CN102452845A - 一种具有选择性的活性炭陶瓷及其制备方法 - Google Patents

一种具有选择性的活性炭陶瓷及其制备方法 Download PDF

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CN102452845A
CN102452845A CN2010105223614A CN201010522361A CN102452845A CN 102452845 A CN102452845 A CN 102452845A CN 2010105223614 A CN2010105223614 A CN 2010105223614A CN 201010522361 A CN201010522361 A CN 201010522361A CN 102452845 A CN102452845 A CN 102452845A
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active carbon
carbon ceramic
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董良杰
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Luohe micro ceramic purifying material Co., Ltd.
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Henan Tianyuan Environmental Protection High-Tech Co ltd
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Abstract

一种具有选择性的活性炭陶瓷,它主要由下述重量份的原料制成:污泥30-70、高岭土2-15、金属M或金属M的氧化物1-5,所述的具有选择性的活性炭陶瓷具有非晶状Si-C-M结构,其比表面积为400-500m2/g。本发明采取用造纸业废水、食品工业、和污水处理厂剩余污泥和高岭土并添加了农作物壳皮废弃物等配方,进行无氧加热烧制、微波活化多孔陶炭颗粒或粉末,形成一种生物选择性活性炭陶瓷。所得陶炭材料具有选择性吸附苯、酚、多烃类、二甲基硫、硫醚类恶臭物质的功能,用于空气过滤;陶炭并且具有为微生物提供有效的碳源、矿物质用于空气过滤、废水处理的生物媒介滤料;本材料同时具有吸附水中磷酸根离子功能,去除水中富氧成分。

Description

一种具有选择性的活性炭陶瓷及其制备方法
技术领域
[0001] 本发明属于空气过滤新材料和废水处理技术领域,具体涉及一种具有选择性的活性炭陶瓷及其制备方法。
背景技术
[0002] 造纸业废水、食品工业和污水处理厂、处理设施和其它废水生物处理后会产生大量的废弃污泥。因为污泥中含有大量的细菌微生物、重金属、臭味等有害物质,使污泥的无害化处理和再利用成为世界性的技术难题。如污泥中的病原菌、重金属等有害物质使其难以作为肥料应用,传统的处理方法是脱水、干燥,进行垃圾场填埋,但是垃圾场填埋占用大量的场地。另外一种处理方式是采取有氧焚烧的方式以减少污泥体积,但是焚烧过程中产生二恶英等有害物质污染空气。
[0003] 现有的吸附材料主要为活性炭、炭纤维材料等大比表面介质,用于吸附空气、和水中的苯酚类物质,但是活性炭的制作包括果壳类、煤质类的制作需要大量的化石燃料,且产生粉尘污染,成本和价格高昂。而且这些活性炭和纤维,对苯酚类仅停留物理吸附,不具备后续生物介质的消解功能。另外由多孔岩石,炉渣或塑料介质,多孔岩石,炉渣或塑料介质被广泛用作过滤介质或细菌附着生长介质,但是介质又不具备对苯、酚、多烃类、二甲基硫的吸附功能。
[0004] 现有技术中对于污泥的加热或焚烧多是在好氧环境中进行,烧制过程中碳源损失,形成陶粒或灰分、灰渣,并产生大量恶臭废气,生成的材料没有吸附恶臭和脱色功能。另夕卜,现有技术尚没有发现在配方中添加一定的农作物壳皮,把活性炭的吸附功能和生物介质的消解功能结合起来的新材料。
发明内容
[0005] 本发明的目的在于克服现有技术中存在的上述问题,提供一种选择性活性炭陶瓷及其制备方法。
[0006] 为实现上述目的,本发明采用的技术方案如下:
本发明的具有选择性的活性炭陶瓷,它主要由下述重量份的原料制成:污泥30-70、高岭土 2-15、金属或金属氧化物1-5。所述的具有选择性的活性炭陶瓷具有非晶状Si-C-M 结构,其比表面积为400-500 m2/g。
[0007] 所述的污泥为活性污泥,污泥中微生物含量> 70%。
[0008] 本发明的具有选择性的活性炭陶瓷优选由下述重量份的原料制成的:污泥 30-70、高岭土 2-15、金属或金属氧化物1-5、糠8-12。
[0009] 本发明的的具有选择性的活性炭陶瓷最好由下述重量份的原料制成的:污泥 30-70、高岭土 2-15、金属M或金属M的氧化物1_5、糠8_12、碳酸钙3_5。
[0010] 本发明具有选择性的活性炭陶瓷的制备方法,它是按下述步骤进行的:
(1)将生物活性炭陶瓷的原料按上述配方将各原材料混合,利用挤压或者圆盘造粒制作成形,干燥成型;
(2)将步骤(1)制得的成坯置于高温烘炉中真空或在氮气保护下烧制,烘炉温度以 90-110°C /h的升温速率升温到^5-305°C保持广2小时,此间产生的挥发性臭味气体通入煤气炉燃烧,其热量用于自身保温;
(3)烘炉温度以90-110°C /h的升温速率升温到740-760°C保持2_3小时;然后以 150-200°C /h的降温速率降温至室温,得陶炭介质;
(4)将步骤(3)制得的陶炭介质,加入水汽吸收1-1. 5小时,利用工业微波炉的进行活化0. 5-1小时,即得到本发明的生物活性炭陶瓷。
[0011] 步骤(2)中采用真空烧结时,高温烘炉中的真空度为-0. 08-0. 09 Mpa0
[0012] 步骤(2)中采用氮气保护烧结时,高温烘炉中通入氮气的压强为0. 1-0. 12Mpa。
[0013] 本发明中所述的金属M为!^e或Ti或Cu或Si中的任意一种。
[0014] 本发明中的糠可以用草屑代替,此外还可以根据需要添加其它适合的原料,比如液体石蜡、煤粉、膨化土等。
[0015] 本发明的活性炭陶瓷可以根据需要制成直径为0. 1-0. 5cm的柱状颗粒或圆球颗粒,也可以制成直径小于0. 15mm的粉末状材料。
[0016] 本发明的活性炭陶瓷可以用作石油原油残毒、石化废气、汽车尾气等苯类、酚类、 醛类、萘类等物质的吸附达到空气净化和过滤作用;本发明也可应用于生物滤池、滴滤池以及厌氧处理中的颗粒污泥床的生物介质。
[0017] 本发明采取用造纸业废水、食品工业、和污水处理厂剩余污泥和高岭土并添加了农作物壳皮废弃物等配方,进行无氧加热烧制、微波活化多孔陶炭颗粒或粉末,形成一种生物选择性活性炭陶瓷。所得陶炭材料具有选择性吸附苯、酚、多烃类、二甲基硫、硫醚类恶臭物质的功能,用于空气过滤;陶炭并且具有为微生物提供有效的碳源、矿物质用于空气过滤、废水处理的生物媒介滤料;本材料同时具有吸附水中磷酸根离子功能,去除水中富氧成分。本发明的核心理念是废弃物制造兼具吸附功能和生物介质的活性新材料,用于空气净化和废水处理。
[0018] 本发明的活性炭陶瓷具有可收缩的孔隙和固定微生物的功能。技术特点如下: 1、苯、酚类选择性吸附能力
活性炭陶瓷烧制过程中,产生了非晶形Si-C-M的表面活性物质,对苯、酚、萘等具有苯环物质具有特适性吸附结构,标准吸附容量大于350mg/g。对苯、酚、萘类的吸附能力分别为 360mg/g,560mg/g,600mg/go
[0019] 以上石油类残毒物质在海水、或淡水中,对盐类物质不吸附,本发明的活性炭陶瓷对以上物质仍具有350mg/g以上吸附能力。
[0020] 石油原油苯在海水中M小时吸附,1升海水含12000ng/ml,加入10克活性炭陶瓷,24小时吸附,海水中苯含量检测不到。
[0021] 2、对硫醚类物质的吸附于消解能力。硫醚为物质吸附于活性炭陶瓷的微孔表面后,于铁、钛粉类物质反应,生成FeS等物质,从消解掉恶臭。
[0022] 消解能力计算为:消解能力(%)=(吸附容量一酸洗溶出量)/吸附容量X 100%。
[0023] 活性炭陶瓷的化学消解率为总吸附容量的70% — 90%。[0024] 3、微生物生物固定即生物消解能力
烧制工艺采用缺氧环境加热,使污泥中的有机物碳化,不仅保留了下一代微生物生长的碳源,矿物元素可以作为细菌生长的营养,陶炭中的剩余无机元素为所诱获的新一代微生物生长提供了生长元素;可以用于硝化一反硝化过程的脱氮(硝态)的细菌载体。
[0025] 4、固定微生物消解吸附后的苯、酚类。对于含Ilppm酚类物质焦炭废水,全部吸附陶炭并加微生物接种,12小时后苯酚类物质减少一半。
[0026] 5、作为吸附或生物载体使用后的陶炭最为燃料焚烧。干燥的陶炭颗粒具有2000 大卡/kg到3750大卡/公斤的热量,吸附的挥发性物质都可以在600度以上的温度下燃烧。使用后的颗粒可以用作燃料和煤掺合后燃烧。
[0027] 与现有技术相比本发明的有益效果在于:
本发明可收缩活性炭陶瓷可以解决现有技术中存在的许多技术问题:(1)选择吸附苯酚类致癌物质;(2)同时具有对硫醚的吸附和化学消解功能;(3)本发明的活性炭陶瓷新配方和烧制工艺将污泥中重金属元素固定化,在应用过程中不会释放。(4)作为微生物载体进行硝化一反硝化水处理,微生物消解苯酚类物质。(5)使用后的陶炭具有2000ka/kg以上的热值,可于煤粉一起燃烧,解决了固体废物的遗留问题。
[0028] 本发明的材料具有不同直径的圆形颗粒、柱状颗粒、粉体可选择,使本发明的活性炭陶瓷拥有空气、水过滤等更加广泛的应用前景。
[0029] 本发明的活性炭陶瓷的应用,可供选择的用途包括以下任何一种:
1、作为空气净化剂材料,吸附空气中苯类、酚类、甲醛、多烃类等挥发和半挥发性物质。 例如作为透气纱袋装填,吸附新装修的地板、家具等有机释放物;化工厂挥发气体排放的吸附剂;汽车尾气的残留物等净化。
[0030] 2、含酚、苯类废水的处理吸附剂,例如装填入吸附塔吸附炸药、焦炭、陶瓷等行业的废水,进行终端净化处理。
[0031] 3、石油泄漏残毒在水体中的过滤和生物消解材料。原油泄漏后的致癌物质主要有苯类、酚类、多烃类污染物质,特别是在海水中,陶炭颗粒或粉末可以快速、有选择地吸附, 从而降低这些物质的环境危害。
[0032] 4、制作具备吸附功能陶炭工艺品、防臭鞋垫添加剂。
[0033] 5、作为生化介质用于污水处理,例如污水处理厂用的生物滤池滤料。由于活性炭陶瓷在烧制过程中施行缺氧烧制,微生物中的有机质被直接碳化。存留的碳素可以被微生物作为碳源利用,所以用活性炭陶瓷作为过滤材料,在消化和反硝化工程中不需要添加碳源。现有污水处理脱氮过程中,都需要添加甲醇或葡萄糖等作为碳源维持微生物的生长和新陈代谢。
[0034] 6、用作清理湖泊的富营养化。生化华陶瓷可以直接以吊装在网箱或网桶中以吸附兼性微生物以处理水中的有机污染物。
[0035] 7、陶瓷颗粒表面粗糙有助于改善厌氧处理的过程。
[0036] 8、用作转基因细菌固定化的活性炭陶瓷。
附图说明
[0037] 图1是本发明的活性炭陶瓷的电子扫描3000倍的照片。具体实施方式
[0038] 实施例1
本实施例的具有选择性的活性炭陶瓷,由下述重量份的原料制成:污泥30、高岭土 2、 铁粉1。
[0039] 其制备方法如下:
(1)将生物活性炭陶瓷的原料按上述配方将各原材料混合,利用挤压或者圆盘造粒制作成形,干燥成型;
(2)将步骤(1)制得的成坯置于高温烘炉中真空下烧制,高温烘炉中的真空度为-0. 08-0. 09 Mpa0烘炉温度以90°C /h的升温速率升温到300°C保持1. 5小时,此间产生的挥发性臭味气体通入煤气炉燃烧,其热量用于自身保温;
(3)烘炉温度以90°C /h的升温速率升温到740°C保持3小时;然后以150°C /h的降温速率降温至室温,得陶炭介质;
(4)将步骤(3)制得的陶炭介质,加入水汽吸收1. 5小时,利用工业微波炉的进行活化 0. 5小时,即得到本发明的生物活性炭陶瓷。
[0040] 本实施例的具有选择性的活性炭陶瓷具有非晶状Si-C-Fe结构,其比表面积为 400 m2/g。
[0041] 实施例2
本实施例的具有选择性的活性炭陶瓷,由下述重量份的原料制成:污泥50、高岭土 10、铜粉3、麦糠8。
[0042] 其制备方法如下:
(1)将生物活性炭陶瓷的原料按上述配方将各原材料混合,利用挤压或者圆盘造粒制作成形,干燥成型;
(2)将步骤(1)制得的成坯置于高温烘炉在氮气保护下烧制,高温烘炉中通入氮气的压强为0. 1-0. 12Mpa。烘炉温度以100°C /h的升温速率升温到300°C保持1. 5小时,此间产生的挥发性臭味气体通入煤气炉燃烧,其热量用于自身保温;
(3)烘炉温度以100°C /h的升温速率升温到750°C保持2. 5小时;然后以180°C /h的降温速率降温至室温,得陶炭介质;
(4)将步骤(3)制得的陶炭介质,加入水汽吸收1. 2小时,利用工业微波炉的进行活化 0. 8小时,即得到本发明的生物活性炭陶瓷。
[0043] 本实施例的具有选择性的活性炭陶瓷具有非晶状Si-C-Cu结构,其比表面积为 420 m2/g。
[0044] 实施例3
本实施例的具有选择性的活性炭陶瓷,由下述重量份的原料制成:污泥30-70、高岭土 2-15、Zn 1-5、糠 8-12、碳酸钙 3-5。
[0045] 其制备方法如下:
(1)将生物活性炭陶瓷的原料按上述配方将各原材料混合,利用挤压或者圆盘造粒制作成形,干燥成型;
(2)将步骤(1)制得的成坯置于高温烘炉中在氮气保护下烧制,高温烘炉中通入氮气的压强为O. 1-0. 12Mpa。烘炉温度以110°C /h的升温速率升温到305°C保持1小时,此间产生的挥发性臭味气体通入煤气炉燃烧,其热量用于自身保温;
(3)烘炉温度以110°C /h的升温速率升温到760°C保持2小时;然后以200°C /h的降温速率降温至室温,得陶炭介质;
(4)将步骤(3)制得的陶炭介质,加入水汽吸收1小时,利用工业微波炉的进行活化1 小时,即得到本发明的生物活性炭陶瓷。
[0046] 本实施例的具有选择性的活性炭陶瓷具有非晶状Si-C-Si结构,其比表面积为 460 m2/g。
[0047] 实施例4
本实施例的具有选择性的活性炭陶瓷,由下述重量份的原料制成:污泥70份,麦糠10 份,高岭土 2份,还原铁粉1份,膨化土 2份。
[0048] 其制备方法同实施例2的制备方法。
[0049] 本实施例的具有选择性的活性炭陶瓷具有非晶状Si-C-狗结构,其比表面积为 500 m2/g。
[0050] 实施例5
本实施例的具有选择性的活性炭陶瓷,由下述重量份的原料制成:污泥34-55份,二氧化钛8-10份,碳酸钙3-4份,高岭土 8-10份,液体蜡1-2份,氧化铜粉体5_6份。
[0051] 其制备方法同实施例2的制备方法,制备成在空气过滤作为过滤器用的直径小于 0. 1-0. 5cm的柱状活性炭陶瓷。
[0052] 本实施例的具有选择性的活性炭陶瓷具有非晶状Si-C-狗结构,其比表面积为 460 m2/g。
[0053] 实施例6
本实施例的具有选择性的活性炭陶瓷,由下述重量份的原料制成:造纸工业污泥65 份,碳酸钙8份,粘土 15份,草屑6-8份,锌粉1份,铁粉1-3份,煤粉1-3份。
[0054] 其制备方法同实施例2的制备方法,制备成在用于化工废水反应器的直径小于 0. 1-0. 5cm的球状活性炭陶瓷。
[0055] 本实施例的具有选择性的活性炭陶瓷具有非晶状Si-C-狗结构,其比表面积为 460 m2/g。
[0056] 本发明的活性炭陶瓷的性能试验方法及试验结果如下: 1、炼油厂烟气/废气过滤实验
将IOOg直径0. 5毫米的颗粒装入5厘米直径玻璃筒;加入15毫升水保持颗粒的湿润度,苯类挥发物质含量0. 5ug/L,去除率大于98%。空气流量5升/分钟;在线GC-MT同质及时检测,测定去除率,100克陶粒在不同阶段的去除率,0 - 36立方米98% ;36 一 68立方米,90% ;68 - 100立方米;达到85%得去除率;100 — 300立方米,80%。
[0057] 2、静态空气中苯、二甲苯和甲醛吸附实验
2立方米密封容器;污染物初始浓度挥发苯2毫克/立方米;甲醛2毫克/立方米;二甲苯1. 8毫克/立方米;吊装5克生物陶炭尼龙袋;测定M小时吸附速度。全静止、无混合吸附实验
吸附试验结果如下:
Figure CN102452845AD00081
3、海水中苯系物吸附试验
实验方法:(1)取秦皇岛天然海水50升导入封闭容器大桶,按1 :1000加入原油,封闭振荡M小时,得母液带测定。(2)加入20克生物陶炭与纱袋中,吊放入海水桶中,继续封闭振荡。(3)按照0,2,4,8,12,24,72,96小时分别取样20毫升,密闭送检。(4)用气质质朴联检仪器检测苯酚类各物质的含量,得下表格结果。 [0058]
Figure CN102452845AD00082
Figure CN102452845AD00091

Claims (8)

1. 一种具有选择性的活性炭陶瓷,其特征在于:它主要由下述重量份的原料制成:污泥30-70、高岭土 2-15、金属M或金属M的氧化物1_5,所述的具有选择性的活性炭陶瓷具有非晶状Si-C-M结构,其比表面积为400-500 m2/g。
2.根据权利要求1所述的具有选择性的活性炭陶瓷,其特征在于:所述的污泥为活性污泥,污泥中微生物含量> 70%。
3.根据权利要求1或2所述的具有选择性的活性炭陶瓷,其特征在于:它主要由下述重量份的原料制成,污泥30-70、高岭土 2-15、金属M或金属M的氧化物1_5、糠8_12。
4.根据权利要求3所述的具有选择性的活性炭陶瓷,其特征在于:它由下述重量份的原料制成,污泥30-70、高岭土 2-15、金属M或金属M的氧化物1_5、糠8_12、碳酸钙3_5。
5.根据权利要求4所述的具有选择性的活性炭陶瓷,其特征在于它由下述重量份的原料制成的:所述的金属M为!^e或Ti或Cu或Si中的任意一种。
6.权利要求1所述的具有选择性的活性炭陶瓷的制备方法,其特征在于它是按下述步骤进行的:(1)将生物活性炭陶瓷的原料按上述配方将各原材料混合,利用挤压或者圆盘造粒制作成形,干燥成型;(2)将步骤(1)制得的成坯置于高温烘炉中真空或在氮气保护下烧制,烘炉温度以 90-110°C /h的升温速率升温到^5-305°C保持广2小时,此间产生的挥发性臭味气体通入煤气炉燃烧,其热量用于自身保温;(3)烘炉温度以90-110°C /h的升温速率升温到740-760°C保持2_3小时;然后以 150-200°C /h的降温速率降温至室温,得陶炭介质;(4)将步骤(3)制得的陶炭介质,加入水汽吸收1-1. 5小时,利用工业微波炉的进行活化0. 5-1小时,即得到本发明的生物活性炭陶瓷。
7.根据权利要求6所述的具有选择性的活性炭陶瓷的制备方法,其特征在于它是按下述步骤进行的:步骤(2)中高温烘炉中的真空度为-0. 08-0. 09 Mpa0
8.根据权利要求6所述的具有选择性的活性炭陶瓷的制备方法,其特征在于它是按下述步骤进行的:步骤(2)中高温烘炉中通入氮气的压强为0. 1-0. 12Mpa。
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CN102730911A (zh) * 2012-07-10 2012-10-17 辽宁大学 一种降解废水中苯酚的方法
CN104226251A (zh) * 2014-09-29 2014-12-24 镇江华域环保设备制造有限公司 一种氧化改性活性炭吸附剂及其制备方法
CN104973680A (zh) * 2015-07-27 2015-10-14 宁波江东仑斯福环保科技有限公司 一种高效多用污水处理剂及利用其处理污水的方法
CN105000602A (zh) * 2015-07-27 2015-10-28 宁波江东仑斯福环保科技有限公司 一种城市污水综合处理剂及其制备方法和应用
CN105016444A (zh) * 2015-07-24 2015-11-04 刘雷 一种高效污水处理剂及利用其处理污水的方法
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CN105152290A (zh) * 2015-07-24 2015-12-16 刘雷 一种污水综合处理剂及其制备方法和应用
CN105174329A (zh) * 2015-10-16 2015-12-23 张瑞侠 一种以焦磷酸钠为增效剂的污水处理剂
CN105198012A (zh) * 2015-08-07 2015-12-30 刘广利 一种多用污水处理剂及利用其处理污水的方法
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CN102730911A (zh) * 2012-07-10 2012-10-17 辽宁大学 一种降解废水中苯酚的方法
CN104226251A (zh) * 2014-09-29 2014-12-24 镇江华域环保设备制造有限公司 一种氧化改性活性炭吸附剂及其制备方法
CN105110385A (zh) * 2015-07-24 2015-12-02 刘雷 一种高效多用污水处理剂及利用其处理污水的方法
CN105152290A (zh) * 2015-07-24 2015-12-16 刘雷 一种污水综合处理剂及其制备方法和应用
CN105016444A (zh) * 2015-07-24 2015-11-04 刘雷 一种高效污水处理剂及利用其处理污水的方法
CN105000602A (zh) * 2015-07-27 2015-10-28 宁波江东仑斯福环保科技有限公司 一种城市污水综合处理剂及其制备方法和应用
CN104973680A (zh) * 2015-07-27 2015-10-14 宁波江东仑斯福环保科技有限公司 一种高效多用污水处理剂及利用其处理污水的方法
CN105198012A (zh) * 2015-08-07 2015-12-30 刘广利 一种多用污水处理剂及利用其处理污水的方法
CN105036218A (zh) * 2015-09-09 2015-11-11 韩功篑 一种环保型污水处理剂及制备方法
CN105174329A (zh) * 2015-10-16 2015-12-23 张瑞侠 一种以焦磷酸钠为增效剂的污水处理剂
CN106390997A (zh) * 2016-09-28 2017-02-15 广州凯耀资产管理有限公司 一种汽车尾气净化催化剂及其制备方法和运用
CN106693878A (zh) * 2017-01-23 2017-05-24 江苏省农业科学院 水产养殖水质改善及尾水净化用填料颗粒、其制备方法及包含其的反应器
CN106693878B (zh) * 2017-01-23 2018-07-10 江苏省农业科学院 水产养殖水质改善及尾水净化用填料颗粒、其制备方法及包含其的反应器

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