聚合硅酸硫酸铝及其在造纸工业中的应用
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摘要
利用硫酸铝、硅酸钠和铝酸钠在实验室一步合成了各种碱化度和硅铝比的聚合硅酸硫酸铝,并对其结构特征、结构形态、水解脱稳性、动电特性、絮凝性能以及对各种造纸废水的混凝处理效果和与阳离子及两性淀粉组成微粒子体系时对麦草浆的助留/助滤性能和助留机理进行了探讨。
利用红外和X—射线衍射技术对聚合硅酸硫酸铝的结构特征研究表明:聚合硅酸硫酸铝与聚合硫酸铝具有相似的多羟基聚铝结构,其中的硅以与铝类似的结构形态参与了与其它羟基铝的配位聚合,使之常温结晶行为与聚合硫酸铝不同,但其最终会水解形成与无定形氢氧化铝类似的物质。
利用~(27)Al-NMR和Al-Ferron逐时络合比色法对聚合硅酸硫酸铝的结构特征研究表明:提高硅铝比使同一碱化度的聚合硅酸硫酸铝聚合程度略有降低。聚合硅酸硫酸铝和聚合硫酸铝的聚合均未通过Al_(13)途径。稀释使聚合硅酸硫酸铝趋于聚集成更大的分子,且碱化度越高者,这一趋势越明显。在一般的抄纸pH范围和应用浓度下,聚合硅酸硫酸铝主要以代表胶状聚合大分子的Al_c形式存在,且碱化度越高,相应Al_c的量越高。自来水中的杂离子缩小了pH对聚合硅酸硫酸铝结构形态的影响,且多羟基配合物组分Al_b的含量相对较高。因此,在较宽的pH范围内,Al_b、Al_c成为聚合硅酸硫酸铝在自来水稀释的水溶液中的主要结构形态。
利用逐时测定水解产物吸光度的方法对聚合硅酸硫酸铝的水解脱稳性能研究表明:聚合硅酸硫酸铝易水解脱稳,且其水解脱稳速度及水解沉淀物浓度随碱化度的增加而提高,随硅铝比增加的而下降。pH越高,其水解脱稳速度越快。
利用微电泳技术对聚合硅酸硫酸铝的动电特性研究表明:聚合硅酸硫酸铝的等电点和硫酸铝相近,约为pH5。但其所带电荷
A series of polyaluminum silicate sulfates with different basicities and Si / Al molar ratios were synthesized by the reactions of alum with sodium silicate and sodium aluminate. And their structure characteristics, aluminum species, stability of hydrolysis, electrokinetic properties and coagulation performance were studied. Their applications as coagulants in wastewater treatment and as microparticles in microparticle retention aid systems were investigated. Retention mechanism of amphoteric starch / PASS was proposed.The structure characteristics of polyaluminum silicate sulfate (PASS) were analyzed by means of infrared and X-ray diffraction spectra. It was found that the PASS had similar structures with polyaluminum sulfate (PAS), the silicon in PASS complexed with the other polyhydroxy aluminum at same behavior with aluminum. PASS was more stable against hydrolysis and had different crystallization behavior with PAS in environmental temperatures.The aluminum species in PASS aqueous solutions were identified with 27~A1-NMR and Al-Ferron complex timed colorimetric method. As expected that the degree of polymerization of PASS increased with the basicities but decreased with the Si/ Al molar ratios. No Al_(13) was found in PASS and PAS, but a considerable amount of Al_b, which represents the polynuclear aluminum species, were detected. PASS tended to aggregate to form larger molecules with dilution. And, the higher the basicity, the larger the trend. At the pH of papermaking PASS existed mainly as the form of Al_c, which represents the large colloid molecules of aluminum in the aluminum consistency often
used in papermaking. The hetero-ions in tap water lessened the discrepancy caused by pH, and increased the amount of Alb, consequently, Alb and Alc became the major aluminum species at the pH of papermaking.The hydrolysis destability of PASS was investigated by measuring the variation of the precipitate concentration with time caused by hydrolysis using spectrophotometric method. The results showed that the hydrolysis destability of PASS increased with basicity and pH, decreased with Si/Al molar ratio.The eletrokinetic characteristics of PASS were examined with microeletrophoretic method. The isoelectric point of PASS when titrated with NaOH was at approximately pH5, that is just agreement with alum at same conditions. Yet, its absolute values of Zeta potential either before or after the isoelectric point were larger than that of alum. The higher the basicity, the larger the absolute values of the Zeta potential of PASS. The Si/Al molar ratio only had negligible effect on the Zeta potential, especially for the positive value before isoelectric point. The absolute values of Zeta potential also increased with the stirring, but the isoelectric pH was hardly changed. The isoelectric pH for PASS was shown to be higher when it was diluted with tap water instead of deionized water, but the absolute values both before and after its isoelectric point became smaller.The coagulation - flocculation of PASS was investigated with kaolin suspension. The results showed that the dominated mechanism of coagulation - flocculation of PASS for removal of turbidity was not the charge neutralization. The most effective PASS for removal of turbidity had the basicity of 50% as well as Si/A! molar ratio of 0.05. The higher the basicity of PASS, The lower the most effective pH of
kaolin suspension for removal of turbidity.When treated the self-made deinked wastewater for removal of turbidity, chromaticity and COD with coagulation - flocculation method, PASS and PAS both were more effective coagulants than alum. However, PASS had a higher removal efficiency of chromaticity, PAS had a higher removal efficiency of COD. PASS with higher basicity (50%) had a higher removal efficiency of turbidity; PASS with lower basicity (30%) had a higher removal efficiency of COD and chromaticity . The higher the basicity , the lower the most effective pH for the removal of turbidity, chromaticity and COD. For the same PASS, the most effective pH for the removal of turbidity, chromaticity and COD were decreased according as above order. When the deinked wastewater was coagulated and flocculated by the synergism of PASS and CPAM, the floes produced were large and heavy, therefore, its settling velocity increased. Yet, CPAM had little effects on the removal efficiency of turbidity, chromaticity and COD.When the pulping and papermaking combined effluent and their medium-sector effluent that include screened, cleaned as well as bleaching effluents were treated with PASS, the similar results were obtained, but the most effective pH for the removal of turbidity was lower than that of chromaticity and COD for the combined effluent, and the medium-sector effluent was easier to obtain higher removal rates of turbidity, chromaticity and COD.The retention tests on wheat straw pulps were carried out by making and weighing the handsheets as well as measuring their ash contents with standard methods. The drainage tests were conducted by measuring the beating degree of furnish with straw pulps. The results showed that PASS/cationic or amphoteric starch were more effective
retention and drainage systems than their counterpart starch at all pH scope from slightly acid to alkaline papermaking, but they had better retention and drainage effects on wheat straw pulps at neutral / alkaline pH. The PASS / amphoteric starch system was more effective on retention and drainage of wheat straw pulps than PASS/cationic starch because amphoteric starch itself was more effective than cationic starch. The PASS/cationic or amphoteric starch systems behaved more like starch itself in retention and drainage characteristics at low starch dosage. Yet, they behaved more like microparticle system at higher starch dosage.The retention effects of PASS/amphoteric starch on wheat straw pulp were tested further with dynamic drainage jar (DDJ) fitted with 70 mesh screen. Similar results.were obtained with above test. The discrepancy was that amphoteric starch/PASS behaved like microparticle system at all starch dosage. The dosage between starch and PASS for most effective retention on wheat straw pulp had a relationship of compensation. More information was obtained from DDJ test. The addition sequence, that is the addition of starch followed by PASS, the simultaneous addition of starch and PASS, the addition of PASS followed by starch, included different retention mechanism. The stirring time after PASS addition at 500rpm had great effect on the retention of wheat straw pulps. The longer the time, the lower the retention. However, the stirring time at 750rpm before PASS addition had little effect on the retention. The retention decreased only when the starch-formed floes were destroyed by long time stirring at higher speed. The shear forces after starch addition also had remarkable effect on the retention of wheat straw pulps. Either low (less than 900rpm) or high (more than 11 OOrpm) shear forces could be
利用红外和X—射线衍射技术对聚合硅酸硫酸铝的结构特征研究表明:聚合硅酸硫酸铝与聚合硫酸铝具有相似的多羟基聚铝结构,其中的硅以与铝类似的结构形态参与了与其它羟基铝的配位聚合,使之常温结晶行为与聚合硫酸铝不同,但其最终会水解形成与无定形氢氧化铝类似的物质。
利用~(27)Al-NMR和Al-Ferron逐时络合比色法对聚合硅酸硫酸铝的结构特征研究表明:提高硅铝比使同一碱化度的聚合硅酸硫酸铝聚合程度略有降低。聚合硅酸硫酸铝和聚合硫酸铝的聚合均未通过Al_(13)途径。稀释使聚合硅酸硫酸铝趋于聚集成更大的分子,且碱化度越高者,这一趋势越明显。在一般的抄纸pH范围和应用浓度下,聚合硅酸硫酸铝主要以代表胶状聚合大分子的Al_c形式存在,且碱化度越高,相应Al_c的量越高。自来水中的杂离子缩小了pH对聚合硅酸硫酸铝结构形态的影响,且多羟基配合物组分Al_b的含量相对较高。因此,在较宽的pH范围内,Al_b、Al_c成为聚合硅酸硫酸铝在自来水稀释的水溶液中的主要结构形态。
利用逐时测定水解产物吸光度的方法对聚合硅酸硫酸铝的水解脱稳性能研究表明:聚合硅酸硫酸铝易水解脱稳,且其水解脱稳速度及水解沉淀物浓度随碱化度的增加而提高,随硅铝比增加的而下降。pH越高,其水解脱稳速度越快。
利用微电泳技术对聚合硅酸硫酸铝的动电特性研究表明:聚合硅酸硫酸铝的等电点和硫酸铝相近,约为pH5。但其所带电荷
A series of polyaluminum silicate sulfates with different basicities and Si / Al molar ratios were synthesized by the reactions of alum with sodium silicate and sodium aluminate. And their structure characteristics, aluminum species, stability of hydrolysis, electrokinetic properties and coagulation performance were studied. Their applications as coagulants in wastewater treatment and as microparticles in microparticle retention aid systems were investigated. Retention mechanism of amphoteric starch / PASS was proposed.The structure characteristics of polyaluminum silicate sulfate (PASS) were analyzed by means of infrared and X-ray diffraction spectra. It was found that the PASS had similar structures with polyaluminum sulfate (PAS), the silicon in PASS complexed with the other polyhydroxy aluminum at same behavior with aluminum. PASS was more stable against hydrolysis and had different crystallization behavior with PAS in environmental temperatures.The aluminum species in PASS aqueous solutions were identified with 27~A1-NMR and Al-Ferron complex timed colorimetric method. As expected that the degree of polymerization of PASS increased with the basicities but decreased with the Si/ Al molar ratios. No Al_(13) was found in PASS and PAS, but a considerable amount of Al_b, which represents the polynuclear aluminum species, were detected. PASS tended to aggregate to form larger molecules with dilution. And, the higher the basicity, the larger the trend. At the pH of papermaking PASS existed mainly as the form of Al_c, which represents the large colloid molecules of aluminum in the aluminum consistency often
used in papermaking. The hetero-ions in tap water lessened the discrepancy caused by pH, and increased the amount of Alb, consequently, Alb and Alc became the major aluminum species at the pH of papermaking.The hydrolysis destability of PASS was investigated by measuring the variation of the precipitate concentration with time caused by hydrolysis using spectrophotometric method. The results showed that the hydrolysis destability of PASS increased with basicity and pH, decreased with Si/Al molar ratio.The eletrokinetic characteristics of PASS were examined with microeletrophoretic method. The isoelectric point of PASS when titrated with NaOH was at approximately pH5, that is just agreement with alum at same conditions. Yet, its absolute values of Zeta potential either before or after the isoelectric point were larger than that of alum. The higher the basicity, the larger the absolute values of the Zeta potential of PASS. The Si/Al molar ratio only had negligible effect on the Zeta potential, especially for the positive value before isoelectric point. The absolute values of Zeta potential also increased with the stirring, but the isoelectric pH was hardly changed. The isoelectric pH for PASS was shown to be higher when it was diluted with tap water instead of deionized water, but the absolute values both before and after its isoelectric point became smaller.The coagulation - flocculation of PASS was investigated with kaolin suspension. The results showed that the dominated mechanism of coagulation - flocculation of PASS for removal of turbidity was not the charge neutralization. The most effective PASS for removal of turbidity had the basicity of 50% as well as Si/A! molar ratio of 0.05. The higher the basicity of PASS, The lower the most effective pH of
kaolin suspension for removal of turbidity.When treated the self-made deinked wastewater for removal of turbidity, chromaticity and COD with coagulation - flocculation method, PASS and PAS both were more effective coagulants than alum. However, PASS had a higher removal efficiency of chromaticity, PAS had a higher removal efficiency of COD. PASS with higher basicity (50%) had a higher removal efficiency of turbidity; PASS with lower basicity (30%) had a higher removal efficiency of COD and chromaticity . The higher the basicity , the lower the most effective pH for the removal of turbidity, chromaticity and COD. For the same PASS, the most effective pH for the removal of turbidity, chromaticity and COD were decreased according as above order. When the deinked wastewater was coagulated and flocculated by the synergism of PASS and CPAM, the floes produced were large and heavy, therefore, its settling velocity increased. Yet, CPAM had little effects on the removal efficiency of turbidity, chromaticity and COD.When the pulping and papermaking combined effluent and their medium-sector effluent that include screened, cleaned as well as bleaching effluents were treated with PASS, the similar results were obtained, but the most effective pH for the removal of turbidity was lower than that of chromaticity and COD for the combined effluent, and the medium-sector effluent was easier to obtain higher removal rates of turbidity, chromaticity and COD.The retention tests on wheat straw pulps were carried out by making and weighing the handsheets as well as measuring their ash contents with standard methods. The drainage tests were conducted by measuring the beating degree of furnish with straw pulps. The results showed that PASS/cationic or amphoteric starch were more effective
retention and drainage systems than their counterpart starch at all pH scope from slightly acid to alkaline papermaking, but they had better retention and drainage effects on wheat straw pulps at neutral / alkaline pH. The PASS / amphoteric starch system was more effective on retention and drainage of wheat straw pulps than PASS/cationic starch because amphoteric starch itself was more effective than cationic starch. The PASS/cationic or amphoteric starch systems behaved more like starch itself in retention and drainage characteristics at low starch dosage. Yet, they behaved more like microparticle system at higher starch dosage.The retention effects of PASS/amphoteric starch on wheat straw pulp were tested further with dynamic drainage jar (DDJ) fitted with 70 mesh screen. Similar results.were obtained with above test. The discrepancy was that amphoteric starch/PASS behaved like microparticle system at all starch dosage. The dosage between starch and PASS for most effective retention on wheat straw pulp had a relationship of compensation. More information was obtained from DDJ test. The addition sequence, that is the addition of starch followed by PASS, the simultaneous addition of starch and PASS, the addition of PASS followed by starch, included different retention mechanism. The stirring time after PASS addition at 500rpm had great effect on the retention of wheat straw pulps. The longer the time, the lower the retention. However, the stirring time at 750rpm before PASS addition had little effect on the retention. The retention decreased only when the starch-formed floes were destroyed by long time stirring at higher speed. The shear forces after starch addition also had remarkable effect on the retention of wheat straw pulps. Either low (less than 900rpm) or high (more than 11 OOrpm) shear forces could be
引文
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