基于超循環(huán)理論的草漿造紙水循環(huán)經(jīng)濟(jì)模式與技術(shù)體系研究
發(fā)布時(shí)間：2018-07-21 21:25
【摘要】：中國是一個(gè)制漿造紙和紙張消費(fèi)的大國,以稻草、秸稈、蘆葦?shù)群滩蓊悶樵系牟轁{造紙雖然在造紙行業(yè)中的比重只占15%,但COD排放量卻占造紙行業(yè)總排放量的80%以上。以遼寧為例,遼河流域共有草漿造紙廠200多家,其草漿造紙廢水COD排放量占工業(yè)廢水COD總排放量40%,已經(jīng)成為遼河流域的主要污染源,急待解決。本研究在國家重大科技專項(xiàng)“遼河流域重化工業(yè)節(jié)水減排清潔生產(chǎn)技術(shù)集成與示范工程—造紙行業(yè)節(jié)水減排及清潔生產(chǎn)關(guān)鍵技術(shù)與示范”(2009ZX07208-002-003)研究課題資助下,運(yùn)用自組織超循環(huán)理論,研究草漿造紙產(chǎn)業(yè)的水循環(huán)經(jīng)濟(jì)超循環(huán)模式和技術(shù)支撐體系,實(shí)現(xiàn)草漿造紙行業(yè)的節(jié)水減排和污染治理,為改善遼河流域水環(huán)境質(zhì)量,摘掉遼河重污染的帽子,提供決策依據(jù)。主要研究丙容和結(jié)果如下：(1)論文運(yùn)用超循環(huán)理論分析了草漿造紙水循環(huán)經(jīng)濟(jì)系統(tǒng)的超循環(huán)驅(qū)動(dòng)力的“內(nèi)外催化劑”,提出了產(chǎn)業(yè)政策和法規(guī)標(biāo)準(zhǔn)為“外部催化劑”；清潔生產(chǎn)與可持續(xù)廢水處理技術(shù)為草漿造紙水循環(huán)經(jīng)濟(jì)超循環(huán)模式驅(qū)動(dòng)力的“內(nèi)部催化劑”。通過對(duì)遼寧省各個(gè)行業(yè)污染貢獻(xiàn)率分析,發(fā)現(xiàn)造紙行業(yè)是遼寧產(chǎn)業(yè)結(jié)構(gòu)性污染的主要因素。通過修訂遼寧省污水綜合排放標(biāo)準(zhǔn),促使遼河流域淘汰落后產(chǎn)能、進(jìn)行產(chǎn)業(yè)結(jié)構(gòu)調(diào)整,提升造紙企業(yè)清潔生產(chǎn)與節(jié)水減排技術(shù)的開發(fā)與應(yīng)用,發(fā)揮結(jié)構(gòu)減排和管理減排的重要功能。(2)應(yīng)用超循環(huán)理論構(gòu)建草漿造紙工業(yè)水循環(huán)經(jīng)濟(jì)的超循環(huán)模式。從反應(yīng)循環(huán)層面通過開展清潔生產(chǎn),使造紙企業(yè)實(shí)現(xiàn)源頭減量化,在取水-用水-排水環(huán)節(jié)中提升用水效率,實(shí)現(xiàn)節(jié)水減排；從催化循環(huán)的層面通過開展造紙廢水處理與回用技術(shù)、造紙用水網(wǎng)絡(luò)優(yōu)化的方式大幅提升水的循環(huán)利用效率,節(jié)約新鮮水資源；從超循環(huán)的層面構(gòu)建蘆葦濕地-造紙一體化超循環(huán)復(fù)合生態(tài)系統(tǒng),通過蘆葦濕地深度處理實(shí)現(xiàn)造紙廢水良性二元水循環(huán)。(3)構(gòu)建了超循環(huán)模式的技術(shù)支撐體系。從清潔生產(chǎn)源頭減量化方面,開展了堿性過氧化氫低溫蒸煮清潔制漿法的研究,結(jié)果表明NaOH/H2O2清潔制漿的最佳工藝條件為NaOH用量為10～11%,H202用量為15～18%,二者投料間隔時(shí)間為1 h,總蒸煮時(shí)間為2.5 h；采用NaOH/H2O2清潔制漿工藝較傳統(tǒng)燒堿制漿工藝降低草漿造紙黑液的COD濃度和排放負(fù)荷,生產(chǎn)的紙漿性能和質(zhì)量也得以大副提升。對(duì)制漿黑液資源化方面,開展了黑液合成木質(zhì)素磺酸鈣粘合劑的研究,研究結(jié)果表明,黑液合成木質(zhì)素磺酸鈣粘合劑的適宜反應(yīng)條件為：原液濃縮后,在反應(yīng)釜中首先加入固形物含量5%的甲醛,加熱至60℃反應(yīng)1 h,然后加入固形物含量10%的亞硫酸鈣,升溫至130℃反應(yīng)2 h,木質(zhì)素制備活性炭載體的最佳工藝條件為磷料比為3.5：1,活化溫度500℃,活化時(shí)間60 mmin,粘合劑性能符合產(chǎn)品質(zhì)量標(biāo)準(zhǔn)要求。從水循環(huán)經(jīng)濟(jì)過程方面,開展了梯形平板膜SMBR技術(shù)優(yōu)化研究。通過對(duì)Vries建立的氣泡與豎直平板相互作用模型的分解、演算,重新建立新的數(shù)學(xué)模型描述氣泡與梯型平板膜的相互作用,從而對(duì)SMBR中梯型平板膜組件進(jìn)行優(yōu)化設(shè)計(jì),實(shí)現(xiàn)同等條件下提高曝氣沖刷利用率的目的,結(jié)果表明：對(duì)于半徑較小的小氣泡(0.5-1.51mm)最佳的梯形膜傾斜角度為8.1°,對(duì)于半徑較大的氣泡(1.5～2.5mm)最佳的梯形膜傾斜角度為6.8°,用梯形膜組件的SMBR工藝處理造紙廢水,COD.SS的平均去除率分別為90.5%、95.1%,梯形膜組件比平板膜組件具備更好的抗污染性能；多級(jí)串聯(lián)濕地系統(tǒng)深度處理造紙廢水等草漿造紙水循環(huán)技術(shù)研究。寒冷地區(qū)多級(jí)串聯(lián)濕地系統(tǒng)對(duì)草漿造紙廢水表現(xiàn)出較好的造紙污染物去除效果,該系統(tǒng)中各污染物的脫除效果受進(jìn)水負(fù)荷影響顯著,受溫度影響較小,采用“混凝—氧化溝—?dú)飧 趸痢斕餄竦亍比?jí)組合工藝處理造紙廢水,出水水質(zhì)較穩(wěn)定在COD 20～50 mg/L、SS 10～20 mg/L,達(dá)到了《遼寧省污水綜合排放標(biāo)準(zhǔn)》中排放限值要求；造紙廢水生化處理后經(jīng)氧化塘處理后進(jìn)入葦田深度灌溉蘆葦濕地對(duì)其土壤和地下水的環(huán)境質(zhì)量影響較小,有機(jī)質(zhì)含量有所提高,對(duì)蘆葦生長有一定的促進(jìn)作用。(4)對(duì)蘆葦制漿企業(yè)用水網(wǎng)絡(luò)進(jìn)行了優(yōu)化研究。采用物質(zhì)流分析的方法建立了草漿造紙企業(yè)的用水網(wǎng)絡(luò)優(yōu)化模型與節(jié)水績效評(píng)價(jià)指標(biāo)體系,該模型可以識(shí)別草漿造紙企業(yè)用水系統(tǒng)存在的問題,并且能夠有效的對(duì)制漿造紙企業(yè)用水系統(tǒng)進(jìn)行分析與優(yōu)化。利用草漿造紙企業(yè)的用水網(wǎng)絡(luò)模型,對(duì)遼寧某大型葦漿造紙企業(yè)A進(jìn)行用水網(wǎng)絡(luò)優(yōu)化,節(jié)水效果顯著：噸紙水消耗量減少了49 m3/t,噸紙新鮮水消耗減少98 m3/t,噸紙廢水排放量降低到0 m3/t,水資源效率提升268.1%,水環(huán)境效率提升+∞,水循環(huán)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%.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：F426.83;X793
，
本文編號(hào)：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%.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：F426.83;X793
，
本文編號(hào)：2136904
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