基于超循环理论的草浆造纸水循环经济模式与技术体系研究
发布时间：2018-07-21 21:25
【摘要】：中国是一个制浆造纸和纸张消费的大国,以稻草、秸秆、芦苇等禾草类为原料的草浆造纸虽然在造纸行业中的比重只占15%,但COD排放量却占造纸行业总排放量的80%以上。以辽宁为例,辽河流域共有草浆造纸厂200多家,其草浆造纸废水COD排放量占工业废水COD总排放量40%,已经成为辽河流域的主要污染源,急待解决。本研究在国家重大科技专项“辽河流域重化工业节水减排清洁生产技术集成与示范工程—造纸行业节水减排及清洁生产关键技术与示范”(2009ZX07208-002-003)研究课题资助下,运用自组织超循环理论,研究草浆造纸产业的水循环经济超循环模式和技术支撑体系,实现草浆造纸行业的节水减排和污染治理,为改善辽河流域水环境质量,摘掉辽河重污染的帽子,提供决策依据。主要研究丙容和结果如下：(1)论文运用超循环理论分析了草浆造纸水循环经济系统的超循环驱动力的“内外催化剂”,提出了产业政策和法规标准为“外部催化剂”；清洁生产与可持续废水处理技术为草浆造纸水循环经济超循环模式驱动力的“内部催化剂”。通过对辽宁省各个行业污染贡献率分析,发现造纸行业是辽宁产业结构性污染的主要因素。通过修订辽宁省污水综合排放标准,促使辽河流域淘汰落后产能、进行产业结构调整,提升造纸企业清洁生产与节水减排技术的开发与应用,发挥结构减排和管理减排的重要功能。(2)应用超循环理论构建草浆造纸工业水循环经济的超循环模式。从反应循环层面通过开展清洁生产,使造纸企业实现源头减量化,在取水-用水-排水环节中提升用水效率,实现节水减排；从催化循环的层面通过开展造纸废水处理与回用技术、造纸用水网络优化的方式大幅提升水的循环利用效率,节约新鲜水资源；从超循环的层面构建芦苇湿地-造纸一体化超循环复合生态系统,通过芦苇湿地深度处理实现造纸废水良性二元水循环。(3)构建了超循环模式的技术支撑体系。从清洁生产源头减量化方面,开展了碱性过氧化氢低温蒸煮清洁制浆法的研究,结果表明NaOH/H2O2清洁制浆的最佳工艺条件为NaOH用量为10～11%,H202用量为15～18%,二者投料间隔时间为1 h,总蒸煮时间为2.5 h；采用NaOH/H2O2清洁制浆工艺较传统烧碱制浆工艺降低草浆造纸黑液的COD浓度和排放负荷,生产的纸浆性能和质量也得以大副提升。对制浆黑液资源化方面,开展了黑液合成木质素磺酸钙粘合剂的研究,研究结果表明,黑液合成木质素磺酸钙粘合剂的适宜反应条件为：原液浓缩后,在反应釜中首先加入固形物含量5%的甲醛,加热至60℃反应1 h,然后加入固形物含量10%的亚硫酸钙,升温至130℃反应2 h,木质素制备活性炭载体的最佳工艺条件为磷料比为3.5：1,活化温度500℃,活化时间60 mmin,粘合剂性能符合产品质量标准要求。从水循环经济过程方面,开展了梯形平板膜SMBR技术优化研究。通过对Vries建立的气泡与竖直平板相互作用模型的分解、演算,重新建立新的数学模型描述气泡与梯型平板膜的相互作用,从而对SMBR中梯型平板膜组件进行优化设计,实现同等条件下提高曝气冲刷利用率的目的,结果表明：对于半径较小的小气泡(0.5-1.51mm)最佳的梯形膜倾斜角度为8.1°,对于半径较大的气泡(1.5～2.5mm)最佳的梯形膜倾斜角度为6.8°,用梯形膜组件的SMBR工艺处理造纸废水,COD.SS的平均去除率分别为90.5%、95.1%,梯形膜组件比平板膜组件具备更好的抗污染性能；多级串联湿地系统深度处理造纸废水等草浆造纸水循环技术研究。寒冷地区多级串联湿地系统对草浆造纸废水表现出较好的造纸污染物去除效果,该系统中各污染物的脱除效果受进水负荷影响显著,受温度影响较小,采用“混凝—氧化沟—气浮—氧化塘—苇田湿地”三级组合工艺处理造纸废水,出水水质较稳定在COD 20～50 mg/L、SS 10～20 mg/L,达到了《辽宁省污水综合排放标准》中排放限值要求；造纸废水生化处理后经氧化塘处理后进入苇田深度灌溉芦苇湿地对其土壤和地下水的环境质量影响较小,有机质含量有所提高,对芦苇生长有一定的促进作用。(4)对芦苇制浆企业用水网络进行了优化研究。采用物质流分析的方法建立了草浆造纸企业的用水网络优化模型与节水绩效评价指标体系,该模型可以识别草浆造纸企业用水系统存在的问题,并且能够有效的对制浆造纸企业用水系统进行分析与优化。利用草浆造纸企业的用水网络模型,对辽宁某大型苇浆造纸企业A进行用水网络优化,节水效果显著：吨纸水消耗量减少了49 m3/t,吨纸新鲜水消耗减少98 m3/t,吨纸废水排放量降低到0 m3/t,水资源效率提升268.1%,水环境效率提升+∞,水循环率提升了24.2%。
[Abstract]:China is a big country with pulp and paper consumption, straw pulp, straw, reed and other grasses are used as raw materials, although the proportion of paper making in paper industry is only 15%, but COD emissions account for more than 80% of the total emissions of paper industry. In Liaoning, there are more than 200 pulp and paper mills in the Liaohe River Basin and the COD row of straw pulp wastewater. The total emission of COD of industrial wastewater is 40%, which has become the main source of pollution in the Liaohe River Basin. It is urgent to solve the problem. This study is in the national major science and technology special project "the integration and demonstration project of the clean production technology of the heavy chemical industry in the Liaohe River Basin - the key technology and demonstration of the water saving and emission reduction and the clean production of the paper industry" (2009ZX07208-002-003) Under the support of the research project, the water circulation economy supercirculation model and the technical support system of the straw pulp and paper industry are studied by using the self-organizing supercirculation theory, and the water saving and pollution control of the pulp and paper industry are realized, the water environmental quality of the Liaohe River Basin is improved and the heavy pollution hats of Liaohe River are removed. The results are as follows: (1) in this paper, the super circulation theory is used to analyze the "internal and external catalyst" of the super circulation driving force of the water cycle economic system of straw pulp and paper making, and the industrial policy and the regulations and standards are "external catalyst", and the driving force of the clean production and the sustainable wastewater treatment technology is the driving force of the cycle economic cycle model of the straw pulp making water cycle. Through the analysis of the contribution rate of pollution in various industries in Liaoning Province, it is found that the paper industry is the main factor of industrial structural pollution in Liaoning. Through the revision of the comprehensive sewage discharge standard in Liaoning Province, the lagging capacity of the Liaohe River Basin is eliminated, the industrial structure adjustment is carried out, and the clean production and the technology of water saving and emission reduction in paper making enterprises are promoted. (2) the super circulation model of water recycling economy in straw pulp and paper industry is constructed by using the theory of super circulation. Through the development of clean production from the reaction cycle level, the papermaking enterprise is reduced to the source, and the water efficiency is promoted in the water intake water drainage link and the water saving and emission reduction can be realized. From the level of catalytic cycle, the process of papermaking wastewater treatment and reuse is carried out. The optimization of paper making water network improves the recycling efficiency of water, saves fresh water resources, and constructs a reed wetland - paper integrated super circulation complex ecosystem from the supercirculation level, and makes papermaking wastewater good through the deep treatment of reed wetland. Two yuan water circulation. (3) construction of the technical support system of super circulation mode. From the reduction of the source of clean production, the research on the alkaline hydrogen peroxide low temperature cooking and cleaning pulping method is carried out. The results show that the best process conditions for NaOH/H2O2 cleaning pulping are the amount of NaOH 10 ~ 11%, the dosage of H202 from 15 to 18%, and the interval time of two feeding for 1. H, the total cooking time is 2.5 h, and the COD concentration and discharge load of the black liquor of straw pulp are reduced by the NaOH/H2O2 cleaning pulping process than the traditional caustic soda pulping process. The pulp performance and quality of the produced pulp can also be promoted. The research on the calcium sulfonate binder for black liquor synthesis of black liquor is carried out. The optimum reaction conditions for the synthesis of calcium lignosulfonate binder in black liquor are as follows: after concentration of the raw liquid, a formaldehyde with 5% solid content is first added to the reaction kettle, heated to 60 C for 1 h, and then adding calcium sulfite with solid content of 10%, and heating to 130 centigrade to react 2 h, and the optimum process condition for the preparation of activated carbon by lignin is that the ratio of phosphorus to phosphorus is 3. .5:1, the activation temperature is 500 C and the activation time is 60 mmin. The adhesive performance meets the requirements of the product quality standard. From the water cycle economic process, the optimization of the SMBR technology of the trapezoid flat film is carried out. The decomposition of the model of the interaction between the bubble and the vertical flat plate established by the Vries is calculated and the new mathematical model is reestablished to describe the bubble and ladder. The interaction between the flat plate film and the plate membrane module in SMBR is optimized to achieve the purpose of improving the utilization rate of the aeration scour under the same conditions. The results show that the best trapezoid film angle of the small bubble (0.5-1.51mm) with a smaller radius is 8.1 degrees, and the best trapezoid film tilting for the larger bubbles (1.5 to 2.5mm) with a larger radius is obtained. The oblique angle is 6.8 degrees, and the SMBR process of the trapezoid membrane module is used to treat the papermaking wastewater. The average removal rate of COD.SS is 90.5%, 95.1%. The trapezoid membrane module has better anti pollution performance than the flat membrane module; the multistage series wetland system is deeply treated with the paper pulp and paper water circulation technology of papermaking wastewater. The removal efficiency of papermaking wastewater is better. The removal effect of various pollutants in this system is affected significantly by the influent load and is less affected by the temperature. The three grade combination process of "coagulation - oxidation ditch - air flotation - oxidation pond - reed field wetland" is used to treat papermaking wastewater. The water quality of the effluent is more stable at COD 20~50 M G/L, SS 10~20 mg/L, reached the requirements for the discharge limit of the comprehensive discharge standard of Liaoning Province, and the effect of the reed wetland on the environmental quality of soil and groundwater was less, the content of organic matter was higher and the growth of reed had a certain promotion effect. (4) The water network of the reed pulping enterprise is optimized. The water network optimization model and the water saving performance evaluation index system are established by the method of material flow analysis. This model can identify the problems existing in the water system of the straw pulp and paper enterprises, and can effectively carry out the water system for the pulp and paper enterprises. The water network model of a large reed pulp and paper enterprise in Liaoning is optimized by using the water network model of the pulp and paper making enterprises in Liaoning. The water saving effect is remarkable: the water consumption of tons of paper is reduced by 49 m3/t, the consumption of fresh water in tons paper is reduced by 98 m3/t, the discharge of paper waste water is reduced to 0 m3/t, the water resource efficiency is raised by 268.1%, and the water environment efficiency is raised. The rise + infinity, the water cycle rate increased by 24.2%.
【学位授予单位】：大连理工大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：F426.83;X793
，
本文编号：2136904
[Abstract]:China is a big country with pulp and paper consumption, straw pulp, straw, reed and other grasses are used as raw materials, although the proportion of paper making in paper industry is only 15%, but COD emissions account for more than 80% of the total emissions of paper industry. In Liaoning, there are more than 200 pulp and paper mills in the Liaohe River Basin and the COD row of straw pulp wastewater. The total emission of COD of industrial wastewater is 40%, which has become the main source of pollution in the Liaohe River Basin. It is urgent to solve the problem. This study is in the national major science and technology special project "the integration and demonstration project of the clean production technology of the heavy chemical industry in the Liaohe River Basin - the key technology and demonstration of the water saving and emission reduction and the clean production of the paper industry" (2009ZX07208-002-003) Under the support of the research project, the water circulation economy supercirculation model and the technical support system of the straw pulp and paper industry are studied by using the self-organizing supercirculation theory, and the water saving and pollution control of the pulp and paper industry are realized, the water environmental quality of the Liaohe River Basin is improved and the heavy pollution hats of Liaohe River are removed. The results are as follows: (1) in this paper, the super circulation theory is used to analyze the "internal and external catalyst" of the super circulation driving force of the water cycle economic system of straw pulp and paper making, and the industrial policy and the regulations and standards are "external catalyst", and the driving force of the clean production and the sustainable wastewater treatment technology is the driving force of the cycle economic cycle model of the straw pulp making water cycle. Through the analysis of the contribution rate of pollution in various industries in Liaoning Province, it is found that the paper industry is the main factor of industrial structural pollution in Liaoning. Through the revision of the comprehensive sewage discharge standard in Liaoning Province, the lagging capacity of the Liaohe River Basin is eliminated, the industrial structure adjustment is carried out, and the clean production and the technology of water saving and emission reduction in paper making enterprises are promoted. (2) the super circulation model of water recycling economy in straw pulp and paper industry is constructed by using the theory of super circulation. Through the development of clean production from the reaction cycle level, the papermaking enterprise is reduced to the source, and the water efficiency is promoted in the water intake water drainage link and the water saving and emission reduction can be realized. From the level of catalytic cycle, the process of papermaking wastewater treatment and reuse is carried out. The optimization of paper making water network improves the recycling efficiency of water, saves fresh water resources, and constructs a reed wetland - paper integrated super circulation complex ecosystem from the supercirculation level, and makes papermaking wastewater good through the deep treatment of reed wetland. Two yuan water circulation. (3) construction of the technical support system of super circulation mode. From the reduction of the source of clean production, the research on the alkaline hydrogen peroxide low temperature cooking and cleaning pulping method is carried out. The results show that the best process conditions for NaOH/H2O2 cleaning pulping are the amount of NaOH 10 ~ 11%, the dosage of H202 from 15 to 18%, and the interval time of two feeding for 1. H, the total cooking time is 2.5 h, and the COD concentration and discharge load of the black liquor of straw pulp are reduced by the NaOH/H2O2 cleaning pulping process than the traditional caustic soda pulping process. The pulp performance and quality of the produced pulp can also be promoted. The research on the calcium sulfonate binder for black liquor synthesis of black liquor is carried out. The optimum reaction conditions for the synthesis of calcium lignosulfonate binder in black liquor are as follows: after concentration of the raw liquid, a formaldehyde with 5% solid content is first added to the reaction kettle, heated to 60 C for 1 h, and then adding calcium sulfite with solid content of 10%, and heating to 130 centigrade to react 2 h, and the optimum process condition for the preparation of activated carbon by lignin is that the ratio of phosphorus to phosphorus is 3. .5:1, the activation temperature is 500 C and the activation time is 60 mmin. The adhesive performance meets the requirements of the product quality standard. From the water cycle economic process, the optimization of the SMBR technology of the trapezoid flat film is carried out. The decomposition of the model of the interaction between the bubble and the vertical flat plate established by the Vries is calculated and the new mathematical model is reestablished to describe the bubble and ladder. The interaction between the flat plate film and the plate membrane module in SMBR is optimized to achieve the purpose of improving the utilization rate of the aeration scour under the same conditions. The results show that the best trapezoid film angle of the small bubble (0.5-1.51mm) with a smaller radius is 8.1 degrees, and the best trapezoid film tilting for the larger bubbles (1.5 to 2.5mm) with a larger radius is obtained. The oblique angle is 6.8 degrees, and the SMBR process of the trapezoid membrane module is used to treat the papermaking wastewater. The average removal rate of COD.SS is 90.5%, 95.1%. The trapezoid membrane module has better anti pollution performance than the flat membrane module; the multistage series wetland system is deeply treated with the paper pulp and paper water circulation technology of papermaking wastewater. The removal efficiency of papermaking wastewater is better. The removal effect of various pollutants in this system is affected significantly by the influent load and is less affected by the temperature. The three grade combination process of "coagulation - oxidation ditch - air flotation - oxidation pond - reed field wetland" is used to treat papermaking wastewater. The water quality of the effluent is more stable at COD 20~50 M G/L, SS 10~20 mg/L, reached the requirements for the discharge limit of the comprehensive discharge standard of Liaoning Province, and the effect of the reed wetland on the environmental quality of soil and groundwater was less, the content of organic matter was higher and the growth of reed had a certain promotion effect. (4) The water network of the reed pulping enterprise is optimized. The water network optimization model and the water saving performance evaluation index system are established by the method of material flow analysis. This model can identify the problems existing in the water system of the straw pulp and paper enterprises, and can effectively carry out the water system for the pulp and paper enterprises. The water network model of a large reed pulp and paper enterprise in Liaoning is optimized by using the water network model of the pulp and paper making enterprises in Liaoning. The water saving effect is remarkable: the water consumption of tons of paper is reduced by 49 m3/t, the consumption of fresh water in tons paper is reduced by 98 m3/t, the discharge of paper waste water is reduced to 0 m3/t, the water resource efficiency is raised by 268.1%, and the water environment efficiency is raised. The rise + infinity, the water cycle rate increased by 24.2%.
【学位授予单位】：大连理工大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：F426.83;X793
，
本文编号：2136904
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