CN102933507A - 海水脱盐设备和高纯度盐的生产 - Google Patents
海水脱盐设备和高纯度盐的生产 Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 95
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000013535 sea water Substances 0.000 title description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000001223 reverse osmosis Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 239000012267 brine Substances 0.000 claims description 18
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 18
- 238000001728 nano-filtration Methods 0.000 claims description 16
- 239000002562 thickening agent Substances 0.000 claims description 15
- 239000012466 permeate Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
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- 239000012465 retentate Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 15
- 238000000746 purification Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract 1
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- 238000011084 recovery Methods 0.000 description 9
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- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
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- 239000002699 waste material Substances 0.000 description 4
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
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Abstract
本发明公开了一种用于生产高纯度的盐或浆料产品的整体脱盐和盐设备。来自脱盐设备的截留物流用作盐设备的进料流。将盐设备进料流过滤以有效除去硫酸根,这防止在盐设备装置中结垢。该过滤也可降低进料的钙、镁、碳酸氢盐或其它成分的水平,这也可防止在盐设备装置中结垢。所述盐设备生产高纯度盐产品,而不使用化学纯化。
Description
发明背景。
发明领域
本发明主要涉及脱盐、盐生产和水生产。具体地,本发明涉及将盐水脱盐截留物(reject)流转化为纯盐的方法,其中该脱盐方法可经由热方法或经由膜方法。
相关技术的描述
如在2008年12月30日提交的美国专利申请12/345,856(该申请通过引用结合到本文中)中所述的,数世纪以来,通常通过使用露天蒸发泻湖或热浓缩装置和方法,通过蒸发浓缩海水或另一种天然存在的盐水而生产食盐。许多现代的工业过程需要充分高纯度的盐,例如实质不含不期望的化学或味道成分的氯化钠盐。这种高纯度盐可由一些天然地质层组开采,并且还可通过浓缩和处理步骤除去存在于起始溶液中的主要的不需要的杂质而得自其它咸水。
当不能得到新鲜的水时,在历史上已由天然的咸水或微咸水生产适于饮用的高品质水或纯水,开始时通过热方法例如冷冻或蒸馏,更近来,通过膜方法例如反渗透或膜蒸气渗透,和/或通过混合式膜/热方法。当由含盐的进料起始时,所有这些水生产方法仅回收或纯化存在于进料中的一部分水,并且通常生产比初始进料流实质上更浓缩的废盐水。
一个问题在于,海水和其它天然咸水含有许多溶质和杂质,因此,如果期望高品质盐,则纯水生产过程的富含盐的侧流,即,反渗透水处理的浓缩的截留物或蒸馏过程的残余物,包括限制通量或处理速率和/或水侧的回收率二者的其它固体,必须在盐水侧上除去。这些溶解的固体可能为腐蚀性的,并且在盐设备蒸发器和结晶器中结垢。当前,在盐水侧上引入化学品以防止或降低结垢。这些化学品昂贵并且降低盐纯度。
因此,需要非化学纯化溶液以降低或防止在盐设备中结垢。
发明概述
本发明涉及盐水脱盐和盐设备。所述脱盐设备具有进料流和截留物流。所述脱盐设备截留物流用作盐设备进料流。过滤器从所述盐设备进料流选择性除去结垢物类。另外的装置将已过滤的盐设备进料加工成为高纯度潮湿的盐或浆料。
附图简述
由本文的说明书和权利要求书以及附图,可以理解本发明的这些和其它方面,附图显示结构细节和说明性实施方案,其中:
图1示意性说明根据本发明的一个实施方案用于整体生产盐和出水的系统;和
图2为显示对于一个代表性设备计算的在盐设备进料和相应的过滤器渗透物流中成分的代表性浓度的水品质表。
发明详述
本文在整个说明书和权利要求中使用的近似语言,可用于修饰任何可容许变化而不导致其相关的基本功能改变的数量表示。因此,被一个或多个术语例如“约”修饰的值不局限于指定的精确值。在至少一些情况下,近似语言可相应于测量该值的仪器的精度。范围限度可组合和/或互换,并且除非上下文或语言说明另外的情况,否则这些范围被指定并包括本文陈述的所有子范围。除了在操作实施例中或当另外说明时,否则在说明书和权利要求中使用的涉及成分的量、反应条件等的所有数字或表述应理解为在所有情况下被术语“约”修饰。
“任选”或“任选地”是指随后描述的事件或情况可能发生或者可能不发生,或者随后指定的材料可能存在或者可能不存在,并且该描述包括事件或情况发生或者材料存在的情况,以及事件或情况不发生或者材料不存在的情况。
本文使用的术语“包含”、“包括”、“具有”或它们的任何其它变体旨在涵盖非排他的内含物。例如,包括要素列表的过程、方法、制品或设备不必仅局限于那些要素,而是可包括该过程、方法、制品或设备未明确列出的或固有的其它要素。
除非上下文明确指出另外的情况,否则单数形式“一”、“一个”和“该”包括复数对象。
本发明公开了一种用于生产纯水和盐或浆料产品二者的整体设备,可行地有效提供具有高纯度的盐,同时降低或防止在盐设备中的蒸发器和结晶器中结垢,而不使用化学纯化。
在图1中公开了包含脱盐设备20和盐设备40的联合脱盐和盐设备10。在该实施方案中,脱盐设备20包含海水或微咸水进料22、纯水渗透物流A1、截留物流B1和任选的废物流C1。脱盐设备进一步包含预处理部分24、任选的纳米过滤(NF)部分26和反渗透(RO)部分28。
在操作中,进料22通过预处理部分24,随后前进至任选的NF部分26。NF部分26产生废物流C1,并将进料流22引到RO部分28中。RO部分28产生纯水渗透物流A1和截留物流B1。截留物流B1变为盐设备进料流41。在其中NF部分26不存在的一些实施方案中,进料22从预处理部分24通到RO部分28中。
预处理部分24为已知的类型(例如,粗筛、介质过滤器、絮凝和澄清、超滤、双重介质和/或其它预处理过程),并且除去悬浮的固体和实质部分的有机物质。
脱盐设备20可为具有截留物流B1的任何标准盐水反渗透(SWRO)脱盐设备或任何标准热多效蒸馏(MED)脱盐设备或任何标准热多级闪蒸(MSF)脱盐设备,其使取自盐水来源(例如海洋、大海或有咸味的水体)的水脱盐。
盐设备40包含进料流41、蒸馏物流A2、截留物流C2和潮湿的盐或浆料S。盐设备40进一步包含NF部分42、任选的浓缩器部分43、蒸发器部分44和结晶器部分48。在一些实施方案中,任选的浓缩器部分43为RO部分。
在操作中,进料41通过NF部分42,并作为渗透物离开,随后前进至至任选的浓缩器部分43。NF部分42也产生废物流C2,并且任选的浓缩器部分43产生渗透物流A3。在作为浓缩物离开任选的浓缩器部分43之后,进料41前进至蒸发器部分44,并作为浓缩物离开,随后进入结晶器部分48。蒸发器部分44也产生蒸馏物流A2。进料41作为潮湿的盐或浆料S离开结晶器部分48。在其中浓缩器部分43不存在的一些实施方案中,进料41从NF部分42直接通到蒸发器部分44中。
在图1中,NF部分42从进料41选择性除去结垢物类。这种结垢物类可包括硬性离子(例如,钙和镁)和硫酸根(例如,天然的二价和多价硫离子)。NF部分42实现硫酸根的充分降低,除去二价离子,同时至少稍微选择性地通过一价物质。NF部分42在相对低的进料压力下操作,并优选包括若干阶段,使得沿着进料41传递的NF部分42渗透物占进料体积的约70%至约80%或更多,实现高水回收率。该NF部分42渗透物形成中间渗透物流,其构成的进料41实质不含结垢硫酸根,相对贫二价离子,并且富含一价盐(主要为NaCl),其中总溶解固体(TDS)为进料TDS的约2/3。优选NF部分42包含双极(2-pass)纳米过滤系统。NF部分42采用与在美国专利申请12/345,856中的NF部分26类似的方式构造和操作,该专利申请在上文通过引用结合。
在一个实施方案中,NF部分42截留(reject)具有多于一个负电荷的阴离子,取决于形状和尺寸截留阳离子,截留分子量大于200-300道尔顿的有机物。孔径为约0.0009-0.0085微米左右。另外,NF部分42一般的操作压力为约70-400psig,其中最大操作压力为约600psig。NF部分42的最大压降为跨元件12psi和每壳体50psi。NF部分42的一般操作通量为约8-20GFD。
此外,在一些实施方案中,NF部分42可在降低的pH下操作,优选在小于7.0的pH下,以增强钙和镁去除。另外,在一些实施方案中,NF部分42平均每级(pass)截留小于约30%的氯根、大于约90%的硫酸根、大于约68%的钙和大于约77%的镁。
因此,在本发明的一方面,NF部分42消除了对用以防止在NF部分42下游的装置(例如任选的基于膜的浓缩器43、蒸发器44和结晶器48)中结垢的单独的化学纯化阶段的需要。此外,通过以超过99%的纯度结晶,NF部分42使得盐能连续回收,这满足用于氯碱(chlor-alkali)、苏打灰生产或其它使用者应用的预期纯度标准(例如,NaCl纯度水平和不存在关键的污染物)。
此外NF部分42使得任选的浓缩器部分43能以高回收率作用于NF部分42渗透物上而不结垢且不使用抗结垢剂来生产纯出水和充分浓缩的截留物流。
任选的RO部分43可为海水RO、微咸水RO或其它RO系统。NF部分42使得RO部分43能以高回收率作用于NF部分42渗透物上而不结垢且无需抗结垢剂来生产纯出水和充分浓缩的截留物流。通过举例说明,双极NF部分42可以约70%-约80%回收率操作,并且RO部分43可包括第三阶段高压力盐水回收阶段,以约70%至约80%或更高的回收率作用于该NF渗透物上,给出在盐设备40中从约50%至约70%或更多的总回收率。
此外,RO部分43截留物流的浓缩可通过热方法或其它蒸发器部分44。蒸发器部分44也可包括浓缩器,例如蒸发盐水浓缩器,优选例如降膜蒸发器的单元,并且可使用蒸气再压缩机单元操作,用于增强的能量效率和增大的水回收率。机械蒸气压缩单元可用于增强蒸发效率,同时在该部分中回收另外的水。在一个实施方案中,蒸发器部分44为产生另外的纯水或蒸馏物A2同时进一步浓缩进料41的机械蒸气压缩机。通过举例说明,存在于通向浓缩/盐生产阶段的RO部分截留物流B1中的约70%至约90%或更多的水可回收作为另外的水。
在结晶器部分48中,高纯度盐产品结晶,并且源于蒸馏物A4的另外的纯水产生。高纯度盐可作为潮湿的盐或作为盐浆料从蒸发器/离心机回路提取,其中流温度可容易地使用例如机械蒸气再压缩控制,以提供过饱和盐溶液和优化氯化钠结晶。结晶器部分48可通过引晶驱动,使得产出盐从沉淀和离心回路有效和连续地取出,并且,通过允许从回路小的周期性泄料(blowdown)以保持剩余的不想要的物类(例如钾)在结晶器部分48中低于饱和和低于可能损害结晶或产品品质的水平,可增强结晶和产品的纯度二者。对此,低于约1%的初始盐水进料体积或3%的结晶器体积的清洗(purge)就足够,导致从生产高度纯化的NaCl产品中几乎零-液体排放(ZLD)的过程。
替代地说明,在脱盐设备20中,进料22向下游通到预处理部分24,其从进料22除去悬浮的固体和实质部分的有机物质。进料22随后向下游行进至任选的NF部分26中。进料22作为渗透物离开NF部分26,并且浓缩物作为废物流C1离开NF部分26。RO部分28位于NF部分26的下游,并且从位于上游的NF部分26接收进料22。渗透物作为渗透物流A1离开RO部分28,并且浓缩物作为截留物流B1离开RO部分28。在下游,截留物流B1离开脱盐设备20,变为盐设备进料41,并进入盐设备40。
在进入盐设备40后,进料41向下游行进至NF部分42中。进料41作为渗透物离开NF部分42,并且浓缩物作为截留物流C2离开NF部分42。任选的浓缩器部分43位于NF部分42的下游,并且从NF部分42接收进料41。渗透物作为渗透物流A3离开浓缩器部分43,并且浓缩物作为进料41离开,并且向下游行进至蒸发器部分44。蒸发器部分44从位于上游的浓缩器部分43接收进料41。蒸发器部分44从进料41除去水,并将进料41向下游送至结晶器部分48。通过蒸发器部分44从进料41除去的水形成蒸馏物流A2。结晶器部分48从位于上游的蒸发器部分44接收进料41。结晶器部分48从进料41除去水并且向下游输出潮湿的盐或浆料S。通过结晶器部分48从进料41除去的水形成蒸馏物流A4。预期一些实施方案可包括位于结晶器部分48下游的干燥器,以接收潮湿的盐或浆料S和生产干燥的盐。
转向图2,其显示图1的盐设备40的一些代表性操作条件,NF部分42有效除去硫酸根,并且可大大降低进料41的钙、镁、碳酸氢根或其它成分的水平。图2显示在进料41和NF部分42渗透物流中主要的溶解物类的浓度。通过NF部分42从进料41除去至少约99%的硫酸根、约90%的钙和约95%的镁。优选地,NF部分42除去至少约99.9%的硫酸根、约95%的钙和约98%的镁。此外,NF部分42通过进料41中的至少约50%的氯根。优选地,NF部分42通过进料41中的至少约70%的氯根。NF膜可为这样的膜,例如,但不限于,由The Dow Chemical Company (Midland,Michigan)和GE Osmonics (Minnetonka,Minnesota)通常销售的用于硫酸根去除的膜;得自the Dow Chemical Company (Midland,Michigan) Filmtec line的SWNF膜;得自GE Osmonics (Minnetonka,Minnesota)的DK系列或SeaSoft膜;和得自Toray (Poway,California)的海水NF膜。GE Osmonics膜可具有特别高的硫酸根截留率,该截留率相对独立于进料浓度。这使得能使用两个或多个阶段的NF以实现高回收率。
有利地,在NF部分42中去除实质部分的钙和镁大大降低在盐设备的常规纯化阶段中所需的化学品的数量。计算显示,对于生产106,000 m3的纯水/天或854,000吨盐/年的脱盐设备,化学品节省是显著的。不使用NF部分42,除去二价离子以(a) 避免在结晶器中结垢和(b) 保持自结晶器的清洗(以下进一步讨论)的NaOH和Na2CO3的量最小限度为329,411吨NaOH/年消耗量和92,927吨Na2CO3/年消耗量。如本文描述的使用NF部分42处理的流计算的相应的数字为0吨NaOH/年消耗量和0吨Na2CO3/年消耗量,因此增加的化学品节省为329,411吨NaOH/年和92,927吨Na2CO3/年。在NaOH的价格为$0.10/kg 和Na2CO3的价格为$0.25/kg时,这转化为每年对NaOH节省$32,940,000和对Na2CO3节省$23,230,000。除了直接的化学品节省以外,通过使纯化步骤处理通常较低水平的二价杂质安排,通到结晶器的流得到可靠处理,大大降低结垢倾向,并且使用较小的体积、不太频繁的清洗操作,同时确保剩余的杂质不会达到影响结晶或损害盐产品纯度的浓度。
虽然已结合以上描述的具体实施方案描述了本发明,但是显然许多改变、组合、修改和变体对于本领域技术人员来说是显而易见的。因此,以上描述的本发明的优选的实施方案仅旨在为说明性,而不是限制性含义。在不偏离本发明的精神和范围的情况下,可以作出各种改变。因此,本发明的技术范围不仅包括以上描述的那些实施方案,而且包括落入所附权利要求的范围内的所有实施方案。
本书面描述使用实施例来公开本发明,包括最佳方式,并且使本领域技术人员能够实践本发明,包括制备和使用任何装置或系统和进行任何结合的方法。本发明可取得专利的范围由权利要求限定,并且可包括本领域技术人员想到的其它实例。这些其它实例如果具有与权利要求的字面语言没有不同的结构要素,或者如果包括与权利要求的字面语言具有非实质差异的等同结构要素,则旨在处于权利要求的范围内。
Claims (20)
1. 一种盐水脱盐和盐设备,所述设备包含:
脱盐设备,所述脱盐设备具有进料流和截留物流;
盐设备,所述盐设备包含:
进料流,所述脱盐设备截留物流形成所述盐设备进料流的至少一部分;
过滤器,以从所述盐设备进料流选择性除去结垢物类,以产生经过滤的盐设备进料流;和
用于将所述经过滤的盐设备进料流加工成为高纯度的潮湿的盐或浆料的装置。
2. 权利要求1的盐水脱盐和盐设备,其中所述过滤器从所述盐设备进料流除去至少约99%的硫酸根,并且通过所述盐设备进料流中至少约50%的氯根。
3. 权利要求2的盐水脱盐和盐设备,其中所述过滤器从所述盐设备进料流除去至少约99.9%的硫酸根。
4. 权利要求3的盐水脱盐和盐设备,其中所述过滤器从所述盐设备进料流除去至少约90%的钙和至少约95%的镁。
5. 权利要求4的盐水脱盐和盐设备,其中所述过滤器从所述盐设备进料流除去至少约95%的钙和至少约98%的镁。
6. 权利要求5的盐水脱盐和盐设备,其中所述过滤器为纳米过滤部分。
7. 权利要求6的盐水脱盐和盐设备,其中所述纳米过滤部分为双极纳米过滤系统;其中所述纳米过滤部分平均每级截留小于约30%的氯根、大于约90%的硫酸根、大于约68%的钙和大于约77%的镁。
8. 权利要求7的盐水脱盐和盐设备,其中所述用于将所述经过滤的进料流加工成为潮湿的盐或浆料的装置包含:
蒸发器部分和结晶器部分;
所述蒸发器部分适于从所述纳米过滤部分接收渗透物;
所述结晶器部分适于从所述蒸发器部分接收浓缩物。
9. 权利要求8的盐水脱盐和盐设备,其中所述盐设备可包括位于所述纳米过滤部分和所述蒸发器部分之间的任选的浓缩器部分。
10. 权利要求9的盐水脱盐和盐设备,其中所述浓缩器部分为反渗透部分。
11. 权利要求8的盐水脱盐和盐设备,其中所述脱盐设备还包含:
预处理部分,和反渗透部分;
所述脱盐设备进料流适于通过所述预处理部分并进入所述反渗透部分;
所述反渗透部分接收所述脱盐设备进料流并产生渗透物流和截留物流,所述截留物流适于进料至所述脱盐设备截留物流。
12. 权利要求8的盐水脱盐和盐设备,其中所述脱盐设备还包含:
预处理部分、纳米过滤部分和反渗透部分;
所述脱盐设备进料流适于通过所述预处理部分并引到所述纳米过滤部分中;
所述纳米过滤部分产生渗透物流和截留物流,所述纳米过滤部分渗透物流被引到所述反渗透部分中;
所述反渗透部分产生渗透物流和截留物流,所述反渗透截留物流限定所述脱盐设备截留物流。
13. 一种生产盐的方法,所述方法包括:
将盐水脱盐设备截留物流引到盐设备进料流中;
选择性过滤所述盐设备进料流以除去结垢物类;和
将所述经过滤的进料流加工成为高纯度的潮湿的盐或浆料。
14. 权利要求13的方法,其中所述选择性过滤从所述盐设备进料流除去至少约99%的硫酸根。
15. 权利要求14的方法,其中所述选择性过滤从所述盐设备进料流除去至少约99.9%的硫酸根。
16. 权利要求15的方法,其中所述选择性过滤从所述盐设备进料流除去至少约90%的钙和至少约95%的镁。
17. 权利要求16的方法,其中所述选择性过滤从所述盐设备进料流除去至少约95%的钙和至少约98%的镁。
18. 权利要求17的方法,其中使用纳米过滤部分来选择性过滤所述设备进料流,所述纳米过滤部分可在降低的pH下操作,以增强钙和镁去除。
19. 权利要求18的方法,其中所述纳米过滤部分为双极纳米过滤系统。
20. 权利要求19的方法,其中通过以下将所述经过滤的进料流加工成为潮湿的盐或浆料:
蒸发器部分和结晶器部分;
所述蒸发器部分从所述过滤器接收所述经过滤的进料流;和
所述结晶器部分从所述蒸发器部分接收所述经过滤的进料流。
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Also Published As
Publication number | Publication date |
---|---|
ZA201300034B (en) | 2014-06-25 |
AU2011268443B2 (en) | 2016-09-08 |
EP2582636A1 (en) | 2013-04-24 |
PE20130915A1 (es) | 2013-08-26 |
CL2012003478A1 (es) | 2013-10-18 |
CA2801926C (en) | 2018-06-26 |
AU2011268443A1 (en) | 2013-01-10 |
US20110303607A1 (en) | 2011-12-15 |
MX2012014841A (es) | 2013-02-07 |
WO2011159743A1 (en) | 2011-12-22 |
BR112012031131A2 (pt) | 2016-11-01 |
US8647509B2 (en) | 2014-02-11 |
CA2801926A1 (en) | 2011-12-22 |
SG186287A1 (en) | 2013-01-30 |
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