CN109126838A - 一种臭氧催化剂的制备方法 - Google Patents

一种臭氧催化剂的制备方法 Download PDF

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CN109126838A
CN109126838A CN201811091759.XA CN201811091759A CN109126838A CN 109126838 A CN109126838 A CN 109126838A CN 201811091759 A CN201811091759 A CN 201811091759A CN 109126838 A CN109126838 A CN 109126838A
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active carrier
catalyst
compound
ozone catalyst
copper
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甘成模
黄德金
甘玲
甘宇
黎婷
张艳稻
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Jiangxi Pingxiang Chengyu Ceramic Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06Halogens; Compounds thereof
    • B01J27/08Halides
    • B01J27/122Halides of copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8892Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/10Solids characterised by their surface properties or porosity
    • B01J35/1004Surface area
    • B01J35/1019100-500 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/10Solids characterised by their surface properties or porosity
    • B01J35/1052Pore diameter
    • B01J35/10612-50 nm
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds

Abstract

本发明公开了一种臭氧催化剂的制备方法,包括以下步骤:1)称取活性载体材料通过造粒后烘干,在氮气保护下于500‑700℃焙烧制备活性载体;所述活性载体材料为拟薄水铝石与竹炭、石墨的混合物;2)在活性载体上采用浸渍或喷淋法负载锰化合物、铜化合物;3)将负载锰化合物、铜化合物的活性载体晾干后置于180‑280℃中烘干2‑6h完成催化剂的复活成型制得臭氧催化剂;本发明的催化剂在污水处理中,可根据单相和多相催化氧化工艺,也可适应静态水除污和动态水除污,并具备脱吸油污及污染水源脱色效果。

Description

一种臭氧催化剂的制备方法
技术领域
本发明涉及催化剂制备技术领域,具体讲是一种臭氧催化剂的制备方法。
背景技术
臭氧具备极强的氧化性,使其能与污水中的多种色基团发生反应。虽然臭氧能氧化污水中很多有机物,目的是将有机物的化学键断开,由大分子降解为无色的小分子,但在脱色除油工艺中还存在不足之处,尤为在低温的污水处理时,和有机物的反应选择性差;单纯利用臭氧化氧化工艺、对有机污染物的处理能力较低。
发明内容
本发明所要解决的技术问题是,克服以上现有技术的缺点:提供一种臭氧催化剂的制备方法。以拟薄水铝石、竹炭和石墨等作为载体,通过合理温度焙烧后冷却至常温,然后将适量的锰化合物、铜化合物的溶解液体采用喷淋法或者浸渍法分布到载体的孔道和表面层,最终制备成催化剂。
本发明的技术解决方案如下:一种臭氧催化剂的制备方法,包括以下步骤:
1)称取活性载体材料通过造粒后烘干,在氮气保护下于500-700℃焙烧制备活性载体;所述活性载体材料为拟薄水铝石与竹炭、石墨的混合物;
2)在活性载体上采用浸渍或喷淋法负载锰化合物、铜化合物;
3)将负载锰化合物、铜化合物的活性载体晾干后置于180-280℃网带窑炉中焙烧2-12h完成催化剂的复活成型制得臭氧催化剂。
竹炭:纤维度高,良好的中孔和蜂孔结构、脱吸速率快,不怕油污、净化效果好;石墨:耐酸、耐碱、耐有机溶剂的腐蚀、导电、导热比一般金属高百倍、含碳量60-80以上,化学性质稳定;
所述锰化合物为二氧化锰。
所述铜化合物为氧化铜、氯化铜中一种或两种。
二氧化锰:是两性氧化物,在酸性介质中是一种强氧化剂,高活性、放电性能优异;氯化铜:氧化剂、消毒剂、石油馏分的脱臭和脱硫。
步骤2)中所述锰化合物的重量为活性载体重量的5-7%。
步骤2)中所述铜化合物的重量为活性载体重量的3-4%。
本发明的有益效果是:增加化学氧化反应,通过氧催化氧化作用的活性,污水中的COD大分子量物质中键能较弱的化合键断开,生成分子量较小的物质,有效改变难生物降解的有机物结构,使其转化为有利降解的有机物质。
本发明的催化剂特殊造孔条件,是根据碳与铜等原料的微电解法技术思路,通过电化学的氧化还原过程,加深对污水中的COD完全适合催化剂的脱吸附和净化效果。催化剂的比表较大,吸附和脱附率好,在污水处理过程中,对水不会产生二次污染,充分体现到本发明的催化剂节能、环保。
本发明的催化剂在污水处理中,可根据单相和多相催化氧化工艺,也可适应静态水除污和动态水除污,并具备脱吸油污及污染水源脱色效果,是目前同类催化剂不可具备的条件。
本发明催化剂适用于炼油废水处理、印染、造纸、医药、化肥、农药、酒厂、焦化、冶金、养殖等多种污水的净化处理,处理过程中不留任何后遗症,确保催化剂不粉碎、不落粉,不会造成二次污染,催化剂使用效果好,使用寿命长。
电解氧化法是当前最先进的氧化技术,本发明结合电解氧化法特别有助于提升臭氧降解污水中的有机物,有助于污水中的脱色效果,使除污达到净化、节能、环保的效果。本发明可配合用于催化臭氧电解氧化方法对各种污水中的有机污染物的深度净化处理研发。产品脱吸附效果明显,可反复多次再生使用。
具体实施方式
下面用具体实施例对本发明做进一步详细说明,但本发明不仅局限于以下具体实施例。
实施例1
称取拟薄水铝石100kg,竹炭15kg,石墨15kg放入混料机混10min后,把水喷入混料机内再行混合60min,使原料的潮湿度均匀,通过粉碎机进行精细粉碎后放入捏合机加水或液体粘接剂进行捏合2h后,通过不同规格的模板、造粒制备所需规格如柱形或球形的载体颗粒。
将载体颗粒表面晾干后,进入烘干机于150℃烘干2h,然后氮气保护下于焙烧温度550-700℃焙烧2小时制得活性载体。
将冷却至常温的活性载体放置12h,做好浸渍法或喷淋法的前期准备。
称取二氧化锰,氯化铜分别放入容器内溶解成溶液备用;其中二氧化锰的重量为待浸渍或喷淋的活性载体重量的6.5-7%,氯化铜的重量为待浸渍或喷淋的活性载体重量的3.8-4%。
分别采用二氧化锰溶液,氯化铜溶液浸渍或喷淋活性载体,浸渍一次的时间为32h,喷淋一次的时间为26h,完成催化剂负载工艺,采用浸渍法每种溶液浸渍一次即可,喷淋法每种溶液喷淋两次为宜。
对负载合格催化剂,晾12-24h后,置于180℃-260℃网带窑炉中完成催化剂的复活成型。
催化剂臭氧分解率:150min 100%。比表面>390㎡/g,有效吸附孔径为>16nm,脱油污>43ppm/m³,脱色效果>98.7%。
实施例2
称量二氧化锰:8.75kg,氧化铜:4.95kg,拟薄水铝石90kg,竹炭20kg,石墨20kg。
拟薄水铝石、竹炭、石墨的称量为活性载体量,生产载体的方式与过程与实施例1相同。
负载工艺同实施例1。
催化剂:臭氧分解率:(180min)98.2%,比表面>410㎡/g,有效吸附孔径:>18.2nm,脱油污>45ppm,脱色效果>98.1%。
实施例3
称取 拟薄水铝石80kg,竹炭20kg,石墨30kg,二氧化锰8.5kg,氧化铜5kg。制备方法同实施例1,其中催化剂载体颗粒焙烧温度450-600℃,焙烧时间3h;
二氧化锰,氧化铜采用浸渍法吸入载体内,时间>32h, 置于网带窑于180℃-270℃焙烧2-6小时完成催化剂的复活成型。
催化剂臭氧分解率(200min以内)为97.9%,比表面>426㎡/g,有效吸附孔径:>18.6nm,脱油污>47ppm,脱色效果>97.6%。
实施例4
称取 拟薄水铝石100kg,竹炭15kg,石墨15kg,二氧化锰8.7kg,氯化铜4.9kg。
催化剂的制作过程同实施例1。
实验检测结果:催化剂的氧化分解率(150min)=92.0%,比表面积>340㎡/g,脱油污>31ppm,脱色效果>84.6%,催化剂有效吸附孔径>10nm。
以上仅是本发明的特征实施范例,对本发明保护范围不构成任何限制。凡采用同等交换或者等效替换而形成的技术方案,均落在本发明权利保护范围之内。

Claims (5)

1.一种臭氧催化剂的制备方法,其特征在于:包括以下步骤:
1)称取活性载体材料通过造粒后烘干,在氮气保护下于500-700℃焙烧制备活性载体;所述活性载体材料为拟薄水铝石与竹炭、石墨的混合物;
2)在活性载体上采用浸渍或喷淋法负载锰化合物、铜化合物;
3)将负载锰化合物、铜化合物的活性载体晾干后置于180-280℃中烘干2-6h完成催化剂的复活成型制得臭氧催化剂。
2.根据权利要求1所述的臭氧催化剂的制备方法,其特征在于:所述锰化合物为二氧化锰。
3.根据权利要求1所述的臭氧催化剂的制备方法,其特征在于:所述铜化合物为氧化铜、氯化铜中一种或两种。
4.根据权利要求1所述的臭氧催化剂的制备方法,其特征在于:步骤2)中所述锰化合物的重量为活性载体重量的5-7%。
5.根据权利要求1所述的臭氧催化剂的制备方法,其特征在于:步骤2)中所述铜化合物的重量为活性载体重量的3-4%。
CN201811091759.XA 2018-09-19 2018-09-19 一种臭氧催化剂的制备方法 Pending CN109126838A (zh)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002363544A (ja) * 2001-06-04 2002-12-18 Sinto Brator Co Ltd 球状投射材の製造方法及び投射材
WO2013057079A1 (en) * 2011-10-17 2013-04-25 Fundació Privada Institut Català D'investigació Química (Iciq) Process for water oxidation comprising the use of a polyoxometalate compound as water oxidation catalyst
CN104525206A (zh) * 2014-12-04 2015-04-22 格丰科技材料有限公司 一种去除废水中cod的多孔臭氧催化剂及其制备方法
CN106256426A (zh) * 2015-06-18 2016-12-28 中国石油化工股份有限公司 一种用于催化臭氧氧化的催化剂及其制备方法
CN108479784A (zh) * 2018-04-04 2018-09-04 清华大学 一种双载体臭氧催化剂和模块化催化氧化废水处理装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002363544A (ja) * 2001-06-04 2002-12-18 Sinto Brator Co Ltd 球状投射材の製造方法及び投射材
WO2013057079A1 (en) * 2011-10-17 2013-04-25 Fundació Privada Institut Català D'investigació Química (Iciq) Process for water oxidation comprising the use of a polyoxometalate compound as water oxidation catalyst
CN104525206A (zh) * 2014-12-04 2015-04-22 格丰科技材料有限公司 一种去除废水中cod的多孔臭氧催化剂及其制备方法
CN106256426A (zh) * 2015-06-18 2016-12-28 中国石油化工股份有限公司 一种用于催化臭氧氧化的催化剂及其制备方法
CN108479784A (zh) * 2018-04-04 2018-09-04 清华大学 一种双载体臭氧催化剂和模块化催化氧化废水处理装置

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