阳树脂油污染的处理技术

哇噻 · 发表于 2007-8-19 11:08:42

阳树脂油污染的处理技术赵振声　（中石化长岭分公司动力厂　湖南　岳阳市　414012）  [内容摘要]  本文对阳离子交换树脂被油污染对生产造成的影响进行分析，并对阳树脂油污染的处理技术及实际应用方法进行了阐述。通过这种方法解决了生产中的实际问题，并取得了良好的经济效益及社会效益。[关键词]  阳离子交换树脂；油；污染；处理  一　前言 逆流有顶压再生离子交换器（固定床）电电厂水处理使用广泛的水处理设备，我单位采用的设备规格为Φ3000×7525，使用的阳树脂是D001大孔强酸性阳离子交换树脂。共有5台阳固定床，阳树脂全部被油污染后，其工作交换容量下降，树脂水流分布不均匀，周期制水量明显下降。再生操作难度加大，再生特别困难，再生频繁。对安全生产造成很大的威胁。本文就其污染原因及处理方法进行分析。 二　原因分析大部分炼油企业的自备热电厂，从有利能源的利用考虑，化学水处理的工业用生水通过换热器加热后进行除盐系统。工艺流程框图如图1。由于我厂炼的原油是高含硫原油，对设备腐蚀严重，造成装置换热器泄漏。2002年3月由于炼油生产装置换热器泄漏，致使动力厂的装置来热水带油严重，恰好动力厂的生水换热器也泄漏。从而使低温水中的油串至生水，导致生水带油严重，且油主要是重质油，生水进入阳离子交换器后，其中的油被阳树脂截流，由于生产系统一直不能停，油不断地被阳树脂截流，使阳树脂被污严重染。阳树脂被油严重污染后，其内部孔隙被油分子填充，表面也覆盖了一层油膜，树脂外观颜色由正常的淡黄色变成棕黑色，树脂因油膜互相粘结在一起，导致其工作交换容量下降，树脂水流分布不均匀，周期制水量明显下降。由于油膜的存在，使树脂在水中的浮力增大，造成再生时树脂上浮，压脂层破坏，起不到压脂作用，使树脂流失严重，再生操作难度加大，再生频繁。供水困难，对安全生产造成很大的威胁。阳树脂(D001)被油污染的含油量分析及离子交换树脂性能部分数据如表1。

哇噻 · 发表于 2007-8-19 11:09:22

表1：离子交换树脂性能部分数据<DIV align=center> <table class="MsoNormalTable" cellspacing="0" cellpadding="0" width="450" border="0" style="MARGIN: auto auto auto 48.8pt; WIDTH: 337.2pt; BORDER-COLLAPSE: collapse; mso-padding-alt: 0cm 0cm 0cm 0cm;"><tbody><tr style="HEIGHT: 14.25pt; mso-yfti-irow: 0; mso-yfti-firstrow: yes;"><td valign="bottom" nowrap="nowrap" width="207" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; BORDER-TOP: windowtext 1pt solid; PADDING-LEFT: 0.75pt; PADDING-BOTTOM: 0cm; BORDER-LEFT: windowtext 1pt solid; WIDTH: 155pt; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 14.25pt; BACKGROUND-COLOR: transparent; mso-border-alt: solid windowtext .5pt;">指标内容</td><td valign="bottom" nowrap="nowrap" width="59" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; BORDER-TOP: windowtext 1pt solid; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 44pt; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 14.25pt; BACKGROUND-COLOR: transparent; mso-border-top-alt: solid windowtext .5pt; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">污染前</td><td valign="bottom" nowrap="nowrap" width="88" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; BORDER-TOP: windowtext 1pt solid; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 66.2pt; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 14.25pt; BACKGROUND-COLOR: transparent; mso-border-top-alt: solid windowtext .5pt; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">污染后</td><td valign="bottom" nowrap="nowrap" width="96" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; BORDER-TOP: windowtext 1pt solid; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 72pt; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 14.25pt; BACKGROUND-COLOR: transparent; mso-border-top-alt: solid windowtext .5pt; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">指标值</td></tr><tr style="HEIGHT: 15.75pt; mso-yfti-irow: 1;"><td valign="bottom" nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; PADDING-BOTTOM: 0cm; BORDER-LEFT: windowtext 1pt solid; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt; mso-border-left-alt: solid windowtext .5pt;">平均周期制水量m3</td><td nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">7926</td><td nowrap="nowrap" width="88" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 66.2pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">5100</td><td nowrap="nowrap" width="96" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 72pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">/</td></tr><tr style="HEIGHT: 15.75pt; mso-yfti-irow: 2;"><td valign="bottom" nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; PADDING-BOTTOM: 0cm; BORDER-LEFT: windowtext 1pt solid; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt; mso-border-left-alt: solid windowtext .5pt;">工作交换容量mol/m3</td><td nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">1126</td><td nowrap="nowrap" width="88" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 66.2pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">615.6</td><td nowrap="nowrap" width="96" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 72pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">1080~1260</td></tr><tr style="HEIGHT: 15.75pt; mso-yfti-irow: 3;"><td valign="bottom" nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; PADDING-BOTTOM: 0cm; BORDER-LEFT: windowtext 1pt solid; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt; mso-border-left-alt: solid windowtext .5pt;">体积换容量（全交）mmol/ml</td><td nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">/</td><td nowrap="nowrap" width="88" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 66.2pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">0.95</td><td nowrap="nowrap" width="96" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 72pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">≥1.8</td></tr><tr style="HEIGHT: 15.75pt; mso-yfti-irow: 4;"><td valign="bottom" nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; PADDING-BOTTOM: 0cm; BORDER-LEFT: windowtext 1pt solid; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt; mso-border-left-alt: solid windowtext .5pt;">湿真密度g/ml</td><td nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">/</td><td nowrap="nowrap" width="88" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 66.2pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">1.05</td><td nowrap="nowrap" width="96" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 72pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 15.75pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">1.16~1.24</td></tr><tr style="HEIGHT: 28.5pt; mso-yfti-irow: 5; mso-yfti-lastrow: yes;"><td nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; PADDING-BOTTOM: 0cm; BORDER-LEFT: windowtext 1pt solid; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 28.5pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt; mso-border-left-alt: solid windowtext .5pt;">含油量</td><td nowrap="nowrap" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 28.5pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">无油</td><td width="88" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 66.2pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 28.5pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">严重油污染</td><td nowrap="nowrap" width="96" style="BORDER-RIGHT: windowtext 1pt solid; PADDING-RIGHT: 0.75pt; PADDING-LEFT: 0.75pt; BORDER-LEFT-COLOR: #ece9d8; PADDING-BOTTOM: 0cm; WIDTH: 72pt; BORDER-TOP-COLOR: #ece9d8; PADDING-TOP: 0.75pt; BORDER-BOTTOM: windowtext 1pt solid; HEIGHT: 28.5pt; BACKGROUND-COLOR: transparent; mso-border-bottom-alt: solid windowtext .5pt; mso-border-right-alt: solid windowtext .5pt;">无油</td></tr></tbody></table></DIV> 由于阳树离子交换脂再生采用的再生液是盐酸（HCl：3%~4%）。对阳树脂中油不能被反应。一直存在树脂中。全部更新树脂费用太高，且树脂的使用寿命未到，所以想方法进行处理

哇噻 · 发表于 2007-8-19 11:10:21

<h1 style="MARGIN: 0cm 0cm 0pt; TEXT-INDENT: 0cm;">三　 分析及实验</h1><h2 style="MARGIN: 0cm 0cm 0pt; TEXT-INDENT: 0cm; LINE-HEIGHT: 20pt; mso-line-height-rule: exactly;">(一)　油污染对树脂使用性能的影响</h2>通过表1中的数据可看出树脂的交换容量已大大的下降，且湿真密度下降，接近于水的比重。对产生造成影响。主要有以下几个方面：<h4 style="MARGIN: 0cm 0cm 0pt; TEXT-INDENT: 24pt; LINE-HEIGHT: 20pt; mso-line-height-rule: exactly; mso-char-indent-count: 2.0;">(1) 由于树脂被油污染，离子交换树脂的交换基团被堵塞，阳树脂的活性基团被油包围，使活性基团被油不可逆的堵塞。从而堵塞了所要交换离子向树脂内部扩散的通道。在再生中也不能被氢根（H＋）离子交换，降低了离子的交换容量。离子交换器周期制水量下降，增加了再生频次，使酸耗量、再生自用水量增加。</h4><h4 style="MARGIN: 0cm 0cm 0pt; TEXT-INDENT: 24pt; LINE-HEIGHT: 20pt; mso-line-height-rule: exactly; mso-char-indent-count: 2.0;">(2) 由于树脂被油污染，有些树脂出现板结，造成阻力增加，离子交换器出力下降很大，原流速达<chmetcnv wst="on" tcsc="0" numbertype="1" negative="False" hasspace="False" sourcevalue="30" unitname="m">30m</chmetcnv>/h
，压降≯0.1Mpa；被污染后最在流速只有<chmetcnv wst="on" tcsc="0" numbertype="1" negative="False" hasspace="False" sourcevalue="15" unitname="m">15m</chmetcnv>/h ，且压降高达0.25Mpa。对大负荷生产产生安全威胁。</h4><h4 style="MARGIN: 0cm 0cm 0pt; TEXT-INDENT: 24pt; LINE-HEIGHT: 20pt; mso-line-height-rule: exactly; mso-char-indent-count: 2.0;">(3) 由于树脂补油污染，有些树脂出现板结，对离子交换器中排造成的压力过大，损坏中排系统。</h4><h2 style="MARGIN: 0cm 0cm 0pt; TEXT-INDENT: 24pt; LINE-HEIGHT: 20pt; mso-line-height-rule: exactly; mso-char-indent-count: 2.0;">(二)　试验</h2><h3 style="MARGIN: 0cm 0cm 0pt; TEXT-INDENT: 0cm; LINE-HEIGHT: 20pt; mso-line-height-rule: exactly;">1 要求</h3>针对油被树脂的污染主要是油被吸收到树脂骨架上或覆盖在树脂颗粒的表面上，造成树脂微孔被树脂堵塞这一特点，考虑到大量的树脂补污染，必须采用能在固定床中进行处理的方法进行，即既要能将树脂中的油除去，又不能对设备中的衬胶产生损坏。考虑到氢氧化钠对矿物油有一定的乳化作用，取一小部分被油污染的阳树脂进行试验。<h3 style="MARGIN: 0cm 0cm 0pt; TEXT-INDENT: 0cm; LINE-HEIGHT: 20pt; mso-line-height-rule: exactly;">2 方法及过程</h3>试验采用方法：将树脂加盐（NaCl）进行转型成Na型树脂――清洗――加一定浓度的氢氧化钠――浸泡、搅拌――清洗――加盐酸（HCl）――清洗。在同一种状态下各作五次。通过试验发现一个循环周期不能达到要求。采用两次循环之后，基本上能达到要求，三次循环，在第二次后没有变化，因此从各方面考虑，二次循环效果最佳。不同浓度的氢氧化钠进行处理。分析数据如表2。从表2　中可看出采用10%左右氢氧化钠进行处理的效果最佳。

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