CN106795010A - 过饱和热水的脱盐方法 - Google Patents
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Abstract
本发明涉及温度为40℃‑80℃的过饱和热水的脱盐方法,包括使所述热水与耐受40℃‑80℃的温度的反渗透膜接触,而无预先的冷却步骤。
Description
技术领域
本发明的目的在于利用反渗透的过饱和热水的脱盐方法。
背景技术
反渗透是从地表水或地下水、尤其是从含盐海水制备饮用水的最常用方法中的一种。
因此存在多种设备用于利用反渗透处理这些过饱和热水,尤其是在沙特阿拉伯。这些设备迄今均根据以下的一系列步骤来设计:
1、在潜水层中泵唧,
2、通过通风冷却装置进行冷却以将水温降低到反渗透膜可接受的水平,
3、任选地,结合了去碳酸化和/或软化和/或脱硅和/或除铁的补充步骤,以提高反渗透效率,
4、然后,在一个或两个阶段中的过滤步骤,以拦住会带来反渗透膜堵塞风险的较细颗粒,
5、注入所谓“螯合剂”的化学试剂,以提高反渗透效率,
6、具有通常为5-10微米的标称截止阀值(但根据设计选择可以在这个范围之上或者之下)的筒式过滤器的步骤,这个步骤的作用在于进行保护以免于偶然到达的悬浮物质,
7、最后,反渗透步骤,其使得能够将水脱盐至其目标用途所需的水平。
当然可以考虑使用没有CO2损失的热交换器,但这类装置远贵于开放通风冷却装置(其提取一部分的待处理水以获得所希望的冷却)并且因此一旦处理流量大于几个m3/h就变得经济上不可行。
为了限制或者避免碳酸盐沉淀,有时进行的操作是在冷却塔的上游注入酸和/或螯合剂,并且这些同样的酸和螯合剂有时作为补充物也在过滤的上游注入。在这两种情况下,这类试剂添加的目的在于降低在冷却塔和过滤器中经过时的沉淀潜力,并且因而保护这些装置免于物质的有害累积。
但这些解决方案具有与在这些热水中存在的某些离子的沉淀相关的重大缺陷。
这是因为,这些水是地下来源的,尤其来源于地下储水层(réservoirs aquifères)中所包括的含水层(nappes)。这些天然水是含盐的并且可包含大量的悬浮物质。
而且,到达冷却塔的这些热水(>40-45℃)来自于深潜水层并且相比于地表天然水因而通常具有低pH(通常低于7.5)并且因而具有可变但高的CO2含量。这些水还包含可变但显著量的钙离子(Ca2+)和碳酸氢根离子(HCO3 -)。它们因而象所有天然水一样符合所谓钙-碳(calco-carbonique)的平衡,所述平衡按照已知的平衡定律决定离子Ca2+、HCO3 -、CO3 2-、H+、OH-以及物质CO2和CaCO3之间的平衡,每种由常数控制并且可由以下的简化方程式表示:
[1]CO2+OH-<=>HCO3 -
[2]HCO3 -<=>H++CO3 2-
[3]Ca2++CO3 2-<=>CaCO3
因此,当在通风冷却装置中经过时,CO2的损失引起pH升高,这超出了平衡pH。为了在这些新条件下恢复平衡状况,水将倾向于根据[2]由碳酸氢根离子HCO3 -产生碳酸根离子CO3 2-。但这种额外的碳酸根则可导致平衡[3]向着出现碳酸钙CaCO3的方向移动,而碳酸钙是不可溶的并且因而会发生沉淀。
而且,向缺乏氧的这种水中供应氧会导致铁的氧化和快速沉淀,所述铁通常以可变量存在,可一直到几个mg/l。如果仅铁沉淀,那么其很大部分会被塔中的水冲洗,但当碳酸钙沉淀时,铁沉淀物往往会加入其中,由此进一步提高了冷却塔中的堵塞负荷。
在冷却塔的交换结构中沉淀物的沉淀和累积具有两个主要缺陷:
1、该结构的重量增加,这是最严重的后果;该结构如果不及时清洁的话甚至会破裂。这种周期性的清洁降低了系统的可利用性。
2、冷却效率的损失,这可能必须要降低设备的流量。
在过滤器中的沉淀物的沉淀和累积导致:
1、可移动装置(如阀、泵)的阻塞,
2、过滤材料的结块,这损害了其过滤能力及其每日的自动清洗,以及
3、堵塞物质的累积,这降低了循环持续时间并且使引向反渗透单元的水的水质劣化。
塔上游的酸化有时被用于减少初始存在的碳酸氢根并且因而降低形成碳酸根的潜力。但是,当使用典型地包含3毫当量碳酸氢根的水时,这将代表可达110mg/l的HCl或者接近300mg/l的38%商业酸的盐酸消耗,这代表了显著的运行成本以及存储困难。而且,下游反渗透系统的转化(回收)非常少从这种去除操作获益,因为钙的含量并没有降低并且由硫酸钙导致的沉淀风险则对于反渗透回收来说仍是限制性因素。
有时还使用螯合剂产品,其将限制或者延迟冷却塔中的沉淀。但这种产品相当昂贵,其在此场所的应用仍然是凭经验的,并且其可由于劣化从过滤器中移除悬浮物质的效率而在过滤方面具有有害的副作用。对于该螯合剂产品来说还可能在与冷却塔中的交换物质或者与过滤器中的过滤物质接触时丧失其效力,这造成了对这些系统有害的后沉淀。
因此,迄今所采用的方法的主要缺陷因而是:
1、冷却塔中以及随后的过滤步骤中的铁和碳酸钙的大沉淀风险,
2、由于累积的沉淀物所导致的塔的冷却效率的损失,
3、冷却塔的维护频率大增,这导致其加速磨损和可利用性的损失,
4、如果不及时进行维护的话则存在冷却塔机械损害的风险,
5、由于在环循过程中累积的沉淀物所导致的过滤步骤的性能损失,
6、过滤介质结块、过滤器的阀阻塞以及过滤器传感器的堵塞和失活的风险,
7、反渗透膜的提高的污泥风险,以及
8、用来限制或消除沉淀的试剂的高成本。
因而需要提供下述这样的方法,该方法使得能够减少甚至避免在冷却塔的交换结构中以及在过滤器中的沉淀物的沉淀和累积。
发明内容
本发明人已经发现,通过取消反渗透之前的冷却步骤,沉淀风险被极大地降低,甚至被消除。
因此,本发明的目的在于温度为40℃-80℃、有利地为40-60℃的过饱和热水的脱盐方法,包括使所述热水与耐受40℃-80℃的温度的反渗透膜接触,而无预先的冷却步骤。
出于本发明的目的,“过饱和热水”被理解为是指地下来源的水,尤其来源于地下储水层中所包括的含水层,并且其主要特征为:
-大于35℃、优选40℃-80℃的温度,
-含盐性质,也即选自下列钙、镁、钠、钾、碳酸根、碳酸氢根、氯根、硫酸根或其混合物的离子的总和大于500mg/l,并且
-高CO2含量,赋予其小于7.5并且优选小于7的平衡pH。
任选地,这些水还包含选自下列的化合物:
-大于50μg/l的铁含量,
-大于25μg/l的锰含量,
-大于10mg/l的二氧化硅含量,
-含量大于10μg/l的胶体形式或者硫化氢形式的硫,
-一种或多种放射性核素,例如镭或铀,使得总α活性大于0.5Bq/l,
或者
-其混合物,
以高含量地。
举例来说,含盐性质的超饱和热水具有以下特性:
温度 | =60℃ |
钙 | =360mg/l |
CO2 | =60mg/l |
pH | =6.7 |
HCO3 | =190mg/l |
铁 | =3mg/l |
锰 | =200μg/l |
二氧化硅 | =15mg/l |
总α活性 | ≥0.5Bq/l |
该热水与反渗透膜的接触可通过本领域技术人员已知的任何技术进行。该水例如可被泵唧并且经由管道引至该膜。
根据本发明,在该方法中采用的反渗透膜可以是耐受40-80℃的温度的任意反渗透膜,尤其是基于聚酰胺和聚砜的膜。
在本发明的一种有利实施方案中,从井中抽取的原水被引至反渗透膜上,而没有压力损失,以避免CO2的损失。
在本发明的一种有利实施方案中,该方法包括来自该反渗透的经脱盐渗透物的冷却步骤。由此则没有任何沉淀风险,而与冷却技术无关。
在本发明的一种有利实施方案中,该方法可包括在该热水与反渗透膜的接触之前的去除悬浮物质的步骤或者添加螯合剂的步骤,或者二者。在原水包含由钻井获得的悬浮物质或者存在包含由钻井获得的悬浮物质的风险的情况下将需要去除悬浮物质的步骤,而螯合剂的添加可以提高通过反渗透的过滤步骤的效率。本领域技术人员知晓根据其常识并且根据待处理水的类型来选择所需的额外步骤。
在本发明的另一有利实施方案中,如果原水的压力不足以确保膜所需的性能,则该热水可在与反渗透膜接触之前通过本领域技术人员已知的任何措施(例如通过使用泵)进行加压。
在另一实施方案中,冷却塔位于反渗透膜的下游,从而降低了与冷却塔的结垢有关的运行成本,而且另外由于所述塔在其流量小于供料流量的渗透物的线路上的定位而降低了投资成本。
有利地,在热水包含镭的情况下,此实施方案允许在反渗透膜上保留放射性核素,尤其是镭或铀。
该渗透的渗透物的这种冷却可避免氡污染环境空气,而氡是一种由镭226的裂变获得的高度不稳定的元素。
除了这些经济优势之外,这种布置还具有消除氡污染大气的风险,因为元素镭和氡在渗透物经过冷却塔之前将会被反渗透膜留住。
通过使用本发明的方法,对于具有以下特性的钻井水来说:
·pH 6.7
·碳酸氢根190mg/l HCO3 -
·钙130mg/l Ca2+
·CO2 60mg/l
·温度50℃,
该反渗透将能够以75%的转化率工作,这与利用如上所述的目前的方法所获得的转化率相同,但对于在站出口处的相同产品水流量来说,冷却塔将仅具有在针对相同恢复温度的目前方法中的塔尺寸的75%。
附图说明
为了进一步说明本发明的方法,下面将描述一种实施模式。当然要指出的是,这仅是一个实施例,完全没有任何限制性含义。在此描述的过程中,将参考附图1,附图1是表示根据本发明的方法的各步骤的图。
具体实施方式
从井(1)抽取的原水通过泵(图中未示出)被立即引向反渗透系统(2),而没有压力破坏,以便避免损失CO2。后者几乎完全穿过该膜到渗透物(产品水侧)。在反渗透系统的上游,压力计(M)测量离开井的原水的出口压力。渗透物然后被冷却到希望的温度并且被引向存储槽(3),然后被运送到使用地点。
根据本发明的方法的主要应用在于处理具有碳酸钙过饱和潜力的热的深层天然水。
不过,这种方法也可应用于生产:
·用于人类消费的水,
·用于供应工业方法的水,例如洗涤水,在生产制造品时所涉及的水,用于供应锅炉的水等,以及,
·用于灌溉的水。
最后,这种方法还可应用于处理来自于工业生产方法(该工业生产方法为大于40-45℃的水带来碳酸钙过饱和潜力)的水,如果希望再循环该水、从其回收成分或者在排放之前对其进行处理的话。
相比于如上所述的迄今使用的方法,根据本发明的方法兼具多种优点:
·消除在所有步骤中的沉淀风险,
·对于相同生产率来说更小尺寸的冷却塔,因为只处理生产的渗透物(盐水排放物当然可被热排放),
·更小尺寸的冷却塔,因为仅与工厂出口处所要求的温度相关联的所需冷却得以减少,
·没有冷却塔堵塞的风险,并且因而具有最大的可利用性和有限的维护成本,
·反渗透上游的过滤步骤是无意义的,因为不再有悬浮物质要被去除,因而使得投资和运行成本显著降低。该步骤仅可在直接从钻井获得的原水中怀疑有悬浮物质时才保留,
·无化学去除碳酸氢根(通过计量加入酸)并且不需要降低冷却塔中和过滤步骤过程中的沉淀风险(通过应用螯合剂),因而使得显著节约运行成本。
Claims (10)
1.温度为40℃-80℃的过饱和热水的脱盐方法,包括使所述热水与耐受40℃-80℃的温度的反渗透膜接触,而无预先的冷却步骤。
2.根据权利要求1的方法,其特征在于,该方法还包括来自该反渗透的经脱盐渗透物的冷却步骤。
3.根据前述权利要求任一项的方法,其特征在于,该方法包括在该热水与反渗透膜的接触之前的去除悬浮物质的步骤或者添加螯合剂的步骤,或者二者。
4.根据前述权利要求任一项的方法,其特征在于,该热水在与反渗透膜接触之前进行加压。
5.根据前述权利要求任一项的方法,其特征在于,该过饱和热水包含选自以下的化合物:钙、镁、钠、钾、碳酸根、碳酸氢根、氯根、硫酸根或其混合物。
6.根据权利要求5的方法,其特征在于,该过饱和热水包含选自以下的化合物:钙、镁、钠、钾、碳酸根、碳酸氢根、氯根、硫酸根或其混合物,其总量为至少等于500mg/l。
7.根据前述权利要求任一项的方法,其特征在于,该过饱和热水还包含选自以下的化合物:铁、锰、二氧化硅、硫或其混合物。
8.根据权利要求2-7任一项的方法,其特征在于,该渗透物被冷却到至少小于45℃并且优选小于40℃的温度。
9.根据前述权利要求任一项的方法,其特征在于,该过饱和热水包含放射性核素。
10.根据前述权利要求任一项的方法,其特征在于,所述热水的渗透物在其经过渗透膜之后被冷却。
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US20090081105A1 (en) * | 2007-09-25 | 2009-03-26 | Bourcier William L | Silica Extraction From Geothermal Water |
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