CN111762963B - 一种高盐高cod污水处理零排放工艺 - Google Patents
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Abstract
本发明属于污水处理领域,尤其涉及一种高盐高COD污水处理零排放工艺。包含分盐浓缩,中水回用,脱稳结晶,除杂蒸发步骤,本发明通过纳滤、冷冻结晶、厌氧氧化三者耦合的方式处理污水。在反渗透处理后添加纳滤进行分盐,将一价与二价杂盐离子分开,再对两种分离液分别进行处理,处理后的母液经厌氧氧化后返回前端重新进入处理系统,从而实现资源的回收利用,废水零排放,以此减少对环境的污染。
Description
技术领域
本发明属于水处理领域,尤其涉及一种高盐高COD污水处理零排放工艺。
背景技术
高盐高COD废水污水处理排放工艺中,现有工艺方法为:来水→预处理→中空超滤+反渗透→结晶→杂盐。即,预处理产生的浓水,直接进入(双膜法)膜分离单元进行浓缩,对于浓缩后的污水一般采用直接蒸发结晶的方法,由于浓缩后的污水量仍非常大,需要较大处理能力的蒸发结晶单元,成本较高;且蒸发结晶出的大量杂盐,无法直接使用,需要进一步处理,导致工艺流程长且处理效果差。
发明内容
为克服上述缺陷,本发明公开一种高盐高COD污水处理零排放工艺,包括如下步骤:
步骤一、生化出水经过预处理单元后,进入一级平板式反渗透单元进行过滤浓缩,过滤浓缩后一级产水直接进入回用水池备用,同时生成一级浓水进入一级平板式纳滤单元;
步骤二、在一级平板式纳滤单元中,一级浓水中的二价离子Ca 2+,SO 4 2-因不能透过平板式纳滤膜而被截留,形成一级纳滤浓水,一级纳滤浓水中,CaSO 4的浓度达到250~500%的过饱和态,然后进入脱稳结晶单元(5)进行脱稳结晶;一级浓水中的一价离子Na+,Cl-,F-,NO 3-,NH 4+透过一级平板式纳滤膜形成一级纳滤产水,进入二级反渗透单元(13)进一步过滤浓缩;
步骤三、在脱稳结晶单元内加入晶种,诱发过饱和态的CaSO 4开始结晶,利用自诱导原理,石膏固体结晶析出,溶液中CaSO 4含量降低的同时得到纯度较高的石膏固体,并生成上清液,即,脱稳产水;
步骤四、脱稳产水经过前面的多倍浓缩导致Ca 2+和Mg 2+含量高,硬度大,因此进入软化沉淀单元进行药剂软化处理以降低硬度,本单元内加入药剂Na 2 CO 3进行软化,经过反应,脱稳产水中的绝大部分Ca 2+,Mg 2+被去除,并生成以Na 2 SO 4为主以及含量极少的二价离子Ca 2+,Mg 2+,SO 4 2-的软化产水;
步骤五、软化产水进入二级纳滤单元进行二次分盐与浓缩,结果是产生二级纳滤浓水与二级纳滤产水,其中,二级纳滤产水进入二级反渗透单元,二级纳滤浓水进入冷冻结晶单元进行冷冻结晶;
步骤六、在冷冻结晶单元内,二级纳滤浓水经冷冻后结晶,过滤,其中,含有Na+,Ca2+,SO 4 2-,COD的上层母液进入厌氧单元进行氧化,氧化后的水COD降低,可返回前端循环再次进行处理;底层结晶主要成分为含水硫酸钠晶体,此晶体进入重结晶单元处理后,产物为无水硫酸钠;
步骤七、一级纳滤产水和二级纳滤产水经过二级反渗透单元过滤后,产生的二级产水进入回用水池回用,二级浓水进入除杂单元,在除杂单元内,利用选择性吸附的方法去除溶液中的杂质离子;其中,斜发沸石吸附F-,硝酸盐专用树脂吸附去除溶液中NO 3-,铵盐专用树脂去除其中的NH 4+,最终F-,NO 3-,NH 4+被除去,只剩余NaCl溶液,NaCl溶液进入蒸发结晶单元蒸发后生成无水NaCl。
发明原理及效果说明:
(1)本工艺中采用首先纳滤的方法进行分盐,将一价离子与二价离子分开,分别处理,可以得到纯净的结晶盐。
(2)经过纳滤浓缩的二价离子含Ca 2+,SO 4 2-,Mg 2+溶液,采用脱稳+软化的方法处理。即,采用膜过滤浓缩,生成过饱和的CaSO 4溶液,在此溶液中引入晶种,结晶出石膏,从而去除浓缩液中的SO 4 2-,对于引入的多余Ca 2+,再加入Na 2 CO 3进行软化,最后,溶液中只剩余Na 2 SO 4。对于此溶液,再采用冷冻结晶的方法,可以结晶出硫酸钠晶体。
由于诱导CaSO 4结晶成石膏属于无相变结晶,无需消耗电能或热能,降低结晶成本的同时得到了纯净的无机盐,减少了后续的分盐工艺。
(3)石膏脱稳+软化过程中,除了结晶出盐类物质外,同时对污水中的COD进行富集,最终进入厌氧氧化单元,COD降低后的产水进入系统前端循环处理,最终无污水排放。
(4)经过纳滤单元分离出的一价离子混合溶液,采用不同介质的过滤器进行过滤和蒸发,分别去除Na+,Cl-,F-,NO 3-,NH 4+一价离子,可以获得达标产水。
附图说明
图1为本发明工艺流程图。
具体实施方式
结合图1所示。本发明高盐高COD污水处理零排放工艺,包括如下步骤:
步骤一、生化出水经过预处理单元1后,进入一级平板式反渗透单元2进行过滤浓缩,过滤浓缩后一级产水直接进入回用水池3备用,同时生成一级浓水进入一级平板式纳滤单元4;
步骤二、在一级平板式纳滤单元4中,一级浓水中的二价离子Ca 2+,SO 4 2-因不能透过平板式纳滤膜而被截留,形成一级纳滤浓水,一级纳滤浓水中,CaSO 4的浓度达到250~500%的过饱和态,然后进入脱稳结晶单元5进行脱稳结晶;一级浓水中的一价离子Na+,Cl-,F-,NO 3-,NH 4+透过一级平板式纳滤膜形成一级纳滤产水,进入二级反渗透单元13进一步过滤浓缩;
步骤三、在脱稳结晶单元5内加入晶种,诱发过饱和态的CaSO 4开始结晶,利用自诱导原理,石膏固体结晶析出,溶液中CaSO 4含量降低的同时得到纯度较高的石膏固体,并生成上清液,即,脱稳产水;
步骤四、脱稳产水经过前面的多倍浓缩导致Ca 2+和Mg 2+含量高,硬度大,因此进入软化沉淀单元6进行药剂软化处理以降低硬度,本单元内加入药剂Na 2 CO 3进行软化,经过反应,脱稳产水中的绝大部分Ca 2+,Mg 2+被去除,并生成以Na 2 SO4为主以及含量极少的二价离子Ca 2+,Mg 2+,SO 4 2-的软化产水;
步骤五、软化产水进入二级纳滤单元7进行二次分盐与浓缩,结果是产生二级纳滤浓水与二级纳滤产水,其中,二级纳滤产水进入二级反渗透单元13,二级纳滤浓水进入冷冻结晶单元8进行冷冻结晶;
步骤六、在冷冻结晶单元内,二级纳滤浓水经冷冻后结晶,过滤,其中,含有Na+,Ca2+,SO 4 2-,COD的上层母液11进入厌氧单元12进行氧化,氧化后的水COD降低,可返回前端循环再次进行处理;底层结晶主要成分为含水硫酸钠晶体,此晶体进入重结晶单元10处理后,产物为无水硫酸钠;
步骤七、一级纳滤产水和二级纳滤产水经过二级反渗透单元13过滤后,产生的二级产水进入回用水池3回用,二级浓水进入除杂单元14,在除杂单元内,利用选择性吸附的方法去除溶液中的杂质离子;其中,斜发沸石吸附F-,硝酸盐专用树脂吸附去除溶液中NO3-,铵盐专用树脂去除其中的NH 4+,最终F-,NO 3-,NH 4+被除去,只剩余NaCl溶液,NaCl溶液进入蒸发结晶单元15蒸发后生成无水NaCl。
Claims (1)
1.一种高盐高COD污水处理零排放工艺,其特征在于:包括如下步骤:
步骤一、生化出水经过预处理单元(1)后,进入一级平板式反渗透单元(2)进行过滤浓缩,过滤浓缩后一级产水直接进入回用水池(3)备用,同时生成一级浓水进入一级平板式纳滤单元(4);
步骤二、在一级平板式纳滤单元(4)中,一级浓水中的二价离子Ca2+,SO4 2-因不能透过平板式纳滤膜而被截留,形成一级纳滤浓水,一级纳滤浓水中,CaSO的浓度达到250~500%的过饱和态,然后进入脱稳结晶单元(5)进行脱稳结晶;一级浓水中的一价离子Na+,Cl-,F-,NO3 -,NH4 +透过一级平板式纳滤膜形成一级纳滤产水,进入二级反渗透单元(13)进一步过滤浓缩;
步骤三、在脱稳结晶单元(5)内加入晶种,诱发过饱和态的CaSO开始结晶,利用自诱导原理,石膏固体结晶析出,溶液中CaSO含量降低的同时得到纯度较高的石膏固体,并生成上清液,即,脱稳产水;
步骤四、脱稳产水经过前面的多倍浓缩导致Ca2+和Mg2+含量高,硬度大,因此进入软化沉淀单元(6)进行药剂软化处理以降低硬度,本单元内加入药剂Na2CO3进行软化,经过反应,脱稳产水中的绝大部分Ca2+,Mg2+被去除,并生成以Na2SO4为主以及含量极少的二价离子Ca2+,Mg2+,SO4 2-的软化产水;
步骤五、软化产水进入二级纳滤单元(7)进行二次分盐与浓缩,结果是产生二级纳滤浓水与二级纳滤产水,其中,二级纳滤产水进入二级反渗透单元(13),二级纳滤浓水进入冷冻结晶单元(8)进行冷冻结晶;
步骤六、在冷冻结晶单元内,二级纳滤浓水经冷冻后结晶,过滤,其中,含有Na+,Ca2+,SO4 2-,COD的上层母液(11)进入厌氧单元(12)进行氧化,氧化后的水COD降低,可返回前端循环再次进行处理;底层结晶主要成分为含水硫酸钠晶体,此晶体进入重结晶单元(10)处理后,产物为无水硫酸钠;
步骤七、一级纳滤产水和二级纳滤产水经过二级反渗透单元(13)过滤后,产生的二级产水进入回用水池(3)回用,二级浓水进入除杂单元(14),在除杂单元内,利用选择性吸附的方法去除溶液中的杂质离子;其中,斜发沸石吸附F-,硝酸盐专用树脂吸附去除溶液中NO3 -,铵盐专用树脂去除其中的NH4 +,最终F-,NO3 -,NH4 +被除去,只剩余NaCl溶液,NaCl溶液进入蒸发结晶单元(15)蒸发后生成无水NaCl。
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