CN1069293A - 使受操作条件和助长腐蚀之媒剂影响的金属表面钝化的系统 - Google Patents
使受操作条件和助长腐蚀之媒剂影响的金属表面钝化的系统 Download PDFInfo
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Abstract
金属表面特别是不锈钢、钛等等表面钝化用的系
统，在化学反应设备中所形成的元素和化合物，特别
是在当其中的温度和压力比环境条件更为苛刻时有
腐蚀作用，在此系统中主要的钝化剂是至少与第二种
辅助剂结合的氧(空气)，而特征在于后者是臭氧
(O3)。
Description
本发明涉及到使受操作条件和助长腐蚀之媒剂影响的设备中金属表面钝化的系统，一般地说涉及到这样一类化工设备中表面的钝化，此类设备中存在和形成有腐蚀性化合物，特别是有关的环境的状态（温度和压力）还加剧上述腐蚀作用。
更具体地说本发明涉及一种用于化工设备中暴露于高腐蚀性化合物的强烈作用下，而且还处在温度和压力条件比环境条件更为苛刻情况下的金属装置的钝化系统。
在与大型工业有关的一个实施例中，本发明是指一种用于尿素合成及处理过程中金属设备的钝化系统。
不影响本发明的一般性，而仅仅是作为最有兴趣的和直接的一个参考例，在由反应物NH3和CO2的合成进行尿素工业生产的工厂中，再加上所形成的各种各样的化合物（尿素除外），它们都是高腐蚀性的，例如或多或少被浓缩的氨基甲酸铵、碳酸铵、尿素本身以及其他种类离子的水溶液。
与上述化合物接触的设备的各种各样零部件的金属表面受到化学侵蚀，影响到金属表面的完整性和效能。
众所周知，尿素的合成是在高温（平均180～215℃）和高压（平均130～400巴）下进行的。从尿素合成工段的下游来看，存在着尚没有转变为尿素的例如氨基甲酸铵之类尿素合成副产品的许多分解阶段，这种氨基甲酸铵经过加热被分解为NH3和CO2并从合成元素中分离出来，作为气态NH3和CO2，它们在相续的冷凝段上冷凝成氨基甲酸铵和/或碳酸铵的水溶液，这一水溶液在合成工段循环，同时尿素在连续冷凝段上浓缩，在减小压力下达到直到最终真空浓缩阶段，由此，获得实质上纯净的溶化的尿素，然后再送到使用各种技术来实施最终阶段处理。
对用于上面指出的这些个阶段的设备的钝化提出了各种系统，这种设备受到了在其中处理的腐蚀性化合物的侵蚀。例如比利时专利625.397号描述了在180℃和270kg/cm2下以氧作为钝化剂用于含19%cr和14%Ni的不锈钢尿素合成反应器表面;通常氧被其他的钝化剂所置换，例如由双氧水和碱金属过氧化物或碱土金属过氧化物。在欧洲专利的0096151号中描述汽提塔用的钝化系统，这里从尿素合成反应器来的流出物在高温和高压下（120kg/cm2和240kg/cm2）之间下处理成带有NH3或CO2的下降的薄膜逆流;对于从这些汽提塔中至少一个的底部引入的由含氧气体组成的第一钝化剂，还添加了作为第二钝化剂的一种液体，它从此汽提塔的上部引入，选自双氧水（过氧化氢）、碱金属的过硫酸盐或过硼酸盐、过醋酸以及有机的过氧化物。
氧可以作为纯氧或与空气混合或与双氧水混合而引入相应设备中。
气体形态的氧在被压缩之前通过把它注入到CO2中而引入，或者注入到进入合成区的氨中而引入，或者作为双氧水从待保护之设备的入口上游处注入到各种液体流中。
正如以前所指出的，具有双氧水的钝化系统在任何情况下都需要同时注入气态氧（或是空气或纯氧）。
上述钝化系统被用来保护金属材料免受腐蚀，这种金属材料则通常是用在生产尿素的工厂中（各种类型的不锈钢、钛等等）。
除了上述的钝化剂之外，还提出其他一些（举例来说，有DE-A-1800755号中所提出的），例如可溶性亚硝酸铵、可溶性亚硝酸钠以及其他还未以工业规模使用过的物质。
现在普遍用来钝化在化工厂各阶段中与溶液和蒸汽接触的金属表面的技术，是把注入到CO2中去的空气和氧气送到合成反应塔中;在一些情况下，除了这种注入形式之外，还把双氧水引入被钝化的设备的液流上游。
被注入到CO2中的氧含量其浓度在0.2%和0.8%体积之间，而这会造成如下所指出的几点困难：
1.以空气形式注入的氧会以氮富集反应器中，这显然会使合成区为惰性气体所富集，从而便形式这样一种气相，其结果将降低反应器中尿素的产率。
2.对于氨的生成而言因为C2来自合成气体的脱碳工段，它就会以这样的比例含有H2、N2、CO、CH4，在此种比例下这些气体与氧在一起便会产生爆炸性混合物。
业已知道，为了避开爆炸区域，注入到CO2中氧的量必须低于0.2%（体积），但是在这些条件下已然看到，金属表面上的保护作用大大降低，而使金属表面遭受到存在于设备中各种各样零件上的液体物质和气体物质两者的腐蚀作用。
本发明的目的在于提供一种工艺，它能消除现代工艺技术的缺点同时允许克服一方面必须要有大量的氧来适合于所要求的钝化目的，另一方面需要避免爆炸的危险这两种相对立的局面。
已出人意料地发现，在钝化用空气中增加少量的臭氧（O3），可使氧含量减少到0.3%体积以下而不影响设备的钝化。
空气和O3的最佳协同氧化作用特别可以获得下列各优点：
3.尿素合成反应器中的惰性气体的显著减少，其优点是尿素产率的提高。
4.反应器中气相减少，从而增加了液相的体积同时也增加了它的滞留时间。
5.避免了爆炸性区域，因为O2不会与相应设备中各阶段中存在的H2、CO、CH4形成爆炸性混合物。
本发明的优点是绝对肯定的而且是非常显著的，这是因为O3生产是以经过充分实验的通常方法完成的，正如最为通常的从排入到大气中的惰性气体中未消除O3的系统那样，这里，环境保护法是禁止把O3释放到大气中去的，因而O3的生产及它的消除乃是从所周知的技术。
CO2中O2的含量允许在0.05%与0.3%（体积）之间变化。同时O3的含量允许在0.01%和0.1%（体积）之间变化。当从下列一组化合物是选取出的一种化合物与O2和O3同时存在时，氧量可以减少到低于0.05%（体积），例如在0.01%和0.05%（体积）之间，这样一组化合物是双氧水（H2O2），碱金属过氧化物，碱性白花酢浆草过氧化物，碱金属过硫酸盐或碱金属过硼酸盐，有机过氧化物及醋酸，而从这组化合物中所选出的第三种化合物则最好是双氧水（H2O2）。
本发明的另一个优点是，O3的浓度可保持很高的水平而不会有爆炸的危险，同时会显著地提高钝化效果，从由氨合成气体之脱碳设备获得之CO2中减少氢气（H2）的含量（以及CO、与CH4的含量），而这最好是使待再生的CO2在进入待再生阶段之前，使富含CO2的溶液通过一附加的预闪蒸处理。
上述的预闪蒸可以简单地在约3巴绝对大气压力下进行。
例子
下面一些例子的意图是打算对照比较被送到合成反应器的CO2的成分和被排出到大气中的惰性气体的成分，既根据先有技术也根据本发明。
以产量为1000吨/日的（t/d）尿素工厂为例：CO2的成分
对照例1
先有技术
合成中所需要的CO2的量及增加空气后的成分表示如下：
CO215610标准立方米/小时 94.93%体积
N2491 " 2.98%体积
H2164 " 1.00℃体积
O298 " 0.60%体积
CO 痕量 " 痕量 体积
CH480 " 0.49% 体积
总计 16443标准立方米/小时 100.00%体积
例2.发明
合成中所需要的CO2的量及添加了用O3增富的空气后的成分表示如下：
CO215610标准立方米/小时 96.77%体积
N2245 " 1.52% "
H2164 " 1.02% "
O229 " 0.18% "
O33 " 0.02% "
CO 痕量 " 痕量 "
CH480 " 0.49% "
总计 16131标准立方米/小时 100.00%体积
可以看到，把本发明与先有技术所需要的氧值相比较，氧的量已显著减少了，同时由于添加了臭氧（O3），钝化效果是相当高的。
在以上两种情况下排出到大气中的惰性气体的成分：
例3
两种混合物的爆炸区域可由通常的方法容易地计算出来，同时将看到按照本发明，它在例3中的混合物是在爆炸界限以外。
本发明以尿素为例作了细致的描述，就有关的侵蚀现象而论，这是最困难的情形同时也颇具代表性。自然，本发明可用于绝大多数类似情形，而更具体地说可用于各种这样的化学过程，其中正如尿素情形，必须用氧（空气）加或不加过氧化物来进行钝化，现在，依据本发明，用添加O3而最协调地改进了钝化。因此，采用这样一些过程是在本发明的范围与精神之内。
Claims (8)
1、一种金属表面特别是不锈钢、钛等等表面钝化用的系统，在用于形成元素和化合物之化学反应的设备中，其中的元素和化合物特别是在温度和压力都较环境更为苛刻的条件下，更具有腐蚀作用，在该系统中主要的钝化剂是至少与第二种辅助剂相结合的氧(空气)，特别在于：后者是臭氧(O3)。
2、如权利要求1所述的系统，特征在于O3是从空气或者从氧中获得的。
3、如权利要求1或2所述的系统，特征在于被加到氧中的O3的量按O2的体积计是在0.01%与0.1%（体积）之间，而O2量则最好小于0.2%（体积）。
4、如权利要求3所述系统，特征在于：从由双氧水（H2O2）、碱金属过氧化物、碱土过氧化物、碱金属过硫酸盐或碱金属过硼酸盐、有机过氧化物及醋酸组成的这组化合物中选出的一种化合物是与氧（O2）和臭氧（O3）同时存在的。
5、如权利要求1、2、3或4中之一所述系统，特别是用来从NH3和CO2合成尿素的和伴随尿素的那些化合物的处理设备的钝化系统，而更具体地说，是用于尿素合成反应和浓缩设备，用于氨基甲酸铵分解和凝聚设备，等等，涉及到Cr、Ni等等，不锈钢、以至钛等等金属表面的钝化系统，特征在于：将添加有O3的空气注入到CO2和/或NH3流的给料和/或再循环流中，和/或注入到其它的液体和/或气体流中。
6、如权利要求5所述系统，特征在于存在于CO2中的氧化剂O3按体积计可以在0.001%和0.3%之间变化。
7、如权利要求6所述系统，其中存在于CO2中的氧化剂O3按体积计算最好在0.01%和0.2%之间变化，此时的CO2有很低的氢含量，并且是从CO2吸收工段将其预闪蒸以除去氢而获得的，其中还有CO与氮，它们是来自在进入到再生塔之前已吸收了CO2之溶液中的。
8、如权利要求5所述系统，特征在于：以液态形式流动时氧化剂O3的浓度可以在2和1000ppm之间变化。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI910715A IT1251524B (it) | 1991-03-18 | 1991-03-18 | Metodo per la passivazione delle superfici metalliche interessate da condizioni e agenti promotori di corrosione |
| IT91A000715 | 1991-03-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069293A true CN1069293A (zh) | 1993-02-24 |
| CN1040463C CN1040463C (zh) | 1998-10-28 |
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| CN92101789A Expired - Lifetime CN1040463C (zh) | 1991-03-18 | 1992-03-16 | 具有金属表面的尿素合成和处理设备的钝化方法 |
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| EP (1) | EP0504621B1 (zh) |
| CN (1) | CN1040463C (zh) |
| AT (1) | ATE146230T1 (zh) |
| CA (1) | CA2063344C (zh) |
| DE (1) | DE69215721D1 (zh) |
| IT (1) | IT1251524B (zh) |
| RU (1) | RU2070230C1 (zh) |
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| DE4242967A1 (de) * | 1992-12-18 | 1994-06-23 | Messer Griesheim Gmbh | Verfahren zum Spülen und Rekonditionieren von Transfersystemen |
| JP2987754B2 (ja) * | 1996-01-17 | 1999-12-06 | 岩谷産業株式会社 | 高純度ガスの配管路での不動態化処理方法 |
| MXPA02012886A (es) * | 2000-06-22 | 2003-05-14 | United States Filter Corp | Control de la corrosion utilizando un donador de peroxido de hidrogeno. |
| US6716359B1 (en) | 2000-08-29 | 2004-04-06 | United States Filter Corporation | Enhanced time-based proportional control |
| NL1016121C2 (nl) * | 2000-09-07 | 2002-03-11 | Dsm Nv | Methode voor het corrosiebestendig maken van metalen. |
| US6620315B2 (en) | 2001-02-09 | 2003-09-16 | United States Filter Corporation | System for optimized control of multiple oxidizer feedstreams |
| US6776926B2 (en) | 2001-08-09 | 2004-08-17 | United States Filter Corporation | Calcium hypochlorite of reduced reactivity |
| CA2457200A1 (en) * | 2001-08-31 | 2003-03-06 | Dsm Ip Assets B.V. | Process for rendering metals corrosion resistant |
| US6991735B2 (en) | 2002-02-26 | 2006-01-31 | Usfilter Corporation | Free radical generator and method |
| US7108781B2 (en) | 2002-02-26 | 2006-09-19 | Usfilter Corporation | Enhanced air and water purification using continuous breakpoint halogenation with free oxygen radicals |
| WO2007146671A2 (en) | 2006-06-06 | 2007-12-21 | Fluid Lines | Ultaviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| US10343939B2 (en) | 2006-06-06 | 2019-07-09 | Evoqua Water Technologies Llc | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| US12103874B2 (en) | 2006-06-06 | 2024-10-01 | Evoqua Water Technologies Llc | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| US9725343B2 (en) | 2007-04-03 | 2017-08-08 | Evoqua Water Technologies Llc | System and method for measuring and treating a liquid stream |
| US20080245737A1 (en) * | 2007-04-03 | 2008-10-09 | Siemens Water Technologies Corp. | Method and system for providing ultrapure water |
| US8753522B2 (en) | 2007-04-03 | 2014-06-17 | Evoqua Water Technologies Llc | System for controlling introduction of a reducing agent to a liquid stream |
| US9365436B2 (en) | 2007-04-03 | 2016-06-14 | Evoqua Water Technologies Llc | Method of irradiating a liquid |
| US8961798B2 (en) | 2007-04-03 | 2015-02-24 | Evoqua Water Technologies Llc | Method for measuring a concentration of a compound in a liquid stream |
| US8741155B2 (en) | 2007-04-03 | 2014-06-03 | Evoqua Water Technologies Llc | Method and system for providing ultrapure water |
| US9365435B2 (en) | 2007-04-03 | 2016-06-14 | Evoqua Water Technologies Llc | Actinic radiation reactor |
| CA2753361A1 (en) | 2009-02-09 | 2010-08-12 | Advanced Biocatalytics Corporation | Cleaning compositions and methods for burnt-on food and oil residues |
| US8591730B2 (en) | 2009-07-30 | 2013-11-26 | Siemens Pte. Ltd. | Baffle plates for an ultraviolet reactor |
| US20140076462A1 (en) * | 2011-03-23 | 2014-03-20 | Ningxia Orient Tantalum Industry Co., Ltd. | Method for passivating tantalum metal surface and apparatus thereof |
| EP2527301B1 (en) | 2011-05-26 | 2016-04-27 | Evoqua Water Technologies GmbH | Method and arrangement for a water treatment |
| ITMI20120013A1 (it) | 2012-01-09 | 2013-07-10 | Saipem Spa | Procedimento per la sintesi di urea comprendente un flusso di passivazione a fondo stripper |
| US11161762B2 (en) | 2015-01-21 | 2021-11-02 | Evoqua Water Technologies Llc | Advanced oxidation process for ex-situ groundwater remediation |
| CA2918564C (en) | 2015-01-21 | 2023-09-19 | Evoqua Water Technologies Llc | Advanced oxidation process for ex-situ groundwater remediation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR1027202A (fr) * | 1949-11-05 | 1953-05-08 | Procédé pour l'obtention de revêtements protecteurs de très liaute résistance | |
| EP0096151B1 (en) * | 1982-06-03 | 1986-07-23 | Montedison S.p.A. | Method for avoiding the corrosion of strippers in urea manufacturing plants |
| US5188714A (en) * | 1991-05-03 | 1993-02-23 | The Boc Group, Inc. | Stainless steel surface passivation treatment |
-
1991
- 1991-03-18 IT ITMI910715A patent/IT1251524B/it active IP Right Grant
-
1992
- 1992-02-24 AT AT92103043T patent/ATE146230T1/de not_active IP Right Cessation
- 1992-02-24 DE DE69215721T patent/DE69215721D1/de not_active Expired - Lifetime
- 1992-02-24 EP EP92103043A patent/EP0504621B1/en not_active Expired - Lifetime
- 1992-03-04 US US07/846,537 patent/US5306355A/en not_active Expired - Lifetime
- 1992-03-16 CN CN92101789A patent/CN1040463C/zh not_active Expired - Lifetime
- 1992-03-17 RU SU925011161A patent/RU2070230C1/ru active
- 1992-03-18 CA CA002063344A patent/CA2063344C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1040463C (zh) | 1998-10-28 |
| EP0504621A1 (en) | 1992-09-23 |
| EP0504621B1 (en) | 1996-12-11 |
| ITMI910715A1 (it) | 1992-09-18 |
| CA2063344A1 (en) | 1992-09-19 |
| IT1251524B (it) | 1995-05-16 |
| US5306355A (en) | 1994-04-26 |
| CA2063344C (en) | 2001-07-03 |
| ATE146230T1 (de) | 1996-12-15 |
| ITMI910715A0 (it) | 1991-03-18 |
| RU2070230C1 (ru) | 1996-12-10 |
| DE69215721D1 (de) | 1997-01-23 |
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