CN101351411A - 去除水中污染物的方法和吸附剂 - Google Patents
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Abstract
本发明涉及一种通过吸附剂与水接触的步骤从水中去除如砷酸盐的溶解的污染物的方法,该吸附剂含有超过10重量%的钛氧化物和超过0.1重量%的室温下水溶性小于0.5克每升水的如硫酸钙的硫酸盐,其中钛氧化物主要为二氧化钛。
Description
技术领域
本发明涉及从水中去除溶解的污染物的方法和吸附剂,特别涉及使用一种含有钛氧化物和硫酸盐或碱的吸附剂。
背景技术
以全文引用的方式并入本文的美国专利6,919,029描述了,使用混于其他物质中的含有钛氧化物的吸附剂,从水中除去如砷化合物的溶解的污染物的一种方法和吸附剂。‘029专利所述的方法和吸附剂性能良好,但处理后的水呈酸性。因此,发明一种有效性类似于‘029专利所述吸附剂,能从水中去除溶解的污染物而不会过度降低处理后的水的pH值的吸附剂,将是本技术领域的进步。
发明内容
本发明提供从水中去除溶解的污染物的一种方法和吸附剂,该吸附剂不仅具有类似于‘029专利所述吸附剂的有效性,而且不会过度降低处理后的水的pH值。本发明所述吸附剂(与‘029专利所述吸附剂相同)包含钛氧化物和(与‘029专利所述吸附剂不同)硫酸盐或碱。
更具体而言,在一个具体实施方案中,本发明提供一种从水中去除溶解的污染物的方法,所述方法包括使吸附剂与水接触的步骤,该吸附剂含有超过10重量%的钛氧化物和超过0.1重量%的室温下水溶性小于0.5克每升水的硫酸盐,其中钛氧化物主要为二氧化钛。
在另一个具体实施方案中,本发明提供一种从水中去除溶解的污染物的方法,该方法包括使吸附剂与水接触的步骤,该吸附剂含有超过10重量%的钛氧化物和超过0.1重量%的室温下水溶性小于0.5克每升水的碱,其中钛氧化物主要为二氧化钛。
在另一个具体实施方案中,本发明提供一种从水中去除溶解的污染物的吸附剂,所述吸附剂含有超过10重量%的钛氧化物和超过0.1重量%的室温下水溶性小于0.5克每升水的硫酸盐,其中钛氧化物主要为二氧化钛。
具体实施方式
本发明提供从水中去除溶解的污染物的一种方法和吸附剂。溶解的污染物包括如‘029专利所列的相同污染物,还可进一步无限制包括溶解的铅、钒、硒、铜、镍、汞和铬。本发明的方法和吸附剂对于去除水中溶解的砷化合物尤为有效。
在一个具体实施方案中,本发明的吸附剂含有超过10重量%的钛氧化物和超过0.1重量%的室温下水溶性小于0.5克每升水的硫酸盐,其中钛氧化物主要是二氧化钛。优选地,超过80重量%的吸附剂具有介于10至60US目的粒度。更优选地,超过80重量%的吸附剂具有介于16至60US目的粒度。更优选地,超过80重量%的吸附剂具有介于25至45US目的粒度。然而,应了解在一些应用中也可使用尺寸更小的吸附剂,比如其中超过80重量%具有介于100至400US目或200至325US目的粒度的一种吸附剂。
本发明的吸附剂优选含有超过0.5重量%的硫酸盐。本发明的吸附剂更优选地含有超过2重量%的硫酸盐。甚至更优选地,本发明的吸附剂含有超过5重量%的硫酸盐。本发明的吸附剂更优选地含有超过10重量%的硫酸盐。优选地,硫酸盐为硫酸钙盐。然而,当硫酸盐为硫酸钙盐时,优选的吸附剂含有基于元素分析少于5重量%的钙。用于测定硫酸盐和钛氧化物形态(例如,硫酸钙可以石膏和/或烧石膏形式存在,而二氧化钛可以锐钛矿或金红石形式存在)和本发明吸附剂的浓度的优选化学分析方法为X射线衍射光谱。本发明的吸附剂中硫的浓度可由X射线荧光分析确定。对本发明吸附剂中钛元素的分析可通过中子活化分析或X射线荧光进行。
优选地,由众所周知的硫酸法制备本发明吸附剂中钛氧化物。优选地,本发明的吸附剂含有基于元素分析超过20重量%的钛。更优选地,本发明的吸附剂含有基于元素分析超过40重量%的钛。
或者,用于本发明的吸附剂可含有超过10重量%的钛氧化物和超过0.1重量%的室温下水溶性小于0.5克每升水的碱,其中钛氧化物主要为二氧化钛。可使用满足上述溶解度范围的任何碱,包括氢氧离子型离子交换树脂。
本发明的方法包括使本发明的吸附剂与水接触的步骤。优选地,水流通过吸附剂的床。
本发明的吸附剂优选通过以下方式制得:在未煅烧硫酸法二氧化钛中加入石灰和水形成浆料,然后挤压该浆料通过模具以形成的棒状颗粒,经过干燥和研磨(以及任选的筛分)以产生适用于具体应用的粒度分布。本发明中石灰的使用有利于制备具有比‘029专利的吸附剂更高机械强度(更低磨耗)和更低体密度的吸附剂。
对比实施例1
将1.06千克未煅烧钛氧化物粉末(具有约80重量%锐钛矿型二氧化钛浓度)与3千克水混合后静置过夜。然后,将混合物在80℃下干燥至少4小时,或者直至其含水量以实验室用湿度天平测定少于10%。将0.97千克所得固体研磨成微细粉末,与89克Ludox牌粘合剂(30重量%胶体SiO2水溶液)和430克水混合、粉碎后得到从三孔(直径1/16英寸)挤压机挤压出的泥料。从挤压机得到的挤出物在80摄氏度下干燥过夜,进而研磨和筛分得到具有介于16至60US目粒度的吸附剂#1。该材料(吸附剂#1)的填充床密度为0.91克每毫升(ASTM测试法B-527)。湿磨耗的测量可通过下述方式进行:在含有80毫升水的广口瓶中加入20×30和30×40目大小的样品各20克。将广口瓶置于辊上并且以85rpm转速滚动30分钟。将瓶内物质倾倒通过60目的筛网,并使筛网在80℃下的空气中干燥6至16个小时。衡量该过程中流失和获取的水分后,由筛网上的水分残留量相比于最初瓶内的水分含量计算得出磨耗%。吸附剂#1的湿磨耗为17%。
将pH值约为7.8的自来水通过0.5升填充有吸附剂#1的过滤柱。处理后的水的初始pH值约为2.3。处理50升水后,处理后的水的pH值约为3.2。处理100升水后,处理后的水的pH值约为3.6。处理150升水后,处理后的水的pH值约为5.0。
实施例1
将1.08克未煅烧钛氧化物粉末(具有约80重量%锐钛矿型二氧化钛浓度)与36克Ca(OH)2和3千克水混合后静置过夜。然后,将混合物在80℃下干燥至少4小时,或者直至其含水量以实验室用湿度天平测定少于10%。将1.04千克所得固体研磨成微细粉末,与94克Ludox牌粘合剂(30重量%胶体SiO2水溶液)和430克水混合,粉碎后得到从三孔(直径1/16英寸)挤压机挤压出的泥料。从挤压机得到的挤出物在80℃下干燥过夜,进而研磨和筛分得到具有介于16至60US目粒度的吸附剂#2。吸附剂#2的填充床密度为0.84克每毫升。该材料的湿磨耗(如对比实施例1中所描述)为6%。
将pH值约为7.8的自来水通过0.5升填充有吸附剂#2的过滤柱。处理后的水的初始pH值约为6.7。处理50升水后,处理后的水的pH值约为6.2。处理100升水后,处理后的水的pH值约为6.3。处理150升水后,处理后的水的pH值约为6.5。
对比实施例2
将1.0千克未煅烧钛氧化物粉末(主要为含有基于元素分析约53重量%的钛,基于元素分析约2.2重量%的硫,和基于元素分析约0.01重量%的钙的锐钛矿二氧化钛,市售为Millennium Chemicals,HuntValley,Maryland的Grade G-3未煅烧超微TiO2)与100克Ludox牌粘合剂(30重量%胶体SiO2水溶液)和水混合,粉碎后得到从三孔(直径1/16英寸)挤压机挤压出的泥料。从挤压机得到的挤出物在80℃下干燥过夜,进而研磨和筛分得到具有介于16至60US目粒度的吸附剂#3。
将含有300ppb砷酸盐(根据NSF/ANSI标准53制备)、pH值约为7.5的水通过内径0.45英寸、长4英寸的填充有吸附剂#3的柱子,水的流速控制在空床接触时间(EBCT)为120秒。定期从处理后的水中取样并分析砷。处理后的水的初始砷浓度低于约1ppb的检测限。处理后的水的初始pH值为2.5(处理830床体积的水后pH值达到7)。处理4,000床体积的水后,排出水的砷浓度约为1ppb。处理6,000床体积的水后,排出水的砷浓度约为10ppb。
实施例2
将1.0千克石灰处理过的未煅烧钛氧化物粉末(主要为含有基于元素分析约52重量%的钛,基于元素分析约1.9重量%的硫,和基于元素分析约2.1重量%的钙的锐钛矿二氧化钛,市售为MillenniumChemicals,Hunt Valley,Maryland的Grade G-2未煅烧超微TiO2)与100克Ludox牌粘合剂(30重量%胶体SiO2水溶液)和水混合,粉碎后得到从三孔(直径1/16英寸)挤压机挤压出的泥料。从挤压机得到的挤出物在80℃下干燥过夜,进而研磨且筛分得到具有介于16至60US目粒度的吸附剂#4。
将含有300ppb砷酸盐(根据NSF/ANSI标准53制备)、pH值约为7.5的水通过内径0.45英寸、长4英寸的填充有吸附剂#4的柱子,水的流速控制在空床接触时间(EBCT)为120秒。定期从处理后的水中取样并分析砷。处理后的水的初始砷浓度低于约1ppb的检测限。处理后的水的初始pH值为5(处理120床体积的水后pH值达到7)。处理4,000床体积的水后,排出水的砷浓度约为1ppb。处理7,500床体积的水后,排出水的砷浓度约为10ppb。
结论
尽管已经参考其优选的具体实施方案描述本发明,但在本文揭示的启示和范围内可进行修改。因此,该申请涵盖应用本文揭示的基本原理而对本发明所做的任何变动、应用或改编。此外,本申请不仅涵盖在本发明所涉及的本领域已知或常规的实施范围内对本文揭示内容的偏离,还涵盖在下述权利要求限制内对本文揭示内容的偏离。
Claims (29)
1、一种从水中去除溶解的污染物的方法,其包括使吸附剂与水接触的步骤,该吸附剂含有超过10重量%的钛氧化物和超过0.1重量%的室温下水溶性小于0.5克每升水的硫酸盐,其中钛氧化物主要为二氧化钛。
2、如权利要求1所述的方法,其中吸附剂含有超过0.5重量%的硫酸盐。
3、如权利要求1所述的方法,其中吸附剂含有超过2重量%的硫酸盐。
4、如权利要求1所述的方法,其中吸附剂含有超过5重量%的硫酸盐。
5、如权利要求1所述的方法,其中吸附剂含有超过10重量%的硫酸盐。
6、如权利要求2所述的方法,其中硫酸盐为硫酸钙盐。
7、如权利要求6所述的方法,其中吸附剂含有基于元素分析少于5重量%的钙。
8、如权利要求3所述的方法,其中硫酸盐为硫酸钙盐。
9、如权利要求8所述的方法,其中吸附剂含有基于元素分析少于5重量%的钙。
10、如权利要求4所述的方法,其中硫酸盐为硫酸钙盐。
11、如权利要求10所述的方法,其中吸附剂含有基于元素分析少于5重量%的钙。
12、如权利要求5所述的方法,其中硫酸盐为硫酸钙盐。
13、如权利要求12所述的方法,其中吸附剂含有基于元素分析少于5重量%的钙。
14、如权利要求1所述的方法,其中吸附剂中的钛氧化物含有由硫酸法制备的二氧化钛。
15、如权利要求7所述的方法,其中吸附剂中的钛氧化物含有由硫酸法制备的二氧化钛。
16、如权利要求9所述的方法,其中吸附剂中的钛氧化物含有由硫酸法制备的二氧化钛。
17、如权利要求11所述的方法,其中吸附剂中的钛氧化物含有由硫酸法制备的二氧化钛。
18、如权利要求13所述的方法,其中吸附剂中的钛氧化物含有由硫酸法制备的二氧化钛。
19、如权利要求1所述的方法,其中吸附剂含有基于元素分析超过20重量%的钛、基于元素分析超过1重量%的硫、基于元素分析少于5重量%的钙,该吸附剂中的钛氧化物含有由硫酸法制备的二氧化钛。
20、如权利要求1所述的方法,其中吸附剂含有基于元素分析超过40重量%的钛、基于元素分析超过2重量%的硫、基于元素分析少于5重量%的钙,该吸附剂中的钛氧化物含有由硫酸法制备的二氧化钛。
21、如权利要求1至20任一项所述的方法,其中溶解的污染物包含砷化合物。
22、一种从水中去除溶解的污染物的方法,其包括使吸附剂与水接触的步骤,该吸附剂含有超过10重量%的钛氧化物和超过0.1重量%的碱,该碱的室温下水溶性小于0.5克每升水,该钛氧化物主要为二氧化钛。
23、如权利要求22所述的方法,其中溶解的污染物包含砷化合物。
24、一种去除水中溶解的污染物的吸附剂,所述吸附剂含有超过10重量%的钛氧化物和超过0.1重量%的室温下水溶性小于0.5克每升水的硫酸盐,其中钛氧化物主要为二氧化钛。
25、如权利要求24所述的吸附剂,其中超过80重量%的吸附剂具有介于10至60US目的粒度。
26、如权利要求24所述的吸附剂,其中超过80重量%的吸附剂具有介于16至60US目的粒度。
27、如权利要求24所述的吸附剂,其中超过80重量%的吸附剂具有介于25至45US目的粒度。
28、如权利要求24所述的吸附剂,其中超过80重量%的吸附剂具有介于100至400US目的粒度。
29、如权利要求24所述的吸附剂,其中超过80重量%的吸附剂具有介于200至325US目的粒度。
Applications Claiming Priority (1)
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PCT/US2006/004028 WO2007089241A1 (en) | 2006-02-02 | 2006-02-02 | Method and sorbant for removing contaminates from water |
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CN101351411A true CN101351411A (zh) | 2009-01-21 |
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US (1) | US20080290035A1 (zh) |
EP (1) | EP1981816A1 (zh) |
CN (1) | CN101351411A (zh) |
WO (1) | WO2007089241A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101785988A (zh) * | 2009-01-23 | 2010-07-28 | 中国科学院金属研究所 | 多元金属氧化物砷吸附材料及其制备方法和应用 |
CN106145288A (zh) * | 2016-08-11 | 2016-11-23 | 李宝全 | 一种不含氯化物的净水剂 |
CN107262019A (zh) * | 2017-08-22 | 2017-10-20 | 同济大学 | 一种改性赤泥及其制备方法和应用 |
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CH590179A5 (zh) * | 1973-11-08 | 1977-07-29 | Ciba Geigy Ag | |
DE2817551C2 (de) * | 1978-04-21 | 1984-07-19 | Kronos Titan-Gesellschaft Mbh, 5090 Leverkusen | Titandioxidhydrat mit besonderer Struktur sowie seine Herstellung |
US5249948A (en) * | 1991-04-08 | 1993-10-05 | Koslow Technologies Corporation | Apparatus for the continuous extrusion of solid articles |
US5189092A (en) * | 1991-04-08 | 1993-02-23 | Koslow Technologies Corporation | Method and apparatus for the continuous extrusion of solid articles |
US5494880A (en) * | 1994-03-23 | 1996-02-27 | The United States Of America As Represented By The United States Department Of Energy | Durable zinc oxide-containing sorbents for coal gas desulfurization |
EP0829299A4 (en) * | 1995-05-26 | 1999-02-10 | Hitachi Chemical Co Ltd | MATERIAL TO CLEAN THE AMBIENT AIR |
US6045700A (en) * | 1996-07-29 | 2000-04-04 | Solutia Inc. | Retrievable organic carbon scavengers for cleaning of contaminated surface water sediments |
US6340711B1 (en) * | 1996-08-30 | 2002-01-22 | Showa Denko K.K. | Particles aqueous dispersion and film of titanium oxide and preparation thereof |
US5821186A (en) * | 1996-11-01 | 1998-10-13 | Lockheed Martin Energy Research Corporation | Method for preparing hydrous titanium oxide spherules and other gel forms thereof |
US6719869B2 (en) * | 1997-03-07 | 2004-04-13 | Koslow Technologies Corporation | Method of stabilizing composite media and media produced thereby |
US6550622B2 (en) * | 1998-08-27 | 2003-04-22 | Koslow Technologies Corporation | Composite filter medium and fluid filters containing same |
US20020052291A1 (en) * | 1999-09-30 | 2002-05-02 | Ranjani Siriwardane | Low temperature sorbents for removal of sulfur compounds from fluid feed streams |
EP1272432A2 (en) * | 2000-04-10 | 2003-01-08 | Midwest Research Institute | Phenol removal pretreatment process |
US7655112B2 (en) * | 2002-01-31 | 2010-02-02 | Kx Technologies, Llc | Integrated paper comprising fibrillated fibers and active particles immobilized therein |
US7497952B2 (en) * | 2002-02-14 | 2009-03-03 | The Trustees Of Stevens Institute Of Technology | Methods of preparing a surface-activated titanium oxide product and of using same in water treatment processes |
US6919029B2 (en) * | 2002-02-14 | 2005-07-19 | Trustees Of Stevens Institute Of Technology | Methods of preparing a surface-activated titanium oxide product and of using same in water treatment processes |
US7473369B2 (en) * | 2002-02-14 | 2009-01-06 | The Trustees Of The Stevens Institute Of Technology | Methods of preparing a surface-activated titanium oxide product and of using same in water treatment processes |
-
2006
- 2006-02-02 CN CN200680050097.0A patent/CN101351411A/zh active Pending
- 2006-02-02 US US12/097,281 patent/US20080290035A1/en not_active Abandoned
- 2006-02-02 WO PCT/US2006/004028 patent/WO2007089241A1/en active Application Filing
- 2006-02-02 EP EP06734388A patent/EP1981816A1/en not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101785988A (zh) * | 2009-01-23 | 2010-07-28 | 中国科学院金属研究所 | 多元金属氧化物砷吸附材料及其制备方法和应用 |
CN101785988B (zh) * | 2009-01-23 | 2013-09-25 | 中国科学院金属研究所 | 多元金属氧化物砷吸附材料及其制备方法和应用 |
CN106145288A (zh) * | 2016-08-11 | 2016-11-23 | 李宝全 | 一种不含氯化物的净水剂 |
CN107262019A (zh) * | 2017-08-22 | 2017-10-20 | 同济大学 | 一种改性赤泥及其制备方法和应用 |
Also Published As
Publication number | Publication date |
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WO2007089241A1 (en) | 2007-08-09 |
EP1981816A1 (en) | 2008-10-22 |
US20080290035A1 (en) | 2008-11-27 |
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