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WO2012055257A1 - 一种具有选择性吸附消解功能的生物陶及其制备方法 - Google Patents

一种具有选择性吸附消解功能的生物陶及其制备方法 Download PDF

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Publication number
WO2012055257A1
WO2012055257A1 PCT/CN2011/076305 CN2011076305W WO2012055257A1 WO 2012055257 A1 WO2012055257 A1 WO 2012055257A1 CN 2011076305 W CN2011076305 W CN 2011076305W WO 2012055257 A1 WO2012055257 A1 WO 2012055257A1
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bioceramic
sludge
selective adsorption
metal
raw materials
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PCT/CN2011/076305
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English (en)
French (fr)
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董良杰
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河南天源环保高科股份有限公司
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Publication of WO2012055257A1 publication Critical patent/WO2012055257A1/zh

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Definitions

  • the invention belongs to the technical field of air filtration new materials and wastewater treatment, and particularly relates to a biological ceramic with selective adsorption digestion function and a preparation method thereof.
  • a large amount of waste sludge is produced after the paper industry wastewater, the food industry and sewage treatment plants, treatment facilities and other wastewaters are biologically treated. Because sludge contains a large amount of harmful substances such as bacterial microorganisms, heavy metals, and odors, the harmless treatment and reuse of sludge has become a worldwide technical problem. For example, harmful substances such as pathogenic bacteria and heavy metals in sludge make it difficult to use as a fertilizer.
  • the traditional treatment method is dehydration, drying, and landfill landfill, but landfills occupy a large number of sites.
  • Another treatment is to use aerobic incineration to reduce sludge volume, but harmful substances such as dioxins are polluted during the incineration process.
  • the existing adsorbent materials are mainly large-surface mediums such as activated carbon and carbon fiber materials, which are used for adsorbing air and phenolic substances in water.
  • activated carbon including the production of shells and coals, requires a large amount of fossil fuels. It also produces dust pollution, which is costly and expensive.
  • these activated carbons and fibers only physically adsorb to the phenols and do not have the digestion function of the subsequent biological medium.
  • porous rock, slag or plastic media, porous rock, slag or plastic media are widely used as filter media or bacterial attachment growth media, but the media does not have adsorption function for benzene, phenol, polyhydrocarbons, dimethyl sulfide. .
  • the heating or incineration of the sludge is mostly carried out in an aerobic environment, the carbon source is lost during the firing process, ceramsite or ash, ash and slag are formed, and a large amount of odorous exhaust gas is generated, and the generated material does not adsorb malodor and Decolorization function.
  • the prior art has not found a new material in which a certain crop skin is added to the formulation, and the adsorption function of the activated carbon and the digestion function of the biological medium are combined.
  • the object of the present invention is to overcome the above problems in the prior art and to provide a bioceramic having a selective adsorption digestion function and a preparation method thereof.
  • the bioceramic having the selective adsorption digestion function of the present invention is mainly made of the following raw materials by weight: sludge 30-70, kaolin 2-15, metal or metal oxide 1-5.
  • the selective bioceramic has an amorphous Si-C-M structure having a specific surface area of 400-500 m2/g.
  • the sludge is activated sludge, and the sludge has a microbial content of 70%.
  • the bioceramic having the selective adsorption digestion function of the present invention is preferably made of the following raw materials by weight: sludge
  • the bioceramic having the selective adsorption digestion function of the present invention is preferably made of the following raw materials by weight: sludge 30-70, kaolin 2-15, metal M or oxide of metal M 1-5, ⁇ 8 -12, calcium carbonate 3-5.
  • the preparation method of the bioceramic having the selective adsorption digestion function of the invention is carried out according to the following steps:
  • the preform obtained in the step (1) is placed in a high-temperature oven under vacuum or fired under nitrogen atmosphere, and the oven temperature is raised to 295-305 ° C at a temperature increase rate of 90-110 ° C / h. 1 ⁇ 2 hours, the volatile odor gas generated here is burned into the gas furnace, and the heat is used for self-insulation;
  • the oven temperature is raised to 740-76 CTC at a temperature increase rate of 90-110 ° C / h for 2-3 hours; then cooled to room temperature at a cooling rate of 150-200 ° C / h to obtain a biological ceramic medium;
  • the bio-ceramic medium obtained in the step (3) is added to the water vapor for 1-1.5 hours, and activated by an industrial microwave oven for 0.5-1 hour to obtain the bioceramic of the present invention.
  • step (2) When vacuum sintering is used in step (2), the vacuum in the high temperature oven is -0.08-0.09 Mpa.
  • the pressure of nitrogen gas in the high temperature oven is 0.1-0.12 MPa.
  • the metal M described in the present invention is any one of Fe or Ti or Cu or Zn.
  • the crucible in the present invention may be replaced by grass clippings, and other suitable raw materials such as liquid paraffin, coal powder, expanded soil and the like may be added as needed.
  • the bioceramic of the present invention can be formed into columnar particles or pellets having a diameter of 0.1 to 0.5 cm as needed, or a powdery material having a diameter of less than 0.15 mm.
  • the bio-ceramic having the selective adsorption digestion function of the invention can be used for the adsorption of benzene, phenols, aldehydes, naphthalenes and the like of petroleum crude oil residual oil, petrochemical waste gas, automobile exhaust gas, etc. to achieve air purification and filtration; It can be applied to biofilters, trickling filters, and biological media for granular sludge beds in anaerobic treatment.
  • the invention adopts a formulation of waste water and food industry of the papermaking industry, and waste sludge and kaolin of the sewage treatment plant and adds the waste material of the crop crust, and performs the anaerobic heating firing, the microwave activation of the porous bioceramic particles or the powder, forming a kind Bioselective bioceramics.
  • the obtained bioceramic material has the function of selectively adsorbing odorous substances of benzene, phenol, polyhydrocarbons, dimethyl sulfide and thioethers, and is used for air filtration; bio-ceramic and has an effective carbon source and mineral for microorganisms.
  • Biofilter media for air filtration and wastewater treatment this material also has phosphate ion work in adsorbed water Can remove oxygen-rich ingredients from water.
  • the core concept of the present invention is waste manufacturing a new active material with both adsorption and biological media for air purification and wastewater treatment.
  • the bioceramic of the present invention has a function of shrinkable pores and immobilization of microorganisms.
  • the technical features are as follows:
  • a surface active material of amorphous Si-C-M is produced, and a benzene ring material such as benzene, phenol or naphthalene has an adsorption structure with a specific adsorption capacity of more than 350 mg/g.
  • the adsorption capacities for benzene, phenol, and naphthalene are 360 mg/g, 560 mg/g, and 600 mg/g, respectively.
  • the above petroleum-based residual substances are not adsorbed to the salty substances in seawater or fresh water, and the bioceramics of the present invention still have an adsorption capacity of 350 mg/g or more.
  • the petroleum crude oil benzene is adsorbed in seawater for 24 hours, 1 liter of seawater contains 12000 ng/ml, 10 g of bio-potassy is added, and adsorption is carried out for 24 hours, and the benzene content in seawater is not detected.
  • the chemical digestion rate of bio-ceramics is 70%-90% of the total adsorption capacity.
  • microbial biological fixation is the ability of biological digestion
  • the firing process is heated in an anoxic environment to carbonize the organic matter in the sludge, which not only retains the carbon source for the growth of the next generation of microorganisms, but also acts as a nutrient for the growth of bacteria.
  • the remaining inorganic elements in the biological pottery are the new ones that are trapped.
  • a generation of microbial growth provides growth elements; a bacterial carrier that can be used for denitrification (nitrate) in a nitrification-denitrification process.
  • Bio-ceramics used as adsorption or biological carriers are the most fuel incineration.
  • the dried bioceramic particles have a heat of 2000 kg/kg to 3750 kcal I kg, and the adsorbed volatile substances can be burned at temperatures above 600 degrees.
  • the used particles can be used as a fuel and coal after combustion.
  • the invention has the beneficial effects that the bio-ceramic having the selective adsorption digestion function of the invention can solve many technical problems existing in the prior art: (1) selective adsorption of phenolic carcinogens; (2) At the same time, it has the function of adsorption and chemical digestion of thioether; (3) The new biological formula of the invention and the firing process will make the sludge heavy The metal element is immobilized and will not be released during application. (4) Nitrification-denitrification water treatment as a microbial carrier, and microbial digestion of phenolic substances. (5) After use, the bio-ceramic has a calorific value of 2000 ka/kg or more, which can be burned together with pulverized coal to solve the problem of leaving solid waste.
  • the material of the present invention has round particles of different diameters, columnar particles, and powders, and the biological pottery of the present invention has a wider application prospect such as air and water filtration.
  • the alternative uses include any of the following:
  • an air purifier material it adsorbs volatile and semi-volatile substances such as benzene, phenols, formaldehyde, and hydrocarbons in the air.
  • volatile and semi-volatile substances such as benzene, phenols, formaldehyde, and hydrocarbons in the air.
  • it is used as a breathable yarn bag to absorb organic discharges such as newly-decorated floors and furniture; an adsorbent for volatile gas emitted from chemical plants; and a residue of automobile exhaust gas.
  • adsorbents containing phenol and benzene wastewater such as waste water loaded into adsorption towers for adsorbing explosives, coke, ceramics, etc., for terminal purification treatment.
  • biochemical medium for sewage treatment such as biological filter media for sewage treatment plants. Since the bio-ceramic is subjected to anoxic firing during the firing process, the organic matter in the microorganism is directly carbonized. The remaining carbon can be used as a carbon source by the microorganisms, so the use of bio-ceramics as a filter material does not require the addition of a carbon source in the digestion and denitrification projects. In the existing sewage treatment and denitrification process, it is necessary to add methanol or glucose as a carbon source to maintain the growth and metabolism of microorganisms.
  • Bio-ceramics Used to clean up the eutrophication of lakes.
  • Bio-ceramics can be directly hoisted in cages or net buckets to adsorb facultative microorganisms to treat organic contaminants in the water.
  • the surface roughness of the bioceramic particles helps to improve the process of anaerobic treatment.
  • Fig. 1 is a photograph showing a 3000-fold electronic scanning of a bioceramic of the present invention.
  • the bioceramic particles have 1-3 m voids and irregular structures inside, and are selected to adsorb benzene and phenols.
  • Example 1 The bioceramic having the selective adsorption digestion function of the present embodiment is made of the following raw materials by weight: sludge 30, kaolin 2, and iron powder 1.
  • the preparation method is as follows:
  • the preform obtained in the step (1) is placed in a high-temperature oven and fired under vacuum.
  • the vacuum degree in the high-temperature oven is -0.08-0.09 Mpao, and the oven temperature is raised at a temperature increase rate of 90 ° C / h. Maintaining at 300 ° C for 1.5 hours, the volatile odor gas generated here is burned into the gas furnace, and the heat is used for self-heating;
  • the bio-ceramic medium obtained in the step (3) was subjected to water vapor absorption for 1.5 hours, and activated by an industrial microwave oven for 0.5 hour to obtain the bio-bioceramic of the present invention.
  • the selective bioceramic of the present embodiment has an amorphous Si-C-Fe structure having a specific surface area of 400 m2.
  • the bioceramic having the selective adsorption digestion function of the present embodiment is made of the following raw materials by weight: sludge
  • the preparation method is as follows:
  • the preform obtained in the step (1) is placed in a high-temperature oven and fired under a nitrogen atmosphere, and the pressure of the nitrogen gas introduced into the high-temperature oven is 0.1-0.12 MPa.
  • the oven temperature is raised to 300 ° C at a heating rate of 100 ° C / h for 1.5 hours, and the volatile odor gas generated here is burned into a gas furnace, and the heat is used for self-heating;
  • the oven temperature is raised to 750 ° C at a heating rate of 100 ° C / h for 2.5 hours; then cooled to room temperature at a cooling rate of 180 ° C / h to obtain a biological ceramic medium;
  • the bio-ceramic medium obtained in the step (3) was subjected to water vapor absorption for 1.2 hours, and activated by an industrial microwave oven for 0.8 hours to obtain the bio-bioceramic of the present invention.
  • the selective bioceramic of the present embodiment has an amorphous Si-C-Cu structure having a specific surface area of 420 m2.
  • the bioceramic having the selective adsorption digestion function of the present embodiment is made of the following raw materials by weight: sludge 30-70, kaolin 2-15, Zn l-5, ⁇ 8-12, calcium carbonate 3-5.
  • the preparation method is as follows:
  • the preform obtained in the step (1) is placed in a high-temperature oven and fired under a nitrogen atmosphere, and the pressure of the nitrogen gas introduced into the high-temperature oven is 0.1-0.12 MPa.
  • the oven temperature is raised to 305 ° C at a heating rate of 110 ° C / h for 1 hour, and the volatile odor gas generated here is burned into a gas furnace, and the heat is used for self-heating;
  • the bio-ceramic medium obtained in the step (3) was absorbed by water vapor for 1 hour, and activated by an industrial microwave oven for 1 hour to obtain the bio-bioceramic of the present invention.
  • the selective bioceramic of the present embodiment has an amorphous Si-C-Zn structure having a specific surface area of 460 ml/g o.
  • the bioceramic having the selective adsorption digestion function of the present embodiment is made of the following raw materials by weight: 70 parts of sludge, 10 parts of wheat bran, 2 parts of kaolin, 1 part of reduced iron powder, and 2 parts of expanded soil.
  • the preparation method is the same as the preparation method of Example 2.
  • the selective bioceramic of this embodiment has an amorphous Si-C-Fe structure having a specific surface area of 500 m2/go.
  • the bioceramic having the selective adsorption digestion function of the present embodiment is made of the following raw materials by weight: 34-55 parts of sludge, 8-10 parts of titanium dioxide, 3-4 parts of calcium carbonate, 8-10 parts of kaolin, 1-2 parts of liquid wax, 5-6 parts of copper oxide powder.
  • the preparation method is the same as the preparation method of Example 2, and is prepared into a columnar bioceramic having a diameter of less than 0.1 to 0.5 cm for use as a filter for air filtration.
  • the selective bioceramic of this embodiment has an amorphous Si-C-Fe structure having a specific surface area of 460 m2/g.
  • the bioceramic having the selective adsorption digestion function of the present embodiment is made of the following raw materials by weight: 65 parts of paper industry sludge, 8 parts of calcium carbonate, 15 parts of clay, 6-8 parts of grass clippings, zinc powder 1 Parts, 1-3 parts of iron powder, 1-3 parts of coal powder.
  • the preparation method thereof is the same as the preparation method of the embodiment 2, and is prepared to have a diameter smaller than that used in the chemical wastewater reactor. 0.1-0.5 cm spherical bio-ceramic.
  • the selective bioceramic of this embodiment has an amorphous Si-C-Fe structure having a specific surface area of 460 m2/g.
  • the performance test method and test results of the bioceramic of the present invention are as follows:
  • 1,2-Dichlorobenzene-D4% 60-130 87.0 90.3 90.8 the detection report of the removal effect of the bio-ceramic of the present invention on benzene, toluene and xylene in indoor air.
  • the unit that has been photographed by the speculative unit may not be used for commercial or commercial promotion; 3 ⁇ 4

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Description

一种具有选择性吸附消解功能的生物陶及其制备方法
技术领域
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吸附消 解功能的生物陶及其制备方法。
背景技术
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。
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。
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。 另外， 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
本发明的目的在于克服现有技术中存在的上述问题，提供一种具有选择性吸附消解 功能的生物陶及其制备方法。
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吸附消解功能的生物陶， 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生物陶具有非晶 状 Si-C-M结构， 其比表面积为 400-500 m2/g。
所述的污泥为活性污泥， 污泥中微生物含量 70%。 本发明的具有选择性吸附消解功能的生物陶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。
本发明的具有选择性吸附消解功能的生物陶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。
本发明的具有选择性吸附消解功能的生物陶的制备方法， 它是按下述步骤进行的：
( 1 ) 将生物陶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 295-305°C保持 1~2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 740-76CTC保持 2-3小时； 然后以 150-200°C/h的降温速率降温至室温， 得生物陶介质；
(4) 将步骤 （3) 制得的生物陶介质， 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陶。
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 Mpa。
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。 本发明中所述的金属 M为 Fe或 Ti或 Cu或 Zn中的任意一种。
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。
本发明的生物陶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。
本发明的具有选择性吸附消解功能的生物陶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。
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、 微波活化多孔生物陶颗粒或粉末， 形成 一种生物选择性生物陶。 所得生物陶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； 生物陶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。
本发明的生物陶具有可收縮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
生物陶烧制过程中， 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/g。
以上石油类残毒物质在海水、 或淡水中， 对盐类物质不吸附， 本发明的生物陶对以 上物质仍具有 350mg/g以上吸附能力。
石油原油苯在海水中 24小时吸附， 1升海水含 12000ng/ml， 加入 10克生物陶， 24 小时吸附， 海水中苯含量检测不到。
2、 对硫醚类物质的吸附于消解能力。 硫醚为物质吸附于生物陶的微孔表面后， 于 铁、 钛粉类物质反应， 生成 FeS等物质， 从消解掉恶臭。
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 %。
生物陶的化学消解率为总吸附容量的 70 %— 90 %。
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， 生物陶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。
4、 固定微生物消解吸附后的苯、 酚类。对于含 llppm酚类物质焦炭废水， 全部吸 附生物陶并加微生物接种， 12小时后苯酚类物质减少一半。
5、作为吸附或生物载体使用后的生物陶最为燃料焚烧。干燥的生物陶颗粒具有 2000 大卡/ kg到 3750大卡 I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。
与现有技术相比本发明的有益效果在于：本发明的具有选择性吸附消解功能的生物 陶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 )本发明的生物陶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 ) 使用后的生物陶具有 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。
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， 使本发明的生 物陶拥有空气、 水过滤等更加广泛的应用前景。
本发明的生物陶的应用， 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。
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。
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， 生物陶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。
4、 制作具备吸附功能生物陶工艺品、 防臭鞋垫添加剂。
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。 由于生物陶 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， 所以用生物陶作为过滤材料， 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。
6、 用作清理湖泊的富营养化。 生物陶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。
7、 生物陶颗粒表面粗糙有助于改善厌氧处理的过程。
8、 用作转基因细菌固定化的生物陶。
附图说明
图 1是本发明的生物陶的电子扫描 3000倍的照片。 生物陶颗粒内部有 1— 3um的空隙和不 规则结构， 选择吸附苯、 酚类物质。
具体实施方式
实施例 1 本实施例的具有选择性吸附消解功能的生物陶， 由下述重量份的原料制成： 污泥 30、 高岭土 2、 铁粉 1。
其制备方法如下：
( 1 ) 将生物生物陶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 Mpao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， 得生物陶介质；
(4) 将步骤 （3) 制得的生物陶介质， 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生物陶。
本实施例的具有选择性的生物陶具有非晶状 Si-C-Fe结构，其比表面积为 400 m2 实施例 2
本实施例的具有选择性吸附消解功能的生物陶， 由下述重量份的原料制成： 污泥
50、 高岭土 10、 铜粉 3、 麦糠 8。
其制备方法如下：
( 1 ) 将生物生物陶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， 得生物陶介质；
(4) 将步骤 （3) 制得的生物陶介质， 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生物陶。
本实施例的具有选择性的生物陶具有非晶状 Si-C-Cu结构，其比表面积为 420 m2 实施例 3
本实施例的具有选择性吸附消解功能的生物陶， 由下述重量份的原料制成： 污泥 30-70、 高岭土 2-15、 Zn l-5、 糠 8-12、 碳酸钙 3-5。
其制备方法如下：
( 1 ) 将生物生物陶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 0.1-0.12Mpa。 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， 得生物陶介质；
(4)将步骤 （3 )制得的生物陶介质， 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生物陶。
本实施例的具有选择性的生物陶具有非晶状 Si-C-Zn结构，其比表面积为 460 ml/ g o 实施例 4
本实施例的具有选择性吸附消解功能的生物陶， 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 。
其制备方法同实施例 2的制备方法。
本实施例的具有选择性的生物陶具有非晶状 Si-C-Fe结构，其比表面积为 500 m2/go 实施例 5
本实施例的具有选择性吸附消解功能的生物陶， 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。
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的柱状生物陶。
本实施例的具有选择性的生物陶具有非晶状 Si-C-Fe结构，其比表面积为 460 m2/g。 实施例 6
本实施例的具有选择性吸附消解功能的生物陶， 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。
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的球状生物陶。
本实施例的具有选择性的生物陶具有非晶状 Si-C-Fe结构，其比表面积为 460 m2/g。 本发明的生物陶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 100g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 %。
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 I立方米； 吊装 5克生物生物陶尼龙袋；测定 24小时吸附速度。全静止、 无混合吸附实验， 吸附试验结果如表 1。
表 1静态空气中苯、 二甲苯和甲醛吸附实验结果
Figure imgf000009_0001
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 24小时， 得母液带测定。 （2) 加入 20克生物生物陶 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， 48， 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， 结果见表 2。
表 2海水中苯系物吸附试验结果
/ __ 样品原号 （吸附时间） 0 (ck) 1 (2小时） 2 (4小时） 分析项目 -—
检测编号 YJ10073001 YJ10073002 YJ10073003 挥发性有机物 单位 报出限 0 2 4 苯 ng/mL 1.00 11725 9042 4393 甲苯 ng/mL 1.00 5151 4042 1357 乙苯 ng/mL 1.00 341 230 130 间对二甲苯 ng/mL 1.00 1223 824 170 邻二甲苯 ng/mL 1.00 765 598 326 苯乙録 ng/mL 1.00 <1.00 <1.00 <1.00 替代物回收率 % 控制限
二溴氟甲烷 % 60- 130 98.3 94.0 100.8 氟苯 % 60- 130 96.7 92.5 98.1 甲苯 -D8 % 60- 130 94.5 92.2 95.6
4-溴氟苯 % 60- 130 97.1 93.1 97.7
1, 2-二氯苯 -D4 % 60- 130 95.6 91.2 97.9 样品原号 3 (8小时) 4 (12小时） 5 (24小时）
Figure imgf000010_0001
检测编号 YJ10073004 YJ10073005 YJ10073006 挥发性有机物 单位 报出限 8 12 24 苯 ng/mL 1.00 2499 408.9 0 甲苯 ng/mL 1.00 627 2.91 0 乙苯 ng/mL 1.00 1 0 0 间对二甲苯 ng/mL 1.00 1 0 0 邻二甲苯 ng/mL 1.00 107 0 0 苯乙録 ng/mL 1.00 <1.00 <1.00 <1.00 替代物回收率 % 控制限
二溴氟甲烷 % 60- 130 98.7 105 103 氟苯 % 60- 130 94.0 98.1 97.1 甲苯 -D8 % 60- 130 92.5 100 94.9
4-溴氟苯 % 60- 130 91.9 102 95.1
1, 2-二氯苯 -D4 % 60- 130 93.9 102 97.0 样品原号 6 ( 48小时） Ί (72) 8 ( 96) 分析项目
检测编号 YJ10073007 YJ10073008 YJ10073009 挥发性有机物 单位 报出限
苯 ng/mL 1.00 <1.00 23.2 <1.00 甲苯 ng/mL 1.00 <1.00 2.00 <1.00 乙苯 ng/mL 1.00 <1.00 <1.00 <1.00 间对二甲苯 ng/mL 1.00 <1.00 <1.00 <1.00 邻二甲苯 ng/mL 1.00 <1.00 <1.00 <1.00 苯乙録 ng/mL 1.00 <1.00 <1.00 <1.00 替代物回收率 % 控制限
二溴氟甲烷 % 60- 130 91.4 93.6 91.9 氟苯 % 60- 130 88.5 88.7 88.2 甲苯 -D8 % 60- 130 89.4 85.9 89.0
4-溴氟苯 % 60- 130 88.6 85.7 90.5
1, 2-二氯苯 -D4 % 60- 130 87.0 90.3 90.8 、本发明的生物陶对室内空气中的苯、 甲苯、二甲苯的去除效果检测报告。
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Claims

权 利 要 求 书
1. 一种具有选择性吸附消解功能的生物陶，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所述的具有选择性吸附消解功能的生物陶，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所述的具有选择性吸附消解功能的生物陶，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所述的具有选择性吸附消解功能的生物陶，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所述的具有选择性吸附消解功能的生物陶，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 Fe或 Ti或 Cu或 Zn中的任意一种。
6. 权利要求 1所述的具有选择性吸附消解功能的生物陶，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 295-305°C保持 1~2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 740-76CTC保持 2-3小时； 然后以 150-200°C/h的降温速率降温至室温， 得生物陶介质；
(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陶。
7. 根据权利要求 6所述的具有选择性吸附消解功能的生物陶，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 Mpa。
8. 根据权利要求 6所述的具有选择性吸附消解功能的生物陶，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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