聚合氯化锆铝絮凝剂可对有机物高效去除，形成的絮体尺寸较大、密实且沉降性能良好。
(2)在保证总体污染物去除率的前提下，由于相对减少了铝盐的投量，出水中余铝含量较单独投加铝盐絮凝剂显著降低。
(3)聚合氯化锆铝新型絮凝剂稳定性好，可储存2～3个月。
(4)操作方法简单易行，原料易得，成本低廉，实际应用的可能性较大。
具体实施方式
实施例1
取北京市内某河水作为试验用原水，原水浊度为21.8NTU，TOC为12.3mg/L，pH值为7.3，水温为13.8℃。
使用本发明的方法制备的絮凝剂对上述河水进行混凝试验。试验开始前，使用质量浓度为30％的盐酸将原水的pH值调至5.5。此试验的过程为混凝试验开始时投加絮凝剂，同时以500rpm进行1min快速搅拌，然后以50rpm进行15min的慢速搅拌，最后静沉15min后测沉后水的水质。
当原水中有机物含量TOC≥7mg/L时，Zr/Al摩尔比应选自3～5：1范围；碱化度B，指[OH]/[Zr+Al]的摩尔比值应选自0.5～1.5范围，具体的制备过程如下：
(1)配制0.4mol/L(以锆计)的四氯化锆溶液和0.1mol/L(以铝计)的氯化铝溶液；
(2)将配制好的100mL四氯化锆溶液与100mL氯化铝溶液按照Zr/Al摩尔比为4：1进行复配并充分混合；
(3)取50mL的0.5mol/L氢氧化钠溶液使用注射泵以0.1mL/min的速度逐滴加入到步骤(2)中的50mL的复配混合液中，室温25℃下以600rpm持续搅拌至溶液呈无色透明后，静置熟化12小时，得到碱化度B，即[OH]/[Zr+Al]的摩尔比值为1.0，聚合氯化锆铝絮凝剂。
试验结果如下：
Figure PCTCN2017118445-appb-000001
Figure PCTCN2017118445-appb-000002
注：聚合氯化锆铝的投量是以Zr+Al的摩尔计。
说明采取本案的发明方法制备得到聚合氯化锆铝絮凝剂较单独使用氯化铝作为絮凝剂而言，可对pH值为5.5的原水中的浊度和有机物的高效去除，且出水残余铝含量显著降低。证明了本案提出的新方法制备的聚合氯化锆铝絮凝剂在pH值较低的原水中混凝作用的高效性。
实施例2
取北京某公园湖水作为试验用水，原水浊度为5.8NTU，TOC为4.3mg/L，pH值为7.7，水温为12.5℃。
使用本发明的方法制备的絮凝剂对上述河水进行混凝试验。试验开始前，使用质量浓度为0.5mol/L的NaOH溶液将原水的pH值调至8.5。此试验的过程为混凝试验开始时投加絮凝剂，同时以500rpm进行1min快速搅拌，然后以50rpm进行15min的慢速搅拌，最后静沉15min后测沉后水的水质。
当原水中有机物含量TOC＜7mg/L时，Zr/Al摩尔比应选自2～3：1范围；碱化度B，指[OH]/[Zr+Al]的摩尔比值应选自1.5～2.0范围，具体的制备过程如下：
(1)配制0.2mol/L(以锆计)的四氯化锆溶液和0.1mol/L(以铝计)的氯化铝溶液；
(2)将配制好的100mL四氯化锆溶液与100mL氯化铝溶液按照Zr/Al摩尔比为2：1进行复配并充分混合；
(3)取50mL的0.6mol/L氢氧化钠溶液使用注射泵以0.1mL/min的速度逐滴加入到步骤(2)中的50mL的复配混合液中，室温25℃下以600rpm持续搅拌至溶液呈无色透明后，静置熟化12小时，得到碱化度B，即[OH]/[Zr+Al]的摩尔比值为2.0，聚合氯化锆铝絮凝剂。
试验结果如下：
Figure PCTCN2017118445-appb-000003
注：聚合氯化锆铝的投量是以Zr+Al的摩尔计。
说明采取本案的发明方法制备得到聚合氯化锆铝絮凝剂较单独使用氯化铝作为絮凝剂而言，可对pH值为8.5的原水中的浊度和有机物的高效去除，且沉后水中残余铝含量显著降低，充分证明了本案提出的新方法制备的聚合氯化锆铝絮凝剂可在pH值较高的原水中发挥混凝效能的高效性。

Claims (3)

  1. 一种聚合氯化锆铝无机高效絮凝剂的制备方法，其特征在于：所用原料：氯化铝；四氯化锆和氢氧化钠；
    其制备步骤如下：
    (1)称取原料，配制溶液；
    (2)将四氯化锆溶液与氯化铝溶液按照Zr/Al摩尔比为2～5：1进行复配并充分混合；
    (3)将氢氧化钠溶液逐滴加入到步骤(2)中的复配混合液中，调节碱化度B为0.5～2.0，碱化度B是指[OH]/[Zr+Al]的摩尔比值；室温20～25℃下以500～600rpm持续搅拌至溶液呈无色透明后，静置熟化10～12小时，得到聚合氯化锆铝溶液。
  2. 根据权利要求1所述的聚合氯化锆铝无机高效絮凝剂的制备方法，其特征在于，步骤(2)中Zr/Al摩尔比，当原水中有机物含量TOC≥7mg/L时，应选自3～5：1范围；当原水中有机物含量TOC＜7mg/L时，应选自2～3：1范围。
  3. 根据权利要求1所述的聚合氯化锆铝无机高效絮凝剂的制备方法，其特征在于，步骤(3)中当原水中有机物含量TOC≥7mg/L时，碱化度B应选自0.5～1.5范围；当原水中有机物含量TOC＜7mg/L时，碱化度B应选自1.5～2.0范围。
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CN114436385B (zh) * 2022-03-03 2022-11-29 南京大学 一种聚锆混凝剂及其应用
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