CN112591851A - 一种用于从水体中除磷的树脂、制备方法及其应用 - Google Patents
一种用于从水体中除磷的树脂、制备方法及其应用 Download PDFInfo
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- CN112591851A CN112591851A CN202011553288.7A CN202011553288A CN112591851A CN 112591851 A CN112591851 A CN 112591851A CN 202011553288 A CN202011553288 A CN 202011553288A CN 112591851 A CN112591851 A CN 112591851A
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- Prior art keywords
- resin
- water
- preparing
- removing phosphorus
- solution
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- 239000011347 resin Substances 0.000 title claims abstract description 214
- 229920005989 resin Polymers 0.000 title claims abstract description 214
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 80
- 239000011574 phosphorus Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 44
- 150000001768 cations Chemical class 0.000 claims abstract description 43
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- 239000010452 phosphate Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 238000009826 distribution Methods 0.000 claims abstract description 3
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 171
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 84
- 238000005406 washing Methods 0.000 claims description 77
- 238000003756 stirring Methods 0.000 claims description 65
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 30
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 28
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 25
- 238000001179 sorption measurement Methods 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 20
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- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 14
- 229940106681 chloroacetic acid Drugs 0.000 claims description 14
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- 235000011152 sodium sulphate Nutrition 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
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- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
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- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
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- 230000035484 reaction time Effects 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明公开了一种用于从水体中除磷树脂及其制备方法和应用,该树脂粒径为0.5‑0.8mm;具有多孔结构,比表面积为8‑25m2/g,孔径分布为3‑15nm;湿视密度为0.68‑0.74g/cm3;湿真密度为1.12‑1.18g/cm3;树脂含水量以重量百分数计为43‑57%。树脂上负载有镧氧键的官能团使其能够选择性吸附水体中的磷酸根。该树脂的采用弱酸阳树脂负载镧的方式,利用镧氧键对磷酸根的高选择性,能够选择性去除水体中磷的树脂,并且易解析,合成成本低,可以重复利用。能够有效去除富营养化的水和废水中的磷,水体中磷酸根含量可控制在20ppm之内,降低了水体除磷的成本,相较于传统的一次性磷吸附剂具有很大优势。
Description
技术领域
本发明属于功能高分子领域和废水处理领域,具体地,本申请涉及一种用于从水体中除磷的树脂。
背景技术
含磷废水是污染极为严重的典型工业废水之一,其废水中含有大量磷酸盐,主要来自于各种工业原料、农业原料、洗涤剂,一旦处理不当而排入河道将严重污染自然环境。含磷废水会引发水体的富营养化,随即引发赤潮现象,使水体异常,颜色改变,水质变坏,发臭,恶化了水体条件,是水体生态破坏的一种危险信号。近年来,河流、湖泊、海洋等水域的水质恶化现象越来越严重。一般来讲,水体中总磷质量浓度超过20mg/L,即可认为水体处于富营养化。因此,对含磷废水进行有效处理的现实意义巨大。运用针对性的工艺对含磷废水进行有效处理,使其能达到排放标准,是当下环保重视的课题。
含磷废水的典型处理方法有:混凝沉淀法、结晶法、离子交换吸附法、电渗析、反渗透等工艺。目前主要利用铝盐、石灰等能与磷酸根生成难溶磷酸盐沉淀物的方法去除废水中的磷。但是在较低浓度的含磷废水中,该方法效率低、污染大,而离子交换吸附法可以很好地解决这个问题。但现有的除磷离子交换树脂存在选择性较低,吸附较慢,吸附量较低的问题。。本专利主要针对离子交换吸附法进行优化创新,采用镧氧键选择性吸附磷酸根,以此提高树脂的吸附速度和吸附量,同时对磷酸根具有高度选择性。随着我国工业的快速发展,我国的排放标准也日益严苛,因此除磷树脂有广阔的应用前景。
发明内容
通过研究发现,氧化镧通过与磷酸根的配位作用,对磷具有高度选择吸附性,且镧原料价格低廉。但是氧化镧粉体在实际应用中使用不便,需要找到合适的载体以便于实施应用。典型的载体有硅胶、分子筛、活性炭等,同时大孔离子交换树脂也是良好的载体。
针对现有技术的不足,本发明提供了一种用于从水体中除磷的离子交换树脂,并且用碱液易解析,相比现有的除磷技术,使用方便,成本低,不产生二次污染。
本发明提出了一种负载镧的除磷树脂,该树脂的特征是:树脂粒径为0.5-0.8mm;具有多孔结构,比表面积为8-25m2/g,孔径分布为3-15nm;湿视密度为0.68-0.74g/cm3;湿真密度为1.12-1.18g/cm3;树脂含水量为43-57%(w/w);树脂上负载有镧氧键合的官能团使其能够选择性吸附水体中的磷酸根。易与体系中的磷酸根发生离子交换。所述除磷树脂制备方法如下:
步骤(1):将单官能团单体、交联剂、致孔剂、引发剂配制成油相,分散剂和水配制成水相,采用悬浮聚合法制备树脂,聚合完成后将树脂中的致孔剂除去,得到树脂基球;
步骤(2):将树脂基球进行氯化反应、胺化反应,将胺化反应后的树脂加碱进行水解反应得到胺球;
步骤(3):胺球与有机弱酸进行反应,得到弱酸阳树脂;
步骤(4):将镧化合物负载到弱酸阳树脂表面,得到除磷树脂。
更进一步地,所述步骤(1)用的单官能团单体可以是苯乙烯系、丙烯酸系列、丙烯腈系中的一种或几种。
所述步骤(1)用的交联剂可以是二乙烯基苯、二异氰酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种。交联剂占单体的比例(即交联度)为2-30%(W/W);较优选为4-15%(W/W);更优选为5-10%(W/W)。
所述步骤(1)中致孔剂可以是甲苯、异辛烷、汽油、航空汽油、正庚烷、环己烷、液体石蜡、白油中的一种或几种。
所述步骤(1)中引发剂可以是过氧化月桂酰、过氧化苯甲酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过硫酸钾、过硫酸钠、过硫酸铵偶氮二异丁腈、偶氮二异庚腈中的一种或几种。
所述步骤(1)中分散剂可以是聚乙烯醇、明胶、脂肪酸类、脂肪族酰胺类、石蜡类、纤维素类中的一种或几种。
所述步骤(1)中,水相和油相比为10:1-1:1(V/V)。
所述步骤(1)中,悬浮聚合温度为40-100℃,采用梯度升温的办法,第一阶段为40-60℃,第二阶段为60-80℃,第三阶段为80-100℃。
所述步骤(2)中氯化反应时使用的试剂为氯甲醚。氯化反应时使用的催化剂可以是氯化锌、氯化铝、氯化铁、三氟化硼、五氯化铌和三氟甲磺酸盐中的一种或几种。氯化反应时使用的溶剂可以是甲醇、乙醇、丙酮、甲苯、异丙醇、乙醚、甲缩醛中的一种或几种。氯化反应温度为25-50℃,氯化反应时间为1-15h。
所述步骤(2)中胺化反应温度为50-120℃,胺化反应使用试剂为邻苯二甲酰亚胺、乙二胺、六次甲基亚胺、二甲胺、三甲胺、己二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中的一种或几种。
所述步骤(2)中水解反应时使用的催化剂可以是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠、硫酸、硝酸、盐酸中的一种或几种,水解反应温度为85-130℃。
所述步骤(3)中,用于与胺球反应的有机弱酸可以是氯乙酸、氯丙酸、二氯乙酸、亚磷酸+甲醛、焦磷酸+甲醛中的一种或几种,胺球与有机弱酸反应的温度为40-90℃。胺球与有机弱酸反应的催化剂可以是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠中的一种或几种。
所述步骤(4)中,在弱酸阳树脂基体上负载镧化合物时,使用的镧化合物可以是氯化镧、硝酸镧、硫酸镧、磷酸镧及以上镧化合物的水合物中的一种或几种。弱酸阳树脂与镧化合物反应的温度为35-90℃。阳树脂与镧化合物反应时使用的溶剂可以是水、甲醇、乙醇、甲酸、乙二醇、丙二醇、丙三醇、乙酸、丙酸、异丙醇、以及水与以上试剂任意比例互溶配成的溶剂。弱酸阳树脂与镧化合物反应的催化剂可以是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠、氨水中的一种或几种,弱酸阳树脂与镧化合物反应的时间为1-30h。
本发明制备的大孔离子交换树脂,能选择性地吸附水体中的磷酸根、磷酸氢根、磷酸二氢根,并且可再生,几乎不吸附其他阴离子。实际应用中比传统一次性磷吸附剂更经济高效,产生的二次污染更小。
具体实施方式
为了说明本发明的效果,列举实施例对本发明作进一步详细说明,但本发明并不仅限于这些实施例。
实施例1
将30g 55%(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h。聚合完成后,95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为19.4m2/g,孔径中值为8.6nm;湿视密度为0.718g/cm3;湿真密度为1.15g/cm3;树脂含水量为47.9%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为7ppm,停止吸附,水洗2BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硫酸钠溶液,解析5BV,水洗2BV,解析率为85%。
实施例2
将30g 55%(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解形成水相。将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h。95℃下水煮1.5h除去甲苯,洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入10g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃下搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为18.7m2/g,孔径中值为7.6nm;湿视密度为0.723g/cm3;湿真密度为1.14g/cm3;树脂含水量为45.8%(w/w)。
取5ml除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱,吸附50ml后,吸附贫液中磷含量为14ppm,停止吸附,水洗2BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硫酸钠溶液,解析5BV,水洗2BV,解析率为82%。
实施例3
将20g 55%(w/w)的二乙烯苯、80g苯乙烯、50g甲苯、1.2g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中,搅拌下60℃保温2h,80℃保温2h,95℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为17.9m2/g,孔径中值为8.2nm;湿视密度为0.721g/cm3;湿真密度为1.19g/cm3;树脂含水量为46.3%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为21ppm,停止吸附,水洗2BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硫酸钠溶液,解析5BV,水洗2BV,解析率为84%。
实施例4
将30g 55%(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g羟甲基纤维素并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,丙酮100g,加入1g氯化铁作催化剂,在38℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为17.9m2/g,孔径中值为7.2nm;湿视密度为0.731g/cm3;湿真密度为1.21g/cm3;树脂含水量为48.5%。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为17ppm,停止吸附,水洗2BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硫酸钠溶液,解析5BV,水洗2BV,解析率为81%。
实施例5
将30g 55%(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,90℃下胺化8h,然后加入8%(w/w)氢氧化钾15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入15g氯乙酸,缓慢加入40g 20%(w/w)氢氧化钠溶液,60℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为17.9m2/g,孔径中值为6.9nm;湿视密度为0.722g/cm3;湿真密度为1.14g/cm3;树脂含水量为48.3%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为16ppm,停止吸附,水洗2BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硫酸钠溶液,解析5BV,水洗2BV,解析率为83%。
实施例6
将30g 55%(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g硝酸镧,加入300ml 25%(w/w)异丙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为17.7m2/g,孔径中值为7.5nm;湿视密度为0.716g/cm3;湿真密度为1.19g/cm3;树脂含水量为44.8%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为16ppm,停止吸附,水洗2BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硫酸钠溶液,解析5BV,水洗2BV,解析率为83%。
实施例7
将30g 55%(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钾溶液,直到体系pH达到11,50℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为15.6m2/g,孔径中值为10.5nm;湿视密度为0.724g/cm3;湿真密度为1.23g/cm3;树脂含水量为47.2%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为31ppm,停止吸附,水洗2BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硫酸钠溶液,解析5BV,水洗2BV,解析率为82%。
实施例8
将30g 55%(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为19.1m2/g,孔径中值为8.2nm;湿视密度为0.724g/cm3;湿真密度为1.17g/cm3;树脂含水量为46.8%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至6左右。以5BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为31ppm,停止吸附,水洗2BV,配制6%(w/w)的氢氧化钾+5%(w/w)的碳酸钠溶液,解析5BV,水洗2BV,解析率为81%。
实施例9
将20g 55%(w/w)的二乙烯苯、80g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中,搅拌下40℃保温2h,60℃保温2h,75℃保温2h。聚合完成后,95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为17.5m2/g,孔径中值为9.2nm;湿视密度为0.723g/cm3;湿真密度为1.13g/cm3;树脂含水量为48.2%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为17ppm,停止吸附,水洗2BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硫酸钠溶液,解析5BV,水洗2BV,解析率为81%。
实施例10
将30g 55%(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h。聚合完成后,95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入25g磷酸镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为18.4m2/g,孔径中值为7.5nm;湿视密度为0.724g/cm3;湿真密度为1.11g/cm3;树脂含水量为47.2%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为13ppm,停止吸附,水洗2BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硫酸钠溶液,解析5BV,水洗2BV,解析率为85%。
实施例11
将30g 55%(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h。聚合完成后,95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%(w/w)氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为19.4m2/g,孔径中值为8.6nm;湿视密度为0.718g/cm3;湿真密度为1.15g/cm3;树脂含水量为47.9%。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L硫酸溶液将正磷酸钠溶液pH调至8左右。以6BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为32ppm,停止吸附,水洗4BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硝酸钠溶液,解析10BV,水洗4BV,解析率为82%。
实施例12
将30g 55%(w/w)的二乙烯苯、70g丙烯腈、70g异辛烷、1g异丙苯过氧化氢配制为油相,在1L反应釜中加入500ml水,水中加入0.5g羧甲基纤维素并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,65℃保温2h,80℃保温2h。聚合完成后,95℃下水煮1.5h除去异辛烷洗涤得到树脂基球。
向50g树脂中加入六次甲基亚胺15g,80℃下胺化10h;取50g胺球加入18g氯丙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为17.8m2/g,孔径中值为8.2nm;湿视密度为0.727g/cm3;湿真密度为1.18g/cm3;树脂含水量为46.5%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L硫酸溶液将正磷酸钠溶液pH调至8左右。以6BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为31ppm,停止吸附,水洗4BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硝酸钠溶液,解析10BV,水洗4BV,解析率为79%。
实施例13
将12g的N,N-亚甲基双丙烯酰胺、70g丙烯腈、70g航空汽油、1g过氧化二异丙苯配制为油相,在1L反应釜中加入500ml水,水中加入0.5g羟乙基纤维素并搅拌溶解成为水相。将油相加入釜中,搅拌下50℃保温2h,75℃保温2h,90℃保温2h。聚合完成后,95℃下水煮1.5h除去航空汽油洗涤得到树脂基球。
向50g树脂中加入三乙烯四胺15g,95℃下胺化10h;取50g胺球加入18g二氯乙酸,缓慢加入50g 20%(w/w)氢氧化钠溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g硝酸镧,加入300ml 25%(w/w)乙醇溶液,室温下搅拌2h,缓慢滴加200ml 1mol/L氢氧化钠溶液,直到体系pH达到13,60℃搅拌6h,得到除磷树脂;制备的除磷树脂粒径为0.5-0.8mm,具有多孔结构,比表面积为16.3m2/g,孔径中值为7.7nm;湿视密度为0.734g/cm3;湿真密度为1.11g/cm3;树脂含水量为44.7%(w/w)。
取5ml上述除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L硫酸溶液将正磷酸钠溶液pH调至8左右。以6BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为38ppm,停止吸附,水洗4BV,配制8%(w/w)的氢氧化钠+5%(w/w)的硝酸钠溶液,解析10BV,水洗4BV,解析率为81%。
Claims (38)
1.一种用于从水体中除磷的树脂,其特征在于,树脂粒径为0.5-0.8mm;具有多孔结构,比表面积为8-25m2/g,孔径分布为3-15nm;湿视密度为0.68-0.74g/cm3;湿真密度为1.12-1.18g/cm3;树脂含水量以重量百分数计为43-57%;树脂上负载有镧氧键的官能团使其能够选择性吸附水体中的磷酸根。
2.根据权利要求1所述的用于从水体中除磷的树脂,其特征在于,比表面积为12-20m2/g,孔径中值为5-10nm;湿视密度为0.70-0.74g/cm3;湿真密度为1.13-1.17g/cm3;树脂含水量以重量百分数计为46-55%。
3.根据权利要求1所述的用于从水体中除磷的树脂,其特征在于,比表面积为19.4m2/g,孔径中值为8.6nm;湿视密度为0.718g/cm3;湿真密度为1.15g/cm3;树脂含水量以重量百分数计为47.9%。
4.根据权利要求1所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,包括如下步骤:
步骤(1):将单官能团单体、交联剂、致孔剂、引发剂配制成油相,分散剂和水配制成水相,采用悬浮聚合法制备树脂,聚合完成后将树脂中的致孔剂除去,得到树脂基球;
步骤(2):将树脂基球进行氯化反应、胺化反应,将胺化反应后的树脂加碱进行水解反应得到胺球;
步骤(3):胺球与有机弱酸进行反应,得到弱酸阳树脂;
步骤(4):将镧化合物负载到弱酸阳树脂表面,得到除磷树脂。
5.根据权利要求4所述的用于从水体中除磷的树脂的制备方法,其特征在于,步骤(1)中用的单官能团单体可以是苯乙烯系、丙烯酸系列、丙烯腈系中的一种或几种。
6.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(1)用的交联剂可以是二乙烯基苯、二异氰酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种。
7.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(1)中致孔剂可以是甲苯、异辛烷、汽油、航空汽油、正庚烷、环己烷、液体石蜡、白油中的一种或几种。
8.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(1)中引发剂可以是过氧化月桂酰、过氧化苯甲酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过硫酸钾、过硫酸钠、过硫酸铵偶氮二异丁腈、偶氮二异庚腈中的一种或几种。
9.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(1)中分散剂可以是聚乙烯醇、明胶、脂肪酸类、脂肪族酰胺类、石蜡类、纤维素类中的一种或几种。
10.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(1)中,水相和油相比为10:1-1:1V/V。
11.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(1)中,悬浮聚合温度为40-100℃,采用梯度升温的办法,第一阶段为40-60℃,第二阶段为60-80℃,第三阶段为80-100℃。
12.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(2)中氯化反应时使用的试剂为氯甲醚。
13.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(2)中氯化反应时使用的催化剂可以是氯化锌、氯化铝、氯化铁、三氟化硼、五氯化铌和三氟甲磺酸盐中的一种或几种。
14.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(2)中氯化反应时使用的溶剂可以是甲醇、乙醇、丙酮、甲苯、异丙醇、乙醚、甲缩醛中的一种或几种。
15.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(2)氯化反应温度为25-50℃,氯化反应时间为1-15h。
16.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(2)中胺化反应温度为50-120℃。
17.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(2)中胺化反应使用试剂为邻苯二甲酰亚胺、乙二胺、六次甲基亚胺、二甲胺、三甲胺、己二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中的一种或几种。
18.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(2)中水解反应时使用的催化剂可以是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠、硫酸、硝酸、盐酸中的一种或几种。
19.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(2)中水解反应温度为85-130℃。
20.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(3)中,用于与胺球反应的有机弱酸可以是氯乙酸、氯丙酸、二氯乙酸、亚磷酸+甲醛、焦磷酸+甲醛中的一种或几种。
21.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(3)中,胺球与有机弱酸反应的温度为40-90℃。
22.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,所述步骤(3)中,胺球与有机弱酸反应的催化剂是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠中的一种或几种。
23.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,其特征在于,步骤(1)中交联剂占单体的比例即交联度为2-30%W/W。
24.根据权利要求23所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,交联剂占单体的比例为4-15%W/W。
25.根据权利要求24所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,交联剂占单体的比例为5-10%W/W。
26.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,步骤(4)中使用的镧化合物可以是氯化镧、硝酸镧、硫酸镧、磷酸镧及以上镧化合物的水合物中的一种或多种的混合物。
27.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,步骤(4)中弱酸阳树脂与镧化合物反应的温度为15-90℃。
28.根据权利要求27所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,弱酸阳树脂与镧化合物反应的温度为35-90℃。
29.根据权利要求28所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,弱酸阳树脂与镧化合物反应的温度为50-70℃。
30.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,步骤(4)中弱酸阳树脂与镧化合物反应的溶剂是水、甲醇、乙醇、甲酸、乙二醇、丙二醇、丙三醇、乙酸、丙酸、异丙醇中的一种或几种的混合物,以及水与以上试剂任意比例互溶配成的溶剂。
31.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,步骤(4)中弱酸阳树脂与镧化合物反应的催化剂是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠、氨水中的一种或几种。
32.根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法,其特征在于,步骤(4)中弱酸阳树脂与镧化合物反应的时间为1-30h。
33.根据权利要求4所述的一种用于从水体除磷的树脂,其特征在于,制备步骤过程如下:
将30g 55%w/w的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相,在1L反应釜中加入500ml水,水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相,将油相加入釜中,搅拌下50℃保温2h,70℃保温2h,85℃保温2h,聚合完成后,95℃下水煮1.5h除去甲苯洗涤得到树脂基球;
称量50g树脂基球,加入氯甲醚12g,甲缩醛100g,加入1g氯化锌作催化剂,在42℃下搅拌并保温12小时,然后水洗即得到氯化后的树脂;向氯化后的树脂中加入邻苯二甲酰亚胺15g,80℃下胺化10h,然后加入10%氢氧化钠15g,160℃下水解2h,水洗后得到胺球;取50g胺球加入18g氯乙酸,缓慢加入50g 20%氢氧化钠w/w溶液,50℃下反应10h,水洗至中性即得到弱酸阳树脂。
34.根据权利要求1-3中任一所述的一种用于从水体除磷的树脂以及权利要求4-33中任一所述的制备方法制备得到的从水体中除磷的树脂的应用方法,其特征在于,从水体中除磷的应用方法按照以下步骤进行:取一定量的树脂装柱,将含磷酸根的溶液以一定的流速过柱,当出口溶液中磷酸根浓度大于阈值时,停止吸附,使用解析剂解析,然后水洗树脂即可进行下一周期的吸附,水体中磷的残留率在20ppm以下。
35.根据权利要求35所述的一种从水体除磷的树脂的应用方法,其特征在于,从水体除磷的应用方法按照以下步骤进行:取一定量的树脂装柱,将含磷酸根的溶液以1-10BV/h的流速过柱,吸附5-15BV后,当出口溶液中磷酸根浓度大于20ppm时停止吸附,水洗,使用解析剂解析,解析1-15BV后,使用2BV的去离子水清洗树脂即可再次使用。
36.根据权利要求35所述的一种从水体除磷的树脂的应用方法,其特征在于,解析剂可以是1-15%w/w的氢氧化钠溶液,1-15%w/w的硫酸钠溶液,1-15%w/w的碳酸钠溶液或1-15%w/w的硝酸铵溶液中的一种或几种的混合物。
37.根据权利要求35所述的一种从水体除磷的树脂的应用方法,其特征在于,包括如下步骤:取5ml除磷树脂装柱,配制400ppm的正磷酸钠溶液,并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右;以3BV/h的速度过柱,过柱吸附50ml后,吸附贫液中磷含量为7ppm,停止吸附,水洗2BV,配制8%的氢氧化钠+5%的硫酸钠溶液,解析5BV,水洗2BV。
38.根据权利要求35所述的一种从水体除磷的树脂的应用方法,其特征在于,其特征在于,水体中磷酸根含量可控制在20ppm之内。
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Publication number | Priority date | Publication date | Assignee | Title |
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CN113101902A (zh) * | 2021-04-13 | 2021-07-13 | 北京赛科康仑环保科技有限公司 | 用于酸性磷酸酯类萃取体系的吸附材料及制备方法和应用 |
WO2022135494A1 (zh) * | 2020-12-24 | 2022-06-30 | 西安蓝晓科技新材料股份有限公司 | 一种用于从水体中除磷的树脂、制备方法及其应用 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101289241A (zh) * | 2007-04-20 | 2008-10-22 | 罗门哈斯公司 | 从水溶液中除去磷酸盐的方法 |
CN102600810A (zh) * | 2012-03-23 | 2012-07-25 | 南开大学 | 一种孔径均匀的高比表面中孔吸附树脂及制备方法和应用 |
CN104138750A (zh) * | 2014-07-22 | 2014-11-12 | 燕山大学 | 一种利用嵌入型氧化镧复合树脂深度除磷的方法 |
CN104788599A (zh) * | 2015-03-27 | 2015-07-22 | 徐州浩通新材料科技股份有限公司 | 一种大孔弱碱性阴离子交换树脂的制备方法 |
CN105037601A (zh) * | 2015-08-26 | 2015-11-11 | 同济大学 | 一种耐污染型深度软化螯合树脂的合成方法 |
CN105214629A (zh) * | 2015-10-30 | 2016-01-06 | 南京信息工程大学 | 一种生物质基纳米氧化镧除磷复合吸附剂及其制备方法 |
CN105566191A (zh) * | 2016-03-10 | 2016-05-11 | 南京工业大学 | 一种利用超高交联树脂吸附分离叶黄素的方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4399235A (en) * | 1981-05-11 | 1983-08-16 | The Dow Chemical Company | High density ion exchange resins |
GB8817051D0 (en) * | 1988-07-18 | 1988-08-24 | Dow Stade Gmbh | Ion exchange resins beads & processes for preparing them |
CN106179537A (zh) * | 2016-08-05 | 2016-12-07 | 安徽皖东化工有限公司 | 一种除磷用聚苯乙烯多元共聚离子交换树脂的生产方法 |
CN107057004B (zh) * | 2016-10-19 | 2019-06-25 | 南京大学盐城环保技术与工程研究院 | 一种除硝态氮树脂及其制备方法 |
CN110003376B (zh) * | 2019-03-11 | 2021-09-28 | 西安蓝晓科技新材料股份有限公司 | 一种从含镍溶液中制备硫酸镍的螯合树脂制备方法 |
CN112591851A (zh) * | 2020-12-24 | 2021-04-02 | 西安蓝晓科技新材料股份有限公司 | 一种用于从水体中除磷的树脂、制备方法及其应用 |
-
2020
- 2020-12-24 CN CN202011553288.7A patent/CN112591851A/zh active Pending
-
2021
- 2021-12-22 EP EP21909489.3A patent/EP4190754A4/en active Pending
- 2021-12-22 US US18/044,321 patent/US20230331591A1/en active Pending
- 2021-12-22 CA CA3187096A patent/CA3187096A1/en active Pending
- 2021-12-22 WO PCT/CN2021/140580 patent/WO2022135494A1/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101289241A (zh) * | 2007-04-20 | 2008-10-22 | 罗门哈斯公司 | 从水溶液中除去磷酸盐的方法 |
CN102600810A (zh) * | 2012-03-23 | 2012-07-25 | 南开大学 | 一种孔径均匀的高比表面中孔吸附树脂及制备方法和应用 |
CN104138750A (zh) * | 2014-07-22 | 2014-11-12 | 燕山大学 | 一种利用嵌入型氧化镧复合树脂深度除磷的方法 |
CN104788599A (zh) * | 2015-03-27 | 2015-07-22 | 徐州浩通新材料科技股份有限公司 | 一种大孔弱碱性阴离子交换树脂的制备方法 |
CN105037601A (zh) * | 2015-08-26 | 2015-11-11 | 同济大学 | 一种耐污染型深度软化螯合树脂的合成方法 |
CN105214629A (zh) * | 2015-10-30 | 2016-01-06 | 南京信息工程大学 | 一种生物质基纳米氧化镧除磷复合吸附剂及其制备方法 |
CN105566191A (zh) * | 2016-03-10 | 2016-05-11 | 南京工业大学 | 一种利用超高交联树脂吸附分离叶黄素的方法 |
Non-Patent Citations (1)
Title |
---|
湖南省涟源钢铁厂钢铁研究所编: "钢铁原材料化学分析", 31 January 1975, 湖南省人民出版社, pages: 300 - 302 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022135494A1 (zh) * | 2020-12-24 | 2022-06-30 | 西安蓝晓科技新材料股份有限公司 | 一种用于从水体中除磷的树脂、制备方法及其应用 |
CN113101902A (zh) * | 2021-04-13 | 2021-07-13 | 北京赛科康仑环保科技有限公司 | 用于酸性磷酸酯类萃取体系的吸附材料及制备方法和应用 |
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