CN1257006C - 改进的膜式过滤 - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D65/08—Prevention of membrane fouling or of concentration polarisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
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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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
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Abstract
本发明涉及对含有悬浮物质的流出液尤其是水的膜式过滤、特别是微量过滤、超过滤、毫微过滤或反渗透的改进。所述的改进的目的是减少膜的污垢并增强过滤能力。改进的特征在于其中在流出液通过所述的膜之前,向其中加入一定剂量的聚沉试剂,这种试剂破坏悬浮的胶体物质的稳定。剂量比抵偿ζ电势所需剂量少约30至80倍。
Description
本发明涉及对含有悬浮物质的流出液、特别是水的膜式过滤的改进以减少或阻止膜的堵塞并增强后者的过滤能力。
已知过滤(微量过滤、超过滤、毫微(nano-)过滤或反渗透(hyperfiltration))膜对各种类型的物质引起的堵塞是敏感的如:溶解物如有机物质,胶体状态的物质如金属氢氧化物,或一般为悬浮态的物质(悬浮物质或SM)。堵塞使膜的过滤能力大大减弱,能力的减弱不总是可逆的,膜的清洁效力很大程度上依赖于各种因素,如膜上污垢物的有效停留时间、在清洁产物过程中它的相对溶解度以及所述的污垢物与膜的表面之间的化学的或物理-化学相互作用,后者根据构成膜的聚合物的化学组成的变化是非常显注的。
也知道(特别参看“Mémento Teehnique de 1’Eau[WaterTechnical Memorandum]”,卷1,3.1章和4.1章,DEGRMONT出版,1989)聚沉更易于除去悬浮和胶体物质。特别地,本领域普通技术人员知道吸附到如金属氢氧化物上后,通过金属盐的聚沉使得破坏胶体的稳定并沉淀出的某些有机物质成为可能。表征这种现象有几种方法:
·用在实验烧杯中用各种剂量的金属盐的聚沉-絮凝试验并评估,如沉降速度;
·通过测定ζ电势(ZP),特别是作为加入的金属盐的剂量的函数的所述ZP的变化,测定直至使ZP为0时的剂量和由此与得到最佳的聚沉所需的处理水平对应的剂量。
这两种方法定义了称作“最佳聚沉剂量”的聚沉剂的剂量,由本领域普通技术人员得到的经验可知,它是使被处理的水得到最佳澄清处理的剂量和因此会确保膜的最优工作条件(即最少污垢的条件)的剂量。
涉及到这种最佳聚沉剂量的这一处理的缺点是这种剂量是相对较高的并对澄清处理的操作成本和投资相应的设备的成本都有影响。
而且,应该注意多数膜的供应商和毫微过滤(nanofiltration)和反渗透设备的供应商由于担心对膜的担保的丧失,坚持只用具有O或至少非常低含量的作为二价或三价离子的重金属、特别是如亚铁离子的水将料送入它们。
文献中有许多刊物提出了在膜处理的上游使用或注射一种或多种金属盐。应该强调这些刊物提到了接近于使ZP为0的剂量,或至少为接近使所述的ZP为0的所述的最佳剂量的30%或更多的高剂量。
本发明目的是提供一种可能使膜的堵塞最小化或至少减少膜的堵塞并增强它们的过滤能力的方法,同时使此方法更经济。为达到这个目的,需要解决的技术问题如下:
·怎样大大增加比生产通量(膜的l·h-1·m-2);
·怎样从澄清处理中得到最少量的淤浆(例如氢氧化物的),而且,首要地:
·为了处理相同体积的水,怎样减小所需安装的膜的面积。
本所有人以一种对本领域普通技术人员来说真正令人惊奇的方式已观察到,远远少于使被处理的水的ζ电势为0的剂量的聚沉反应物的剂量使得膜的过滤能力显著增强。
因此本发明的主题是对聚集了悬浮物质的流出液尤其是水的膜式过滤,特别是微量过滤、超过滤、毫微过滤或反渗透的改进,以减少膜的堵塞并增强它们的过滤能力,其中它们包括:在被过滤的流出液通过膜之前,向其中加入破坏悬浮态的胶体物质稳定的一定剂量的聚沉反应物,该剂量比使ζ电势为0的剂量少约30至80倍。
根据实施本发明的方法的一种有利的方法,聚沉反应物的所述剂量比使ξ电势为0的剂量少约40至60倍。
本发明的申请的领域是特别宽的。这是因为它特别适合于来自各种来源的水的膜处理,如:
-城市废水,在生物处理和分离后使得得到的SM少于20mg/l;
-不需要预先除去有机物质并且总的有机碳(TOC)含量少于2ml/g的水;和
-未经处理的地表水,具有低TOC,高的胶体浓度并含有少于200mg/l的SM。
当它用于具有内表层(skin)或外表层的不同形状的膜(毛细管状的、管状的、平面状的和螺旋状的膜),具有多种构型(在夹套(casing)中,没有夹套并浸入池(basin)中)时,根据本发明的方法给出了优异的结果。本发明也适用于涉及到娱乐区的喷淋,工厂中废水的回收利用,更一般地,反渗透脱盐工厂的上游预处理的应用中。
由下面给出的关于附图的说明和下面给出的说明性的实施例会明显看出本发明的进一步的特征和优点。图中:
-图1说明在夹套中的膜的上游将聚沉反应物,例如金属盐,特别是铁盐注射入物流的示意图;
-图2说明在没有夹套的浸入的膜的上游注射聚沉反应物的示意图。
两个图中,相同的编号表示相同的或类似的元件。
图1所示的实施方法中,在2处将聚沉反应物注射入被处理的水1中,通过在夹套4中的膜过滤被处理的水/聚沉反应物混合物。***包括再循环回路5。编号3表示经处理水的流出。
图2所示的实施例中,将聚沉反应物2注射入被处理的水1中,通过没有夹套的、浸入在含有被处理水的池中的膜过滤混合物。利用泵排出经处理的水3。
为了使本发明所提供的技术方面和优点清楚地表现出来,下面给出两个实施例。
实施例1:城市废水的处理
对源自如FR-A-2 775 911中所述的一种织物膜生物反应器的城市废水进行生物处理试验。
由反应器输出的水的质量如下:
总COD: 40mg/l
总BOD5: <10mg/l
SM: 5mg/l
TOC: 6mg/l
通过实验室试验发现使ζ电势(ZP)为0的剂量为140mg/l的FeCl3(由纯的FeCl3表示的)。由烧杯内絮凝测出的减少有机物质(在254nm测定UV吸收)的聚沉反应物的最佳剂量为110mg/l。
源自织物膜反应器的被处理水的输出是1m3/h。通过毛细管状超过滤膜的稳定的通量是32l·h-1·m-2。当使用少量的聚沉反应物时,通过管内注入3mg/l的FeCl3(由纯的FeCl3表示的),稳定的通量是100l·h-1·m-2。
每30分钟用5mg/l的氯回洗30秒,不时地,如一月一次,用含氨的柠檬酸回洗。使回洗的水回到织物-膜生物反应器的顶部。
这个实施例中,处理1m3/h没有聚沉反应物,得到35l·h-1·m-2,由此需要28.5m2的膜面积。相反,通过注入3mg/l的FeCl3,得到100l·h-1·m-2,由此需要的膜面积为10m2。这表明改进了285%的通量并节省了至少18.5m2即65%的膜。
加入3mg/l的FeCl3,淤浆产量为8mg/l,而不加聚沉反应物时淤浆产量为5mg/l;然而这仍远远少于用125mg/l的FeCl3会产生的量,即所形成的淤浆多于90mg/l。
很清楚以上报道的实验和它提供的结果与本领域技术人员的经验和现有技术的教导相反。这是因为:
-不完全的澄清(所用聚沉剂剂量明显少于最佳澄清剂量),和
-使用少量的,但仍然远远高于多数膜生产商和供应商禁止的正常含量的聚沉剂(特别是亚铁盐),
使通过膜的通量的增加,
与一般采用的膜的常规使用是完全矛盾的。
实施例2:未经处理的地表水的处理
对源自Seine的原水进行试验,其特征如下:
浊度:15NTU
有机物质 5mg/l O2(KMn04氧化性)
TOC 3mg/l
UV 8mg/l
实验室测试中,使ZP等于0的剂量是55mg/l的FeCl3。
被处理水的输出是150l/h。通过毛细管状超过滤膜的稳定的流量是80l·h-1·m-2。当使用少量的聚沉反应物时,通过管内注入2mg/l的FeCl3(由纯的FeCl3表示的),稳定的通量提高30%。
每30分钟用5mg/l的氯回洗30秒。
这个实施例中,以顺流(downstream)反渗透处理为目的,预处理未处理的地表水,也发现大大节省了膜面积。没有完全除去TOC,但通量提高了。
通过阅读以上描述,发现通过显著增强膜的过滤能力,本发明实际上确实限制了膜的堵塞。这导致了非常明显的经济优势,特别是减少了为处理相同体积的水所被配备的膜的面积。
当然不用说本发明不限于这里提到的和/或描述的实施和/或应用的例子,它包括所有的变化。
Claims (2)
1、用于含有悬浮物质的流出液尤其是水的膜式过滤、特别是微量过滤、超过滤、毫微过滤或反渗透的方法,以减少膜的堵塞并增强它们的过滤能力,其特征在于它包括:在流出液通过所述的膜之前,向其中加入破坏悬浮态的胶体物质稳定的一定剂量的聚沉反应物,其剂量比使ζ电势为O的剂量少约30至80倍。
2、一种方法,其特征在于所述的剂量比使ζ电势为0的剂量少约40至60倍。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR99/15551 | 1999-12-09 | ||
FR9915551A FR2802117B1 (fr) | 1999-12-09 | 1999-12-09 | Perfectionnements apportes a la filtration sur membranes |
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CN1407911A CN1407911A (zh) | 2003-04-02 |
CN1257006C true CN1257006C (zh) | 2006-05-24 |
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US (1) | US6974544B1 (zh) |
EP (1) | EP1239943B1 (zh) |
JP (1) | JP2003525727A (zh) |
KR (1) | KR100734764B1 (zh) |
CN (1) | CN1257006C (zh) |
AT (1) | ATE254951T1 (zh) |
AU (1) | AU768271B2 (zh) |
BR (1) | BR0016248B1 (zh) |
CA (1) | CA2393441C (zh) |
DE (2) | DE1239943T1 (zh) |
DK (1) | DK1239943T3 (zh) |
ES (1) | ES2180463T3 (zh) |
FR (1) | FR2802117B1 (zh) |
IL (1) | IL149668A0 (zh) |
MA (1) | MA25511A1 (zh) |
MX (1) | MXPA02005219A (zh) |
NZ (1) | NZ519287A (zh) |
PT (1) | PT1239943E (zh) |
RU (1) | RU2222371C1 (zh) |
TR (1) | TR200201493T2 (zh) |
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FR2860169B1 (fr) * | 2003-09-30 | 2006-02-03 | Degremont | Procede pour eviter le colmatage des membranes de filtration |
FR2864068B1 (fr) * | 2003-12-18 | 2006-03-03 | Degremont | Procede de traitement de fluides par coagulation sur membranes |
FR2909903B1 (fr) * | 2006-12-19 | 2009-02-27 | Degremont Sa | Procede de gestion optimisee d'une unite de filtration sur membrane,et installation pour sa mise en oeuvre. |
NL2000586C2 (nl) * | 2007-03-30 | 2008-10-02 | Norit Procestechnologie B V | Werkwijze voor het filtreren van een fluïdum. |
FR2922466B1 (fr) * | 2007-10-19 | 2010-06-25 | Degremont | Procede de gestion avancee d'une unite de filtration sur membrane, et installation pour la mise en oeuvre du procede |
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US8491788B2 (en) * | 2007-10-23 | 2013-07-23 | Siemens Industry, Inc. | Process for enhanced total organic carbon removal while maintaining optimum membrane filter performance |
US20090242484A1 (en) * | 2008-04-01 | 2009-10-01 | Ana-Mariana Urmenyi | Environmentally friendly hybrid microbiological control technologies for cooling towers |
DE102008037118B4 (de) * | 2008-08-08 | 2012-10-04 | Vws Deutschland Gmbh | Verfahren und Vorrichtung zur Aufbereitung von Wasser unter Verwendung von Nanofiltration |
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1999
- 1999-12-09 FR FR9915551A patent/FR2802117B1/fr not_active Expired - Fee Related
-
2000
- 2000-10-26 CA CA002393441A patent/CA2393441C/fr not_active Expired - Fee Related
- 2000-10-26 KR KR1020027007269A patent/KR100734764B1/ko not_active IP Right Cessation
- 2000-10-26 EP EP00974574A patent/EP1239943B1/fr not_active Expired - Lifetime
- 2000-10-26 US US10/148,070 patent/US6974544B1/en not_active Expired - Lifetime
- 2000-10-26 MX MXPA02005219A patent/MXPA02005219A/es active IP Right Grant
- 2000-10-26 ES ES00974574T patent/ES2180463T3/es not_active Expired - Lifetime
- 2000-10-26 TR TR2002/01493T patent/TR200201493T2/xx unknown
- 2000-10-26 CN CNB008168288A patent/CN1257006C/zh not_active Expired - Fee Related
- 2000-10-26 NZ NZ519287A patent/NZ519287A/en not_active IP Right Cessation
- 2000-10-26 AT AT00974574T patent/ATE254951T1/de active
- 2000-10-26 JP JP2001543244A patent/JP2003525727A/ja active Pending
- 2000-10-26 RU RU2002118212/12A patent/RU2222371C1/ru not_active IP Right Cessation
- 2000-10-26 PT PT00974574T patent/PT1239943E/pt unknown
- 2000-10-26 AU AU12825/01A patent/AU768271B2/en not_active Ceased
- 2000-10-26 WO PCT/FR2000/002991 patent/WO2001041906A1/fr active IP Right Grant
- 2000-10-26 DE DE1239943T patent/DE1239943T1/de active Pending
- 2000-10-26 DK DK00974574T patent/DK1239943T3/da active
- 2000-10-26 DE DE60006858T patent/DE60006858T2/de not_active Expired - Lifetime
- 2000-10-26 IL IL14966800A patent/IL149668A0/xx not_active IP Right Cessation
- 2000-10-26 BR BRPI0016248-5A patent/BR0016248B1/pt not_active IP Right Cessation
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2002
- 2002-06-04 MA MA26669A patent/MA25511A1/fr unknown
Also Published As
Publication number | Publication date |
---|---|
KR100734764B1 (ko) | 2007-07-06 |
CA2393441A1 (fr) | 2001-06-14 |
PT1239943E (pt) | 2004-04-30 |
DE60006858D1 (de) | 2004-01-08 |
FR2802117B1 (fr) | 2002-02-22 |
DE1239943T1 (de) | 2003-03-20 |
TR200201493T2 (tr) | 2002-10-21 |
DE60006858T2 (de) | 2004-08-26 |
JP2003525727A (ja) | 2003-09-02 |
EP1239943A1 (fr) | 2002-09-18 |
NZ519287A (en) | 2006-11-30 |
BR0016248B1 (pt) | 2009-08-11 |
RU2002118212A (ru) | 2004-02-27 |
AU768271B2 (en) | 2003-12-04 |
CA2393441C (fr) | 2007-07-31 |
ES2180463T3 (es) | 2004-06-16 |
US6974544B1 (en) | 2005-12-13 |
AU1282501A (en) | 2001-06-18 |
BR0016248A (pt) | 2002-08-27 |
MXPA02005219A (es) | 2004-08-23 |
ES2180463T1 (es) | 2003-02-16 |
WO2001041906A1 (fr) | 2001-06-14 |
MA25511A1 (fr) | 2002-07-01 |
KR20020062957A (ko) | 2002-07-31 |
DK1239943T3 (da) | 2004-02-23 |
ATE254951T1 (de) | 2003-12-15 |
RU2222371C1 (ru) | 2004-01-27 |
FR2802117A1 (fr) | 2001-06-15 |
IL149668A0 (en) | 2002-11-10 |
EP1239943B1 (fr) | 2003-11-26 |
CN1407911A (zh) | 2003-04-02 |
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