稻床養(yǎng)雞固廢中殘留抗生素和砷的微波處理研究
發(fā)布時間：2018-08-14 18:52
【摘要】：隨著經(jīng)濟(jì)和物質(zhì)水平快速發(fā)展,雞肉的需求量逐漸增大。越來越多的規(guī)�；s養(yǎng)雞場隨之出現(xiàn),并帶來了數(shù)量巨大的雞糞,亟待處理。四環(huán)素類抗生素(TCs)和洛克沙胂(ROX)是養(yǎng)雞過程中極為常用的兩類藥劑,在雞糞中通常有較多的殘留。目前大量的雞糞常采用傳統(tǒng)的堆肥技術(shù)處理為有機肥,但其中殘留的TCs通常難以降解,而有機砷在堆肥過程中容易轉(zhuǎn)化為毒性更大的無機砷,存在更大的環(huán)境風(fēng)險。而微波催化熱解技術(shù)不僅能有效降解有機污染物,也能穩(wěn)定固化重金屬。本研究以集約養(yǎng)雞業(yè)產(chǎn)生的稻殼雞糞(Rice Husk Chicken Manure,RHCM)為處理對象,分別開展其中殘留TCs的微波熱解技術(shù)和殘留砷的藥劑穩(wěn)化/微波固定聯(lián)用技術(shù)的系統(tǒng)研究,對微波處理系統(tǒng)的作用機理進(jìn)行了探討,并對稻殼雞糞微波制備生物炭的可行性和經(jīng)濟(jì)性進(jìn)行了分析和評估。主要研究結(jié)論包括:(1)在稻殼雞糞中TCs的微波熱降解實驗研究中,對藥劑種類、微波功率、輻照時間等實驗條件對TCs降解的影響進(jìn)行了探討,從結(jié)果可知:碳化硅材質(zhì)容器顯示出優(yōu)越的微波吸收能力而被選為微波熱降解稻殼雞糞中TCs的反應(yīng)容器,Fe SO4·7H2O的加入被證明能夠顯著提升稻床養(yǎng)雞固廢的微波吸收性能,當(dāng)Fe SO4·7H2O固體摻雜量達(dá)到10%(m/m)的質(zhì)量比例,在優(yōu)化實驗微波條件:560W、20min下,兩種TCs的消減率均高于95%。高效液相色譜(HPLC)對降解產(chǎn)物的分析鑒定了TCs在熱解過程中先發(fā)生差向異構(gòu)化、脫水分解反應(yīng),最后母體及產(chǎn)物完全礦化的降解過程。中試微波熱解處理稻殼雞糞中TCs的效果可以滿足項目要求。(2)在稻殼雞糞中砷(As)的穩(wěn)定化實驗研究中,Fe SO4·7H2O展示了比堿性物質(zhì)、鈣鹽、硫化物更強的對砷的穩(wěn)定/固定化作用。而微波高溫固定化技術(shù)與藥劑穩(wěn)定化技術(shù)被本研究證明對As的無害化處理具有協(xié)同作用,其中Fe SO4·7H2O同時起到了共沉淀穩(wěn)定劑和微波敏化劑的關(guān)鍵性作用。在5%(m/m)比例的Fe SO4·7H2O添加量,700W、20min的優(yōu)化微波條件組合下,稻殼雞糞中砷的穩(wěn)定/固化率達(dá)到了96.1%。微波中試研究驗證了此聯(lián)用技術(shù)對批量稻床養(yǎng)雞固廢砷處理的可行性。對洛克沙胂的熱重分析結(jié)果闡明了其在微波熱解過程中先迅速降解為無機砷而后被鐵離子穩(wěn)定及被微波高溫固定。對處理后RHCM的XPS表征揭示了Fe元素主要以Fe2O3和Fe3O4形式存在,而其中As則形成了穩(wěn)定的Fe As O3。(3)對制備產(chǎn)物—稻殼雞糞生物炭進(jìn)行BET、SEM、FTIR等吸附特性、表面形貌和理化性質(zhì)的表征和分析,結(jié)果表明本研究微波熱解產(chǎn)物為介孔物質(zhì),可見發(fā)達(dá)孔隙結(jié)構(gòu)和大量灰分,顆粒尺寸主要集中在10-100μm。碳材料表面官能團(tuán)種類豐富,飽含氮磷等營養(yǎng)元素,且重金屬含量遠(yuǎn)低于標(biāo)準(zhǔn),微生物指標(biāo)同樣符合農(nóng)田利用標(biāo)準(zhǔn)。因此所制備生物炭在土壤改良及土壤修復(fù)領(lǐng)域顯示出良好的市場前景。在研究基礎(chǔ)上完成了連續(xù)化的微波雞糞處理設(shè)備的初步設(shè)計。
[Abstract]:With the rapid development of economy and material level, the demand for chicken is increasing gradually. More and more intensive chicken farms appear, and bring a huge amount of chicken manure, which needs to be dealt with. Tetracycline antibiotics (TCs) and roxarsone (ROX) are two kinds of fungicides commonly used in chicken breeding. At present, a large amount of chicken manure is usually treated as organic manure by traditional composting technology, but the residual TCs is usually difficult to degrade, while organic arsenic is easily converted into inorganic arsenic with greater toxicity during composting, and there is a greater environmental risk. Microwave catalytic pyrolysis can not only effectively degrade organic pollutants, but also stabilize the solidification of heavy metals. In this study, rice husk chicken dung (Rice Husk Chicken manureus) produced from intensive chicken industry was treated with microwave pyrolysis technique of residual TCs and combined technique of stabilization and microwave fixation of residual arsenic. The mechanism of microwave treatment system was discussed, and the feasibility and economy of microwave preparation of biochar from rice husk chicken manure were analyzed and evaluated. The main conclusions are as follows: (1) in the experimental study of microwave thermal degradation of TCs in rice husk chicken manure, the effects of the kinds of medicament, microwave power and irradiation time on the degradation of TCs were discussed. The results showed that the silicon carbide material container showed superior microwave absorption ability and was selected as the reaction container for microwave thermal degradation of TCs in rice husk chicken dung. It was proved that the addition of Fe SO4 7H2O could significantly improve the microwave absorption performance of rice bed chicken solid waste. When the mass ratio of Fe SO4 7H2O solid doping is 10% (m / m), the reduction rate of both TCs is higher than 95% under the optimized microwave condition: 560W / min. Analysis of degradation products by (HPLC) the degradation process of TCs in pyrolysis was characterized by differential isomerization dehydration and decomposition finally the parent and product were completely mineralized. The effect of microwave pyrolysis on the treatment of TCs in rice husk chicken dung could meet the requirements of the project. (2) in the stabilization experiment of arsenic (As) in rice husk chicken dung, Fe SO4 7H2O showed more stable / immobilized arsenic than alkaline substances, calcium salts and sulfides. The technology of microwave immobilization at high temperature and the technology of medicament stabilization have been proved to be synergistic to the innocuous treatment of as, among which Fe SO4 7H2O plays the key role of both coprecipitation stabilizer and microwave sensitizer. Under the optimized microwave condition of adding Fe SO4 7H2O to 5% (m / m) of rice husk chicken manure for 20 min, the stabilization / solidification rate of arsenic reached 96.1%. The microwave pilot study verified the feasibility of the combined technology for the treatment of solid arsenic in batch rice bed chicken. The results of thermogravimetric analysis of roxarsone show that it is rapidly degraded to inorganic arsenic and then stabilized by iron ion and fixed by microwave during microwave pyrolysis. The XPS characterization of treated RHCM revealed that Fe existed mainly in the form of Fe2O3 and Fe3O4, and that as formed a stable Fe as O 3. (3) the preparation product, rice husk chicken manure biochar, was adsorbed by BET-SEMFTIR. The surface morphology and physicochemical properties were characterized and analyzed. The results showed that the microwave pyrolysis product was mesoporous material, developed pore structure and a large amount of ash, and the particle size was mainly concentrated in 10-100 渭 m. The surface functional groups of carbon materials are rich in kinds of nutrient elements such as nitrogen and phosphorus, and the heavy metal content is far below the standard, and the microbial index is also in line with the farmland utilization standard. Therefore, the prepared biochar has a good market prospect in the field of soil improvement and soil remediation. On the basis of the research, the preliminary design of continuous microwave chicken manure treatment equipment was completed.
【學(xué)位授予單位】：華中科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：X713
[Abstract]:With the rapid development of economy and material level, the demand for chicken is increasing gradually. More and more intensive chicken farms appear, and bring a huge amount of chicken manure, which needs to be dealt with. Tetracycline antibiotics (TCs) and roxarsone (ROX) are two kinds of fungicides commonly used in chicken breeding. At present, a large amount of chicken manure is usually treated as organic manure by traditional composting technology, but the residual TCs is usually difficult to degrade, while organic arsenic is easily converted into inorganic arsenic with greater toxicity during composting, and there is a greater environmental risk. Microwave catalytic pyrolysis can not only effectively degrade organic pollutants, but also stabilize the solidification of heavy metals. In this study, rice husk chicken dung (Rice Husk Chicken manureus) produced from intensive chicken industry was treated with microwave pyrolysis technique of residual TCs and combined technique of stabilization and microwave fixation of residual arsenic. The mechanism of microwave treatment system was discussed, and the feasibility and economy of microwave preparation of biochar from rice husk chicken manure were analyzed and evaluated. The main conclusions are as follows: (1) in the experimental study of microwave thermal degradation of TCs in rice husk chicken manure, the effects of the kinds of medicament, microwave power and irradiation time on the degradation of TCs were discussed. The results showed that the silicon carbide material container showed superior microwave absorption ability and was selected as the reaction container for microwave thermal degradation of TCs in rice husk chicken dung. It was proved that the addition of Fe SO4 7H2O could significantly improve the microwave absorption performance of rice bed chicken solid waste. When the mass ratio of Fe SO4 7H2O solid doping is 10% (m / m), the reduction rate of both TCs is higher than 95% under the optimized microwave condition: 560W / min. Analysis of degradation products by (HPLC) the degradation process of TCs in pyrolysis was characterized by differential isomerization dehydration and decomposition finally the parent and product were completely mineralized. The effect of microwave pyrolysis on the treatment of TCs in rice husk chicken dung could meet the requirements of the project. (2) in the stabilization experiment of arsenic (As) in rice husk chicken dung, Fe SO4 7H2O showed more stable / immobilized arsenic than alkaline substances, calcium salts and sulfides. The technology of microwave immobilization at high temperature and the technology of medicament stabilization have been proved to be synergistic to the innocuous treatment of as, among which Fe SO4 7H2O plays the key role of both coprecipitation stabilizer and microwave sensitizer. Under the optimized microwave condition of adding Fe SO4 7H2O to 5% (m / m) of rice husk chicken manure for 20 min, the stabilization / solidification rate of arsenic reached 96.1%. The microwave pilot study verified the feasibility of the combined technology for the treatment of solid arsenic in batch rice bed chicken. The results of thermogravimetric analysis of roxarsone show that it is rapidly degraded to inorganic arsenic and then stabilized by iron ion and fixed by microwave during microwave pyrolysis. The XPS characterization of treated RHCM revealed that Fe existed mainly in the form of Fe2O3 and Fe3O4, and that as formed a stable Fe as O 3. (3) the preparation product, rice husk chicken manure biochar, was adsorbed by BET-SEMFTIR. The surface morphology and physicochemical properties were characterized and analyzed. The results showed that the microwave pyrolysis product was mesoporous material, developed pore structure and a large amount of ash, and the particle size was mainly concentrated in 10-100 渭 m. The surface functional groups of carbon materials are rich in kinds of nutrient elements such as nitrogen and phosphorus, and the heavy metal content is far below the standard, and the microbial index is also in line with the farmland utilization standard. Therefore, the prepared biochar has a good market prospect in the field of soil improvement and soil remediation. On the basis of the research, the preliminary design of continuous microwave chicken manure treatment equipment was completed.
【學(xué)位授予單位】：華中科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：X713
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