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氯化铁与氯化亚铁

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发布时间:2019-09-30 09:06

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氯化铁与氯化亚铁

美国氯化铁总生产能力约52.5万吨/a,共有6家生产厂,最大的生产厂家有PVS技术公司和Eagalbrook 公司,氯化铁生产厂家面临的一个复杂问题是如何保持原材料供应的稳定性。20世纪90年代初钢铁厂开始探索回收(即再生)废酸洗涤液的方案, 目前生产厂家使用的氯化铁原料主要是废酸洗涤液。氯化铁是钢铁厂酸洗液的副产品,因此当钢铁厂开工下降和一些钢铁厂选择回收废盐酸方案时,氯化铁供应就呈现短缺。氯化铁的用户构成为城市废水处理占59%,城市饮用水处理占22%,工业水处理占8%,其余占11%,水处理业是拉动氯化铁需求增长的主要因素。美国氯化铁由于需求增长和主要原材料供应紧张,市场趋紧,但一般说来供需仍处于平衡态势, 2001年1月, PVS公司的氯化铁已提价40美元/t。目前美国氯化铁价格在300-340美元/范围(工业级产品)

水处理行业使用的氯化铁都是氯化铁溶液。生产氯化铁溶液的方法有两种。一种是将铁屑放入水中,然后通入氯气,氯气将铁屑首先氧化成氯化亚铁,然后进一步氧化成氯化铁。

这种方法至今仍然在某些大型自来水公司使用,这种方法的缺陷是由于铁屑的来源复杂,往往含有大量的重金属离子,因此严格来讲无法直接用于饮用水处理。另一种方法是氧化亚铁溶液通过氮氧化物的催化作用,用氧气氧化,得到氯化铁溶液。

、氯化铁的制备1,氯气氧化原理

2FeCl2 = Ch2FeCls

氯气溶于水后部分生成盐酸和次氯酸,另一部分仍以氯气分子的形式存在。Cl2在水中存在下列平衡:

CL2 = H20-HCIO + HCI

氯在水中的溶解度为0. 091mol/L,其中以Cl2形式存在的有0.061 mol/L,以HCIO,HC形式存在的为0.03mol/L,则游离酸含量为(以HCit) 2X0.03 36. 5=2. 171g/L.

2. Cla过量达到饱和时,游离酸的含量

生产时氧化釜中FeCl2投料量为1m",浓度为35%加Cl2 390kg,得产品FeCl,相对密度1.44、浓度41%,假定通入Cl过量,达到饱和,则成品中游离酸的含量为: 2. 171x1× 109/1.44 x10 -0. 15%,达到一级品标准。Cl过量=0.091×1X10 × 36.5 × 10-3-3. 3kg.

3.据产品指标所允许氯气过量的最大限度

一级品要求游离酸含量<0.4%,产品中含HCIO, HCI为

36.5 X10-3X103X2 = 0。0789摩尔/升1х1。44х0.4%×103

相当于氯气过量0.2393mol/L,氧化1m,氯化亚铁氯气可过量0.0239×x10 ×36.5

8. 73kg。实际上当氯气过量8. 73kg时,只有3.3kg溶于水中,其余的则以气体形式逸出反应液。以上计算是以25℃的情况计算的,在实际生产中,反应液的温度为65℃,溶于反应液的氯气将更少。

4,根据产品指标,氯气所允许不足的最大值

当氯气通入量不足时,将有部分FeCl2不能充分氧化,影响产品最终指标. FeCls一等品要求FeCl2含量<0.30%,若投FeCl2 1m时

2FeCl2 = CL2-2FeCla

2X127 71 2x 162.5

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1X1.375 × 35% 10 134 615

得产品1506kg,允许有FeCl: 1506 x0. 30%-4.518kg.氯气可以少通1.26kg,即通人氯气量不能低于化学计算量的百分比为1.26/134=0.9%。

以氯化亚铁为原料生产计量:取10001.氯化亚铁溶液,相对密度为1.33,浓度31%.

放入反应釜中,升温至60~65℃。通入氯气反应,反应结束后,氯化铁溶液的浓度为36%.

酸度检测不出。由此类推,当氯化亚铁溶液投料的含量为35%时,终产品氯化铁溶液的汤度为41%。

从上面计算可以看出为使产品达到质量标准,通入的氯气量不能不足,但可以过量,过量的量可以为化学计算量的百分比=8.73/134=6.5%,因此建议:

①通入氯气时,氯气可以过量的量为化学计算量的3%。

②要求氯气计量的精密度为±2%。

@为避免产品中的余氯在储存运输期继续发生分解反应,反应结束后,通入压缩空气把产品中的余氯压人碱液吸收罐中。

@氧化工艺如果采用亚硝酸盐,反应机理参见聚合氯化铁部分。

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反应条件下,分离出镍后的母液中再加人少量铁粉,恒温搅拌,反应1h,过滤分离,测得母液镍离子浓度仅为3.8mg/L,已低于氯化铁混凝剂标准镍含量。故认为分批投加铁粉比一次投加铁粉除镍效果好。本章由恒信达发布聚合氯化铝  yiwuqipai.com

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