CN110743523A - 一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法 - Google Patents
一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法 Download PDFInfo
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
本发明提供了一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，包括如下步骤：以无定形氧化铝粉末为原料，在滚动造粒过程中，加入硝酸镁等活性金属盐溶液、造孔剂、粘合剂，经过造粒、干燥、焙烧后制成球状催化剂，本发明的含氧化镁或者复合氧化物的催化剂可以重复使用，相同臭氧投入量下，通过本发明的耐盐催化剂的臭氧催化氧化作用，可使煤化工高浓盐水（TDS为1%~10%）处理COD去除效率提高10～50%。
Description
技术领域
本发明涉及催化剂制备技术领域，特别是涉及一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法。本发明的催化剂主要用于臭氧催化氧化去除煤化工高浓盐水（TDS为1%~10%）中的难降解有机污染物。
背景技术
煤化工高浓盐水主要来自于膜浓缩或者热浓缩过程产生的浓水，其TDS为1%~10%，有的甚至高达20% 以上，COD为100~2000 mg/L，且主要为难降解有机物。高COD 可能引起膜污染、蒸发结晶过程有机物污染，限制了废水进一步浓缩或者资源化利用。对于此类废水
的处理，由于盐浓度对微生物的抑制作用，生化法一般难以奏效。活性炭吸附法对有机物去除效果显著，但活性炭吸附容量有限，吸附饱和后再生困难，导致运行费用偏高。多相臭氧催化氧化法通过产生强氧化性的羟基自由基，对水中难降解、高稳定性的有机污染物进行氧化降解，不产生二次污染，成为高浓盐水中有机污染物去除的关键技术之一。
相关研究表明，金属氧化物的表面酸碱位和表面羟基基团被认为是臭氧分解的活性位点。在高浓盐水中，由于Cl-、SO4 2-、CO3 2-、PO4 3-等阴离子的吸附，占据活性位点，使得臭氧催化剂活性下降。现有的臭氧催化剂在高浓盐水中有机物去除效果不佳，不具备耐盐的性能。
MgO具有很好的稳定性和高活性的表面碱性位，对高浓盐水中的Cl-、SO4 2-等阴离子吸附作用弱，优先催化O3生成强氧化性自由基。因此可以通过MgO或者MgO的复合氧化物制备耐盐臭氧催化剂。
发明内容
本发明的目的是制备一种新型耐盐臭氧催化氧化催化剂，该催化剂能大幅度提高煤化工高浓盐水中臭氧的利用率和难降解有机污染物的去除率。
本发明所述的一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，以无定形氧化铝粉末为原料，在滚动造粒过程中，加入金属盐溶液、造孔剂、粘合剂，经过造粒、干燥、焙烧后制成球状催化剂，本催化剂主要用于煤化工高浓盐水中难降解有机污染物的去除，具体包括以下几个步骤：
(a) 启动造粒机，放入无定形氧化铝粉末，加入粘合剂，造粒形成粒径为2～4mm的催化剂内核；
(b)将催化剂内核、无定型氧化铝粉末、金属盐溶液、造孔剂、粘合剂加入造粒机，形成粒径为4～8mm的催化剂成型球体；
(c)将成型球体干燥、焙烧获得臭氧催化剂。
上述新型耐盐臭氧催化剂的制备方法中，金属盐溶液至少含有硝酸镁，同时含有硝酸铜、硝酸锰、硝酸铁、硝酸钴、硝酸铈、硝酸镧等溶液中的一种或多种。
上述新型耐盐臭氧催化剂的制备方法中，所述金属盐溶液的浓度为5～50wt%。
上述新型耐盐臭氧催化剂的制备方法中，造孔剂为聚乙二醇、聚乙烯醇、尿素和碳黑中的一种或多种。
上述新型耐盐臭氧催化剂的制备方法中，粘合剂为水、硅溶胶、铝溶胶中的一种或多种。
上述新型耐盐臭氧催化剂的制备方法中，所述步骤(c)的干燥是在80～150℃条件下干燥4～12小时。
上述新型耐盐臭氧催化剂的制备方法中，所述步骤(c)的焙烧是在500～900℃条件下焙烧2～8小时。
上述新型耐盐臭氧催化剂的制备方法中，所述金属活性组分的负载量为氧化铝总质量的0.5～20wt%。
与现有技术相比，本发明具有如下优点及有益效果：
（1）本发明中制备的新型耐盐臭氧催化氧化催化剂是以MgO或其复合氧化物为主要活性组分的催化剂，利用MgO高活性的表面碱性位，优先催化O3生成强氧化性自由基，对高浓盐水中的Cl-、SO4 2-等阴离子吸附作用弱，提高有机物的去除效率；
（2）本发明通过把具有臭氧催化活性的金属盐溶于水，与氧化铝粉末原料一起滚动造粒、干燥、焙烧，高温烧结过程中，金属盐分解得到的金属氧化物具有微米或者纳米尺寸，均匀分布于氧化铝载体中，附着强度高，催化活性和稳定性强，容易实现大规模的工业化生产。
具体实施方式
实施例1
启动造粒机，放入2kg无定形氧化铝粉末，加入0.1kg铝溶胶粘合剂，造粒形成粒径为2～4mm的催化剂内核；取0.2kg Mg(NO3)2·6H2O溶于水，将0.2kg无定形氧化铝粉末、Mg(NO3)2溶液、0.1kg 聚乙二醇和催化剂内核放入造粒机，在催化剂内核的基础上进行滚动造粒，制备成粒径为4～8mm的催化剂成型球体，然后在100℃干燥12h，600℃焙烧4h得到耐盐臭氧催化剂成品。
本实施例制备的耐盐臭氧催化剂的催化性能评价通过以下方式实现：利用臭氧催化氧化处理某煤化工企业反渗透浓水，TDS为18800mg/L，COD为300mg/L，臭氧投加量200mg/L，反应时间为60min，加入普通臭氧催化剂（以二氧化锰、三氧化二铁为催化活性组分），COD由300mg/L 降低到250 mg/L ；利用本实施例制备的耐盐臭氧催化剂，COD 由300mg/L 降低到150 mg/L，COD去除效率提高33.3%。
实施例2
启动造粒机，放入2kg无定形氧化铝粉末，加入0.1kg铝溶胶粘合剂，造粒形成粒径为2～4mm的催化剂内核；取0.4 kg Mg(NO3)2·6H2O溶于水，将0.2kg无定形氧化铝粉末、Mg(NO3)2溶液、0.1kg 聚乙二醇和催化剂内核放入造粒机，在催化剂内核的基础上进行滚动造粒，制备成粒径为4～8mm的催化剂成型球体，然后在100℃干燥12h，600℃焙烧4h得到耐盐臭氧催化剂成品。
本实施例制备的耐盐臭氧催化剂的催化性能评价通过以下方式实现：利用臭氧催化氧化处理某煤化工企业反渗透浓水，TDS为18800mg/L，COD为300mg/L，臭氧投加量200mg/L，反应时间为60min，加入普通臭氧催化剂（以二氧化锰、三氧化二铁为催化活性组分），COD由300mg/L 降低到250 mg/L ；利用本实施例制备的耐盐臭氧催化剂，COD 由300mg/L 降低到120 mg/L，COD去除效率提高43.3%。
实施例3
启动造粒机，放入2kg无定形氧化铝粉末，加入0.1kg铝溶胶粘合剂，造粒形成粒径为2～4mm的催化剂内核；取0.2 kg Mg(NO3)2·6H2O和0.02kg Cu(NO3)2·3H2O溶于水，将0.2kg无定形氧化铝粉末、Mg(NO3)2和Cu(NO3)2溶液、0.1kg 聚乙二醇和催化剂内核放入造粒机，在催化剂内核的基础上进行滚动造粒，制备成粒径为4～8mm的催化剂成型球体，然后在100℃干燥12h，600℃焙烧4h得到耐盐臭氧催化剂成品。
本实施例制备的耐盐臭氧催化剂的催化性能评价通过以下方式实现：利用臭氧催化氧化处理某煤化工企业高盐浓水，TDS为42800mg/L，COD为190mg/L，臭氧投加量100mg/L，反应时间为60min，加入普通臭氧催化剂（以二氧化锰、三氧化二铁为催化活性组分），COD由190mg/L 降低到150 mg/L；利用本实施例制备的耐盐臭氧催化剂，COD 由190mg/L 降低到100 mg/L，COD去除效率提高26.4%。
实施例4
启动造粒机，放入2kg无定形氧化铝粉末，加入0.1kg铝溶胶粘合剂，造粒形成粒径为2～4mm的催化剂内核；取0.2 kg Mg(NO3)2·6H2O、0.01kg Cu(NO3)2·3H2O、0.02 kg Mn(NO3)2（50wt%）溶液溶于水，将0.2kg无定形氧化铝粉末、金属硝酸盐混合溶液、0.1kg 聚乙二醇和催化剂内核放入造粒机，在催化剂内核的基础上进行滚动造粒，制备成粒径为4～8mm的催化剂成型球体，然后在100℃干燥12h，600℃焙烧4h得到耐盐臭氧催化剂成品。
本实施例制备的耐盐臭氧催化剂的催化性能评价通过以下方式实现：利用臭氧催化氧化处理某煤化工企业高盐浓水，TDS为15000mg/L，COD为250mg/L，臭氧投加量100mg/L，反应时间为60min，加入普通臭氧催化剂（以二氧化锰、三氧化二铁为催化活性组分），COD由250mg/L 降低到200 mg/L；利用本实施例制备的耐盐臭氧催化剂，COD 由250mg/L 降低到150 mg/L，COD去除效率提高15.0%。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (8)
1.一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，其特征在于：以无定形氧化铝粉末为原料，在滚动造粒过程中，加入金属盐溶液、造孔剂、粘合剂，经过造粒、干燥、焙烧后制成球状催化剂，本催化剂主要用于煤化工高浓盐水中难降解有机污染物的去除，具体包括以下几个步骤：
(a) 启动造粒机，放入无定形氧化铝粉末，加入粘合剂，造粒形成粒径为2～4mm的催化剂内核；
(b)将催化剂内核、无定型氧化铝粉末、金属盐溶液、造孔剂、粘合剂加入造粒机，形成粒径为4～8mm的催化剂成型球体；
(c)将成型球体干燥、焙烧获得臭氧催化剂。
2.根据权利要求1所述的一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，其特征在于：金属盐溶液至少含有硝酸镁，同时含有硝酸铜、硝酸锰、硝酸铁、硝酸钴、硝酸铈、硝酸镧等溶液中的一种或多种。
3.根据权利要求1所述的一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，其特征在于：所述金属盐溶液的浓度为5～50wt%。
4.根据权利要求1所述的一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，其特征在于：造孔剂为聚乙二醇、聚乙烯醇、尿素和碳黑中的一种或多种。
5.根据权利要求1所述的一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，其特征在于：粘合剂为水、硅溶胶、铝溶胶中的一种或多种。
6.根据权利要求1所述的一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，其特征在于：所述步骤(c)中的干燥是在80～150℃条件下干燥4～12小时。
7.根据权利要求1所述的一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，其特征在于：：所述步骤(c)中的焙烧是在500～900℃条件下焙烧2～8小时。
8.根据权利要求1所述的一种处理煤化工高浓盐水臭氧催化氧化耐盐催化剂的制法，其特征在于：所述金属活性组分的负载量为氧化铝总质量的0.5～20wt%。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115739101A (zh) * | 2022-09-07 | 2023-03-07 | 南京大学 | 一种双金属负载型臭氧催化剂的可控制备方法及其水处理应用 |
| CN116351411A (zh) * | 2022-12-07 | 2023-06-30 | 四川泸天化麦王临港环保有限责任公司 | 用于金刚烷及其衍生物废水处理的催化剂及其制备和应用 |
| CN115739101B (zh) * | 2022-09-07 | 2024-05-28 | 南京大学 | 一种双金属负载型臭氧催化剂的可控制备方法及其水处理应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115739101A (zh) * | 2022-09-07 | 2023-03-07 | 南京大学 | 一种双金属负载型臭氧催化剂的可控制备方法及其水处理应用 |
| CN115739101B (zh) * | 2022-09-07 | 2024-05-28 | 南京大学 | 一种双金属负载型臭氧催化剂的可控制备方法及其水处理应用 |
| CN116351411A (zh) * | 2022-12-07 | 2023-06-30 | 四川泸天化麦王临港环保有限责任公司 | 用于金刚烷及其衍生物废水处理的催化剂及其制备和应用 |
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