CN1307649A - 二氧化硅和硅酸盐结垢的抑制方法 - Google Patents
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Abstract
公开了一种控制含二氧化硅水垢的沉积和它们粘附到与水性体系相接触的表面的方法,其包括在水性体系中加入下列物质的协同组合物:(a)二亚乙基三胺五亚甲基膦酸和(b)一种选自于下列物质的材料:2膦酰基丁烷－1,2,4－三羧酸;高分子量的、比值为3∶1的、丙烯酸烯丙基羟基－丙基磺酸醚共聚物;环氧乙烷－环氧丙烷嵌段共聚物;聚环氧丁二酸及其盐。
Description
发明领域
本发明涉及控制二氧化硅在水性体系中结垢。更特别地，本发明涉及到在冷却和锅炉水系统中使用包括膦酸的协同组合物抑制二氧化硅/硅酸盐的结垢。
发明背景
许多年来，水垢形成的问题和它的伴随效应给供水系统带来了许多不便。例如水垢趋于积累在各种水系统(如锅炉和冷却水系统)的内壁上，从而降低传热性能并减少流体通过热交换器管的流动。
在某些系统中，一种特别类型的沉积物，二氧化硅，是特别令人讨厌的。其中用于冷却系统的水和制冷工业热交换器的水直接取自于湖，河、池塘或城市水资源，存在有各种含量的溶解和悬浮的固体，包括二氧化硅。在一些工艺例如冷却系统中，当浓缩水或使水循环时，问题就出现了。当水蒸发时，二氧化硅浓度增加，这既使沉积易发生，又加大了沉积的程度。二氧化硅浓度的增加也使单体二氧化硅聚合形成凝胶和/或胶体二氧化硅，胶体二氧化硅能形成粘滞的沉积物。
在冷却水系统中，二氧化硅和硅酸盐化合物在与流经整个系统的水相接触的内部金属表面上形成沉积物。这样，传热效率大大降低，这反过来对冷却水系统的整体操作效率也产生有害的影响。二氧化硅和硅酸盐的沉积既能在如阀、喷嘴和泵这些装置上引起问题，也能在其它导管和管道表面引起问题。
虽然当前的工业冷却系统在将水输入至水系统之前，对它进行了复杂的外部处理如絮凝、过滤、软化等，但是这些操作只是在一定程度上有效的。在所有情况下，外部处理本身并不提供足够的处理，因为泥浆、淤渣、粉沙和如硅酸盐之类的溶解固体能够逃脱这种处理，最终进入系统中。
在自然界中，二氧化硅以大量的结晶的和无定形的形式出现，在水中它们都是微溶的，这导致了不受欢迎的沉积物的形成。硅酸盐是由二氧化硅或硅酸衍生得到的盐，特别是原硅酸盐和偏硅酸盐，它们可化合形成聚硅酸盐。除了碱金属类硅酸盐，所有的这些物质在水中都是微溶的。有可能形成许多不同形式的二氧化硅和硅酸盐沉积物，在其它因素中，沉积物的形成形式依靠温度和水的PH值。
为了解决淤渣、粉沙及包括二氧化硅的沉积问题，已使用了各种方法。USP 5,378,638公开了使用聚醚聚氨基亚甲基膦酸酯控制工业水系统中的二氧化硅/硅酸盐沉积。可单独使用聚醚聚氨基亚甲基膦酸酯，也可与聚合物添加剂组合使用。
USP 5,078,879公开了单独使用2膦酰基丁烷-1,2,4-三羧酸盐或优选地与如羧基/磺基聚合物之类的阴离子聚合物组合使用，以控制水性体系中二氧化硅/硅酸盐沉积物的形成。
USP 4,933,090公开了使用选择性的膦酸酯和任选地使用羧基/磺基/聚环氧烷聚合物，以控制二氧化硅/硅酸盐的沉积。
USP 4,874,527公开了使用亚胺聚合物、膦酸酯和任选的含钼酸盐或硼酸盐离子的物质，以控制水性体系中二氧化硅/硅酸盐的沉积。
USP 5,158,685公开了使用羟基膦酰基乙酸和丙烯酸/烯丙基羟丙基磺酸醚聚合物的组合物控制冷却水系统中二氧化硅/硅酸盐的沉积。
USP 5,300,231公开了聚醚聚氨基亚甲基磷酸酯与羟基膦酰基乙酸或氨基三亚甲基膦酸酯的组合使用，以控制各种工业水系统中的二氧化硅/硅酸盐沉积。
USP 4,405,461公开了包含使用连接至少一对端基的胺或它们的氢卤化物的处理方法，以控制含二氧化硅的水垢的沉积，其中所述端基选自于糠基和由一个或多个羟基和羰基取代的饱和或不饱和烃基。
本发明的详细描述
根据本发明，已发现对减少水性体系中二氧化硅/硅酸盐的沉积来说，包括膦酸的协同组合物是有效的处理剂。本发明的方法包括向被处理的水性体系中加入有效量的包括膦酸的协同组合物。
本发明的对水性体系的处理剂是下列物质的协同组合物：膦酸(a)二亚乙基三胺五(亚甲基膦酸)与(b)2膦酰基丁烷-1,2,4-三羧酸；高分子量的、3∶1的、丙烯酸/烯丙基羟丙基磺酸醚；环氧乙烷-环氧丙烷嵌段共聚物；聚环氧丁二酸及其盐。
二亚乙基三胺五(亚甲基膦酸)是从Solutia购得的，商品名为Dequest2060。2膦酰基丁烷-1,2,4-三羧酸是从Bayer购得的，商品名为BayhibitAM。环氧乙烷-环氧丙烷嵌段共聚物是从BASF购得的，商品名为Pluronic L63和Pluronic L44。聚环氧丁二酸是从贝茨迪尔博恩公司购得的，商品名为Coag 129。
可将有效量的协同组合物加入被处理的水性体系中。这里所用的术语有效量是为控制被处理系统中二氧化硅/硅酸盐的沉积所必要的数量。一般来说，实际基于被处理的水性体系的总重量，有效量在大约1至100ppm的范围内。
这里所用的术语控制二氧化硅/硅酸盐的沉积包括抑制二氧化硅聚合，二氧化硅、硅酸盐、硅酸钙、硅酸镁和硅离子的阈值沉淀抑制，稳定，分散，增溶和/或粒度减小。本发明的处理剂是阈值硅酸盐沉淀抑制剂，它也稳定、分散、增溶二氧化硅和硅酸盐，并且通常减少任何沉淀物质的粒度。
这里所用的水性体系意味着包括含有水的任何类型的系统，包括但并不限于，冷却水系统、锅炉水系统、脱盐系统、气体洗涤器水系统、蒸发器系统、造纸系统、采矿系统和类似的系统。
本发明的协同组合物的组分是熟悉水处理技术的人所熟知的，可从市场上购得。可以任何方便的方式将本发明的处理物质加入水性体系中。将本发明的处理物质可同时分为一批或两批处理或连续地加入水性体系中以在现场形成协同组合物。优选的加入方法是补充水流。另外，其它传统的水处理剂如缓蚀剂可与本发明的处理剂组合使用。
下面参照许多具体的实施例，进一步描述了本发明，实施例是阐述性的，并不限制本发明的范围。
实施例
本发明的协同组合物在水性体系中对二氧化硅/硅酸盐沉积的抑制效率是在搅拌的间歇式逆向渗透装置中测定的。这个装置是受压的水过滤器，其中过滤介质是逆向渗透膜，压力是由压缩氮气提供的。架空的搅拌片安装在膜滤器表面的附近以提供湍流，从而最小化浓度的影响。
将含有100ppm二氧化硅的合成的输入水加入有和无处理剂的装置中。在30-40分钟内，将输入水浓缩近似10倍，从而使实验结束时，水中含有大约1000ppm的二氧化硅。在试验结束时，移去逆向渗透膜，并分析二氧化硅以确定沉积在膜上的二氧化硅。将有化学处理的试验与对照试验(无化学处理)比较，计算二氧化硅抑制百分比。表1总结了所得结论。下列说明标记了处理物质。
说明符号 物质A 亚乙基三胺五(亚甲基膦酸)B 2膦酰基丁烷-1,2,4-三羧酸C 高分子量，3∶1，丙烯酸/烯丙基羟丙基磺酸醚D 环氧乙烷-环氧丙烷嵌段共聚物，HLB=8-12E 环氧乙烷-环氧丙烷嵌段共聚物，HLB=1-7F 聚环氧丁二酸表1处理 输入速率(ppm活性) ％二氧化硅抑制A 10.0 53A/F 7.5/2.5 57A/F 5.0/5.0 46A/F 2.5/7.5 47F 10 49A/D 7.5/2.5 56A/D 5.0/5.0 50A/D 2.5/7.5 59D 10 45A/E 7.5/2.5 58A/E 5.0/5.0 40A/E 2.5/7.5 59E 10 37A/C 7.5/2.5 57A/C 5.0/5.0 54A/C 2.5/7.5 23C 10 23A/B 7.5/2.5 64A/B 5.0/5.0 62A/B 2.5/7.5 56B 10 27
表1中数据表明协同组合物对二氧化硅的控制作用远远大于其中每个组分对二氧化硅有望达到的控制。
虽然参照具体的实施方案描述本发明时，对本领域技术人员来说，本发明的许多其它形式和修改方案是很明显的。所附的权利要求书和本发明意欲包括在本发明精神实质和范围内的所有的明显形式和修改方案。
Claims (6)
1、一种抑制二氧化硅/硅酸盐化合物在与水性体系相接触的表面沉积的方法，其包括向水性体系中加入有效量的下列物质的协同组合物：
(a)二亚乙基三胺五亚甲基膦酸；和
(b)选自于2膦酰基丁烷-1,2,4-三羧酸；高分子量的、比值为3∶1的、丙烯酸/烯丙基羟丙基磺酸醚共聚物；环氧乙烷-环氧丙烷嵌段共聚物；和聚环氧丁二酸及其盐的材料。
2、如权利要求1所述的方法，其中以大约1至100ppm的剂量加入所述的协同组合物。
3、一种在水性体系中增溶二氧化硅和硅酸盐的方法，其包括向水性体系中加入下列物质的协同组合物：
(a)二亚乙基三胺五亚甲基膦酸；和
(b)选自于2膦酰基丁烷-1,2,4-三羧酸；高分子量的、比值为3∶1的、丙烯酸/烯丙基羟丙基磺酸醚共聚物；环氧乙烷-环氧丙烷嵌段共聚物；和聚环氧丁二酸及其盐的材料。
4、如权利要求3所述的方法，其中以大约1ppm至100ppm的剂量加入所述的协同组合物。
5、一种在水性体系中分散二氧化硅和硅酸盐化合物的方法，其包括加入下列物质的协同组合物：
(a)二亚乙基三胺五亚甲基膦酸；和
(b)选自于2膦酰基丁烷-1,2,4-三羧酸；高分子量的、比值为3∶1的、丙烯酸/烯丙基羟丙基磺酸醚共聚物；环氧乙烷-环氧丙烷嵌段共聚物；和聚环氧丁二酸及其盐的材料。
6、如权利要求5所述的方法，其中以大约1ppm至100ppm的剂量加入所述的协同组合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/109,276 US6077440A (en) | 1998-06-30 | 1998-06-30 | Inhibition of silica and silicate deposition |
| US09/109,276 | 1998-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1307649A true CN1307649A (zh) | 2001-08-08 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99808074.8A Pending CN1307649A (zh) | 1998-06-30 | 1999-04-08 | 二氧化硅和硅酸盐结垢的抑制方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6077440A (zh) |
| EP (1) | EP1097258A4 (zh) |
| JP (1) | JP2002519512A (zh) |
| CN (1) | CN1307649A (zh) |
| BR (1) | BR9911762A (zh) |
| CA (1) | CA2336247A1 (zh) |
| WO (1) | WO2000000668A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102459095A (zh) * | 2009-05-22 | 2012-05-16 | 通用电气公司 | 抑制二氧化硅污垢的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6337047B1 (en) | 1998-10-30 | 2002-01-08 | Ashland Inc. | Process for dispersing iron oxide in steam generating boilers |
| US7316787B2 (en) * | 2004-09-17 | 2008-01-08 | General Electric Company | Methods for controlling silica scale in aqueous systems |
| DK1888816T3 (da) * | 2005-06-01 | 2012-07-09 | Ecolab Inc | Alkalisk rensemiddel til rensning af aluminiumsoverflader |
| US8361952B2 (en) | 2010-07-28 | 2013-01-29 | Ecolab Usa Inc. | Stability enhancement agent for solid detergent compositions |
| TWI634083B (zh) * | 2012-03-30 | 2018-09-01 | 羅門哈斯公司 | 矽石垢之協同性控制 |
| CN102976512B (zh) * | 2012-11-14 | 2013-09-04 | 新疆德安环保科技有限公司 | 一种煤化工回用循环冷却水的化学处理方法 |
| US10118848B2 (en) | 2014-06-19 | 2018-11-06 | Dow Global Technologies Llc | Inhibition of silica scale using amine-terminated polyoxyalkylene |
| CN104109861A (zh) * | 2014-08-06 | 2014-10-22 | 浙江省海洋水产研究所 | 新型无磷环保非预膜缓蚀剂 |
| US10081758B2 (en) | 2015-12-04 | 2018-09-25 | Ecolab Usa Inc. | Controlled release solid scale inhibitors |
| WO2017200864A1 (en) | 2016-05-16 | 2017-11-23 | Ecolab USA, Inc. | Slow-release scale inhibiting compositions |
| AR110540A1 (es) | 2016-12-23 | 2019-04-10 | Ecolab Usa Inc | Inhibidores de incrustaciones sólidas de liberación controlada |
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| US3674804A (en) * | 1968-10-17 | 1972-07-04 | Petrolite Corp | Imidazoline phosphonic acids |
| US3766053A (en) * | 1972-06-29 | 1973-10-16 | Nalco Chemical Co | Corrosion inhibitors for refining & petrochemical processing equipment |
| US4172032A (en) * | 1976-10-15 | 1979-10-23 | Nalco Chemical Company | Polyphosphate-based industrial cooling water treatment |
| US4405461A (en) * | 1982-03-26 | 1983-09-20 | Rogers Alfred N | Control of silica scaling in industrial processes |
| US4933090A (en) * | 1987-12-23 | 1990-06-12 | Calgon Corporation | Method for controlling silica/silicate deposition in aqueous systems using phosphonates and carboxylic/sulfonic polymers |
| US4874527A (en) * | 1988-04-28 | 1989-10-17 | Calgon Corporation | Method for controlling silica/silicate deposition in aqueous systems using imines |
| GB8822144D0 (en) * | 1988-09-21 | 1988-10-26 | Ciba Geigy Ag | Compounds |
| US4913823A (en) * | 1988-10-14 | 1990-04-03 | The Mogul Corporation | Process for dissolving and removing scale from aqueous systems |
| GB8829830D0 (en) * | 1988-12-21 | 1989-02-15 | Ciba Geigy Ag | Method for treating water |
| US4900451A (en) * | 1989-02-01 | 1990-02-13 | Betz Laboratories, Inc. | Method of controlling manganese deposition in open recirculating aqueous systems |
| US5078891A (en) * | 1990-03-08 | 1992-01-07 | Betz Laboratories, Inc. | Method of controlling silica deposition in aqueous systems |
| US5147555A (en) * | 1990-05-04 | 1992-09-15 | Betz Laboratories, Inc. | Methods of controlling scale formation in aqueous systems |
| US5078879A (en) * | 1990-07-02 | 1992-01-07 | Calgon Corporation | Method for controlling silica/silicate deposition in aqueous systems using 2-phosphonobutane tricarboxylic acid-1,2,4 and anionic polymers |
| US5158685A (en) * | 1991-07-12 | 1992-10-27 | Betz Laboratories, Inc. | Inhibition of silica and silicate deposition in cooling water systems |
| US5378368A (en) * | 1992-08-05 | 1995-01-03 | Calgon Corporation | Controlling silica/silicate deposition using polyether polyamino methylene phosphonates |
| US5300231A (en) * | 1992-08-05 | 1994-04-05 | Calgon Corporation | Controlling silica/silicate deposition using phosphonate combinations |
| US5616278A (en) * | 1993-08-13 | 1997-04-01 | Betzdearborn Inc. | Inhibition of scale and corrosion in aqueous systems |
-
1998
- 1998-06-30 US US09/109,276 patent/US6077440A/en not_active Expired - Fee Related
-
1999
- 1999-04-08 WO PCT/US1999/007777 patent/WO2000000668A1/en not_active Application Discontinuation
- 1999-04-08 EP EP99918477A patent/EP1097258A4/en not_active Withdrawn
- 1999-04-08 CN CN99808074.8A patent/CN1307649A/zh active Pending
- 1999-04-08 CA CA002336247A patent/CA2336247A1/en not_active Abandoned
- 1999-04-08 JP JP2000557015A patent/JP2002519512A/ja active Pending
- 1999-04-08 BR BR9911762-2A patent/BR9911762A/pt not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102459095A (zh) * | 2009-05-22 | 2012-05-16 | 通用电气公司 | 抑制二氧化硅污垢的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002519512A (ja) | 2002-07-02 |
| EP1097258A1 (en) | 2001-05-09 |
| EP1097258A4 (en) | 2003-06-25 |
| BR9911762A (pt) | 2001-04-03 |
| CA2336247A1 (en) | 2000-01-06 |
| US6077440A (en) | 2000-06-20 |
| WO2000000668A1 (en) | 2000-01-06 |
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