Lyocell纤维生产用溶剂N-甲基吗啉-N-氧化物（NMMO）回收工艺和机理的研究
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摘要
本文探索了Lyocell纤维生产用溶剂N-甲基吗啉-N-氧化物(NMMO)的回收方法，并对回收的机理进行了研究，为选择合适回收工艺和溶剂NMMO多次循环有效使用作理论和生产上的指导。
本文研究了纤维素纤维／NMMO／水纺丝溶液体系中，各种工艺条件对NMMO／纤维素降解的影响；探讨了高效液相色谱法(HPLC)在不同的检测条件下对N-甲基吗啉-N-氧化物(NMMO)及其主要分解产物N-甲基吗啉(NMM)和吗啉(M)的定量检测，建立了用HPLC同时测定NMMO，NMM和M的方法；文中对凝固浴回收液中的悬浮物进行了结构和粒径大小分析，讨论了水质对回收液中的悬浮物大小以及纤维性能的影响；着重探讨了氧化锆陶瓷膜的制备机理，制备工艺条件以及氧化锆陶瓷膜在Lyocell纤维溶剂回收中的具体应用；研究了离子交换树脂去除部分带色杂质和金属离子以及选择性的去除吗啉(M)的机理和具体操作工艺条件；探讨了回收液的氧化脱色和氧化大部分N-甲基吗啉(NMM)到N-甲基吗啉-N-氧化物(NMMO)的工艺条件和简单机理，主要结论如下：
1．研究纤维素／NMMO／H_2O体系的降解与稳定时发现，在NMMO／纤维素体系中，酸性条件以及过高的温度不利于NMMO的稳定，浆液保温放置时间过长，将会增加NMMO的降解，也会加强纤维素的降解。金属离子的存在能够大大催化NMMO的降解，且能增加纤维素的降解；NMMO／纤维素体系中的金属离子含量为600ppm吋，NMMO的降解已经超过30％，而纤维素聚合度降解的更多；金属离子的存在能够降低NMMO／纤维素体系的热稳定性，甚至能使体系达到热失控分解。没食子酸丙酯是比鞣花酸和对苯二酚更有效的抗氧剂，其抗氧机理是捕捉体系中的自由基，从而减少自由基对纤维素的攻击，阻止纤维素的降解。而在NMMO加热浓缩的过程中出现的部分深色物质，主要是因为没食子酸丙酯被氧化成高度共轭的深色的双临苯醌。没食子酸丙酯对体系稳定的最佳浓度是0.4wt％，其和NaOH结合使用作为稳定剂，既能提高体系的热稳定性，又能阻止NMMO和纤维素的降解。
2．本文建立了一种在Lyocell纤维的NMMO溶剂回收中用反相高效液相色谱同时测定NMMO，NMM和M的方法：采用Waters公司的Xterra~(TM)色谱柱通过等梯度洗脱，使NMMO，M和NMM在碱性流动相条件下达到完全分离成为现实，它们的保留时间t_R依次为1.231，1.924和2.726分钟，而且分析周期仅为4分钟。通过均匀设计方法快速选择了最佳流动相，从而得到了分离M，NMM和NMMO的最佳条件为：
流动相：V(缓冲溶液)：V(乙腈)=97：3，其中缓沖溶液为0.02M／L的Na_2CO_3和NaHCO_3缓冲体系，pH也是用此缓冲溶液来调，pH值为10.54；三乙胺的体积分数为0.55％；流速：1ml／min；检测波长：218nm；检测器灵敏度为0.01AUFS；柱温：室温；进样量：10μl。本文确定的HPLC方法操作简便，测定准确，重现性好。NMMO在50～300mg／L范围内有良好的线性关系，最小检出限为50mg／L，平均回收率为96.85±0.48％，平行样(n=5)测定的RSD％低于3.6％；NMM在20-300mg／L范围内有良好的线性关系，最小检出限为20mg／L，平均回收率为98.41±0.45％，平行样(n=5)测定的RSD％低于3.4％；M在20～300 mg／L范围内有良好的线性关系，最小检出限为20mg／L，平均回收率为98.61±0.40％，平行样(n=5)测定的RSD％低于3.1％。
3．研究了纺丝凝固浴中悬浮粒子的结构和水质不同对纤维的部分性能的影响，并首次测定了凝固浴中的悬浮粒子的大小。结果表明：从红外谱图上看出，纺丝的浆粕和凝固浴中的悬浮粒子基本上是一种物质。不论凝固浴是采用蒸馏水还是自来水，粒子的个数平均粒径大概稍大于1μm，与蒸馏水比较起来，用自来水作凝固浴纺出的纤维白度降低了15％，强度降低了9.5％，断裂伸长下降了7.4％。
4．研究了ZrO_2陶瓷膜的制备及其在Lyocell纤维的凝固浴回收中的应用。结果表明：
粒径分布集中在5μm以上的Z_rO_2粒子不适宜于制备陶瓷动态膜。不同粒径的ZrO_2粉体的涂膜液的浓度均集中在0.7～0.8g／L左右。随着错流速度的增大渗透通量也增大，0.2m／s的错流速度为最佳涂膜条件。在涂膜时间到达30分钟后，渗透通量趋于稳定，因此采用30分钟为动态膜的涂膜时间参数。采用平均粒径为4.98μm粉体膜处理的凝固浴中颗粒的粒径较大，采用平均粒径为1.90μm和平均粒径为1.15μm粉体膜处理的凝固浴中颗粒的粒径较小，能够满足纺丝生产的需要。随操作压力的增大，通量开始上升较快，而后上升幅度较小，可以选择在150kPa时的操作压力运行。
5．采用阴离子交换树脂X不仅能去除Lyocell纺丝凝固浴的悬浮物，还能对其有效脱色。阳离子交换树脂Y不仅能去除NMMO的分解产物吗啉，还能去除铁、铜等金属离子，并且有良好的耐疲劳性。本文确定了先经过阴离子交换树脂X，再经过阳离子交换树脂Y的离子交换树脂法溶剂回收工艺，不但能脱色、去除吗啉和铁铜等金属离子，而且操作方便并能循环多次利用，完全能满足大工业生产的需要。经离子树脂交换处理浓缩后的再生NMMO溶剂能有效地溶解纤维素纺丝，所纺制的纤维性能良好。
6．分析了各种条件对氧化脱色反应的影响，并通过正交实验得到了氧化脱色的最佳工艺条件。再生温度对氧化反应的快慢和反应的程度影响很大，50℃、60℃时反应较慢且反应也不彻底，又因70℃时比80℃反应更平稳、好控制，所以优选70℃。H_2O_2加入量对反应进行的快慢和程度有影响，但其主要影响H_2O_2的残余量，以按回收溶液质量的1.0％加入为佳；溶液的PH为8是最佳的，也是适应生产实际要求的；溶液的NMMO浓度不作为最主要的影响因素，故按生产实际来取12％左右，本文用12.2％NMMO。正交实验得到的最佳方案为：再生温度为70℃，H_2O_2的加入量为1.0％，溶液PH为8，凝固浴溶液的浓度为12.2％NMMO。此外，NMM氧化到NMMO的最终工艺条件为：凝固浴溶液的pH为8，氧化反应温度为70℃，反应时间为5小时，H_2O_2加入量以H_2O_2与NMM的摩尔比为1.2。最后，NMM氧化到NMMO的产率为85％。
7．确定了Lyocell纤维生产用溶剂NMMO的回收的最终流程：
10％的NMMO凝固浴水溶液(w／w)→粗虑→精滤(ZrO_2陶瓷膜过滤)→阴离子交换树脂处理→阳离子交换树脂处理→H_2O_2氧化→浓缩到50％的NMMO水溶液(w／w)
In this thesis, the recycle process and mechanism of N-methylmorpholine-N-oxide (NMMO) as a solvent for the lyocell fibers production have been studied. In order to select the optimum recycle process parameter and use NMMO repeatedly, a new recycle process has been developed and the mechanism of the recovery of NMMO has also been investigated.
First of all, the effects of process parameters on the degradation of NMMO and cellulose in the system NMMO·H_2O /cellulose were studied; The quantitative determination of NMMO, N-methylmorpholine (NMM) and morpholine (M) was investigated. The quantity of main NMMO degradation products, i.e. NMM, M, under different conditions were discussed. A high performance liquid chromatography (HPLC) method for the determination and quantification of NMMO, NMM and M was also developed. A study on composition, structure and the sizes of the deformable floccule particles in the coagulation bath has been carried out; The influences of water quality on the properties of fiber and the sizes of the deformable floccule particles were discussed. The preparation mechanism and process of the ZrO_2 ceramic membrane, and the effects of applying the ZrO_2 ceramic membrane on NMMO recovery in lyocell fiber process were further investigated. The effects of operating conditions on removing the colored impurity, metal ions and morpholine (M) by ion exchange resin were investigated and the mechanism of this process was also studied. In addition, the processing conditions and mechanism of the discoloring oxidation reaction and how to oxidize the N-methylmorpholine to N-methylmorpholine-N-oxide were also discussed. The main results obtained are as follows:
1. The study of the degradation and stabilization in cellulose/NMMO/H_2O mixtures indicates that the acid environment and the elevated temperature increases the instability of NMMO, the degradations of NMMO and cellulose increase with heating time, the decompositions of NMMO and cellulose are further accelerated by metal ions. If the concentration of metal ions reaches 600 ppm in the system of NMMO·H_2O /cellulose, more than 30% of NMMO will be decomposed, while cellulose is degraded severely. It is shown that the thermal instability of NMMO/cellulose system in the presence of metal ions would be increased remarkably, even an uncontrollable decomposition process could occur. Propyl gallate could stabilize the NMMO/cellulose system better than hydroquinone and ellagic acid. The mechanism of stabilization using propyl gallate is that it acts as a free radical scavenger agent and inhibits the degradation of cellulose by preventing free radicals to attack cellulose. On the other hand, propyl gallate can be oxidated into highly conjugated bis(ortho-quinone) which is deeply colored. It represents one major reason for the discoloration of concentrating NMMO in the presence of propyl gallate. The optimum concentration of propyl gallate is 0.4wt% in order to stabilize NMMO/cellulose system, propyl gallate in combination with NaOH can not only counteract the degradation of NMMO and cellulose but also considerably increase the thermal stability of NMMO-cellulose-water solution.
2. A HPLC method for the separation and quantitative determination of NMMO,NMM and M from the coagulation bath has been established. The separation is carried out on a Xterra~(TM) C_(18) column. A standard method is employed to optimize the mobile phase, the mobile phase composition is V (0.02mol/L sodium carbonate and sodium bicarbonate buffer containing 0.55% triethylamine, pH10.54) :V (acetonitrile) =97:3. The detection is performed at 218nm and the injection volume is 10μl. A baseline separation is achieved within 4 min and the retention times for NMMO, M and NMM are 1.231 min, 1.924 min and 2.726 min respectively. NMMO,NMM and M show good linearity in the ranges of 50 mg/L to 300 mg/L, 20 mg/L to300 mg/L and 20 mg/L to300 mg/L respectively. The average recoveries is 96.85±0.48% for NMMO, 98.41±0.45% for NMM, and 98.61+0.40% for M. The detection limits for NMM0,NMM and M are 50 mg/L, 20mg/L and 20mg/L, RSD is less than 3.6%, 3.4% and 3.1% respectively. HPLC method is rapid and accurate, and suitable for control of the recovery of NMMO.
3. The composition and structure of the deformable floccule particles in coagulation bath and the effect of water quality on fiber properties are investigated, and the sizes of the deformable floccule particles are also determined. The deformable floccule particles in the coagulation bath show a main characteristic of cellulose from IR spectrum. The deformable particles average size in coagulation bath is bigger than 1μm whatever the coagulation bath is tap water or distilled water. Compared with the distilled water, the whiteness, tenacity and elongation at break of the fiber made from using tap water as coagulation bath decrease 15.5%, 9.5% and 7.4% respectively.
4. The preparation and application of ZrO_2 ceramic membrane in NMMO recycle process. The results show that ZrO_2 powder with size bigger than 5μm and too high or too low concentration of ZrO_2 powder are not suitable to for membrane. The best concentration for ZrO_2 membrane is 0.7-0.8g/l. The permeation flux increases with the cross-flow velocity, and the optimum cross-flow velocity for forming membrane is 0.2m/s. It is found permeation flux will be stable 30 minutes after forming membrane, so the time of forming dynamic membrane should be 30 minutes. The deformable particle sizes are big if the coagulation bath is filtrated through a membrane by using the ZrO_2 powder whose average size is 4.98μm. On the other hand, if the coagulation bath is filtrated through a membrane made by ZrO_2 powder with average size of 1.90μm or 1.15μm, the deformable particle sizes are small and can meet the demand of the recycle process. In addition, with the applied pressure increasing, the permeation flux increases rapidly at first, increases slightly and finally the applied pressure reaches 150kPa.
5. The anion exchange resin X can not only remove the deformable floccule particles in the coagulation bath but also decolorize the coagulation bath, while the cation exchange resin Y can selectively remove morpholine(M) as NMMO degradation product and eliminate metal ions like iron, copper etc, at the same time the cation exchange resin Y has a good fatigue resistance. The regeneration process of the aqueous solutions of NMMO is developed, that is, the coagulation bath to be recycled is treated by the anion exchange resin X firstly, then is treated by the cation exchange resin, the above process discolors the coagulation bath, removes morpholine(M) and eliminates metal ions, and is easy to operate, can be used repeatedly. The recycled NMMO aqueous solution can completely meets the demand of the industrial production for lyocell fibers. In addition, the properties of fiber which is made by recycled NMMO are almost equal to the fibers which are made by virgin NMMO.
6. The factors which influence the discoloring oxidation reaction of the coagulation bath are investigated. The optimum processing condition for the discoloring oxidation reaction is obtained. The results indicate that the regenerating temperature strongly affects the rate and extent of the oxidation reaction and it is found that the optimum regenerating temperature is 70℃. The amount of H_2O_2 mainly affects the remains of H_2O_2 besides influencing the rate and extent of the discoloring oxidation reaction. On the other hand, the NMMO concentration of the coagulation bath is not the main factor which influences the discoloring oxidation reaction. Finally the optimum processing conditions of the discoloring oxidation reaction are that, the regenerating temperature is 70℃, hydrogen peroxide added is 1.0% by weight of the total solution, the pH value of the coagulation bath is 8, and the NMMO concentration of the coagulation bath is 12.2%. The final processing condition of oxidizing N-methylmorpholine to N-methylmorpholine-N-oxide are that, the pH value of the coagulation bath is 8, the oxidation reaction temperature is 70℃, the oxidation reaction time is 5 hours, and hydrogen peroxide employed is 1.2 mole per mole of N-methylmorpholine. In addition, approximately 85% N-methylmorpholine can be converted into N-methylmorpholine-N-oxide.
7. The final recycle process of solvent NMMO for the lyocell fibers production has been established:
Coagulation bath(concentration of NMMO is 10%(w/w))→rough filtrated→fine filtrated (processed by ZrO_2 ceramic membrane)→treated with anion exchange resin→treated with cation exchange resin→oxidized by H_2O_2→concentrated into 50% NMMO aqueous solution (w/w) .
本文研究了纤维素纤维／NMMO／水纺丝溶液体系中，各种工艺条件对NMMO／纤维素降解的影响；探讨了高效液相色谱法(HPLC)在不同的检测条件下对N-甲基吗啉-N-氧化物(NMMO)及其主要分解产物N-甲基吗啉(NMM)和吗啉(M)的定量检测，建立了用HPLC同时测定NMMO，NMM和M的方法；文中对凝固浴回收液中的悬浮物进行了结构和粒径大小分析，讨论了水质对回收液中的悬浮物大小以及纤维性能的影响；着重探讨了氧化锆陶瓷膜的制备机理，制备工艺条件以及氧化锆陶瓷膜在Lyocell纤维溶剂回收中的具体应用；研究了离子交换树脂去除部分带色杂质和金属离子以及选择性的去除吗啉(M)的机理和具体操作工艺条件；探讨了回收液的氧化脱色和氧化大部分N-甲基吗啉(NMM)到N-甲基吗啉-N-氧化物(NMMO)的工艺条件和简单机理，主要结论如下：
1．研究纤维素／NMMO／H_2O体系的降解与稳定时发现，在NMMO／纤维素体系中，酸性条件以及过高的温度不利于NMMO的稳定，浆液保温放置时间过长，将会增加NMMO的降解，也会加强纤维素的降解。金属离子的存在能够大大催化NMMO的降解，且能增加纤维素的降解；NMMO／纤维素体系中的金属离子含量为600ppm吋，NMMO的降解已经超过30％，而纤维素聚合度降解的更多；金属离子的存在能够降低NMMO／纤维素体系的热稳定性，甚至能使体系达到热失控分解。没食子酸丙酯是比鞣花酸和对苯二酚更有效的抗氧剂，其抗氧机理是捕捉体系中的自由基，从而减少自由基对纤维素的攻击，阻止纤维素的降解。而在NMMO加热浓缩的过程中出现的部分深色物质，主要是因为没食子酸丙酯被氧化成高度共轭的深色的双临苯醌。没食子酸丙酯对体系稳定的最佳浓度是0.4wt％，其和NaOH结合使用作为稳定剂，既能提高体系的热稳定性，又能阻止NMMO和纤维素的降解。
2．本文建立了一种在Lyocell纤维的NMMO溶剂回收中用反相高效液相色谱同时测定NMMO，NMM和M的方法：采用Waters公司的Xterra~(TM)色谱柱通过等梯度洗脱，使NMMO，M和NMM在碱性流动相条件下达到完全分离成为现实，它们的保留时间t_R依次为1.231，1.924和2.726分钟，而且分析周期仅为4分钟。通过均匀设计方法快速选择了最佳流动相，从而得到了分离M，NMM和NMMO的最佳条件为：
流动相：V(缓冲溶液)：V(乙腈)=97：3，其中缓沖溶液为0.02M／L的Na_2CO_3和NaHCO_3缓冲体系，pH也是用此缓冲溶液来调，pH值为10.54；三乙胺的体积分数为0.55％；流速：1ml／min；检测波长：218nm；检测器灵敏度为0.01AUFS；柱温：室温；进样量：10μl。本文确定的HPLC方法操作简便，测定准确，重现性好。NMMO在50～300mg／L范围内有良好的线性关系，最小检出限为50mg／L，平均回收率为96.85±0.48％，平行样(n=5)测定的RSD％低于3.6％；NMM在20-300mg／L范围内有良好的线性关系，最小检出限为20mg／L，平均回收率为98.41±0.45％，平行样(n=5)测定的RSD％低于3.4％；M在20～300 mg／L范围内有良好的线性关系，最小检出限为20mg／L，平均回收率为98.61±0.40％，平行样(n=5)测定的RSD％低于3.1％。
3．研究了纺丝凝固浴中悬浮粒子的结构和水质不同对纤维的部分性能的影响，并首次测定了凝固浴中的悬浮粒子的大小。结果表明：从红外谱图上看出，纺丝的浆粕和凝固浴中的悬浮粒子基本上是一种物质。不论凝固浴是采用蒸馏水还是自来水，粒子的个数平均粒径大概稍大于1μm，与蒸馏水比较起来，用自来水作凝固浴纺出的纤维白度降低了15％，强度降低了9.5％，断裂伸长下降了7.4％。
4．研究了ZrO_2陶瓷膜的制备及其在Lyocell纤维的凝固浴回收中的应用。结果表明：
粒径分布集中在5μm以上的Z_rO_2粒子不适宜于制备陶瓷动态膜。不同粒径的ZrO_2粉体的涂膜液的浓度均集中在0.7～0.8g／L左右。随着错流速度的增大渗透通量也增大，0.2m／s的错流速度为最佳涂膜条件。在涂膜时间到达30分钟后，渗透通量趋于稳定，因此采用30分钟为动态膜的涂膜时间参数。采用平均粒径为4.98μm粉体膜处理的凝固浴中颗粒的粒径较大，采用平均粒径为1.90μm和平均粒径为1.15μm粉体膜处理的凝固浴中颗粒的粒径较小，能够满足纺丝生产的需要。随操作压力的增大，通量开始上升较快，而后上升幅度较小，可以选择在150kPa时的操作压力运行。
5．采用阴离子交换树脂X不仅能去除Lyocell纺丝凝固浴的悬浮物，还能对其有效脱色。阳离子交换树脂Y不仅能去除NMMO的分解产物吗啉，还能去除铁、铜等金属离子，并且有良好的耐疲劳性。本文确定了先经过阴离子交换树脂X，再经过阳离子交换树脂Y的离子交换树脂法溶剂回收工艺，不但能脱色、去除吗啉和铁铜等金属离子，而且操作方便并能循环多次利用，完全能满足大工业生产的需要。经离子树脂交换处理浓缩后的再生NMMO溶剂能有效地溶解纤维素纺丝，所纺制的纤维性能良好。
6．分析了各种条件对氧化脱色反应的影响，并通过正交实验得到了氧化脱色的最佳工艺条件。再生温度对氧化反应的快慢和反应的程度影响很大，50℃、60℃时反应较慢且反应也不彻底，又因70℃时比80℃反应更平稳、好控制，所以优选70℃。H_2O_2加入量对反应进行的快慢和程度有影响，但其主要影响H_2O_2的残余量，以按回收溶液质量的1.0％加入为佳；溶液的PH为8是最佳的，也是适应生产实际要求的；溶液的NMMO浓度不作为最主要的影响因素，故按生产实际来取12％左右，本文用12.2％NMMO。正交实验得到的最佳方案为：再生温度为70℃，H_2O_2的加入量为1.0％，溶液PH为8，凝固浴溶液的浓度为12.2％NMMO。此外，NMM氧化到NMMO的最终工艺条件为：凝固浴溶液的pH为8，氧化反应温度为70℃，反应时间为5小时，H_2O_2加入量以H_2O_2与NMM的摩尔比为1.2。最后，NMM氧化到NMMO的产率为85％。
7．确定了Lyocell纤维生产用溶剂NMMO的回收的最终流程：
10％的NMMO凝固浴水溶液(w／w)→粗虑→精滤(ZrO_2陶瓷膜过滤)→阴离子交换树脂处理→阳离子交换树脂处理→H_2O_2氧化→浓缩到50％的NMMO水溶液(w／w)
In this thesis, the recycle process and mechanism of N-methylmorpholine-N-oxide (NMMO) as a solvent for the lyocell fibers production have been studied. In order to select the optimum recycle process parameter and use NMMO repeatedly, a new recycle process has been developed and the mechanism of the recovery of NMMO has also been investigated.
First of all, the effects of process parameters on the degradation of NMMO and cellulose in the system NMMO·H_2O /cellulose were studied; The quantitative determination of NMMO, N-methylmorpholine (NMM) and morpholine (M) was investigated. The quantity of main NMMO degradation products, i.e. NMM, M, under different conditions were discussed. A high performance liquid chromatography (HPLC) method for the determination and quantification of NMMO, NMM and M was also developed. A study on composition, structure and the sizes of the deformable floccule particles in the coagulation bath has been carried out; The influences of water quality on the properties of fiber and the sizes of the deformable floccule particles were discussed. The preparation mechanism and process of the ZrO_2 ceramic membrane, and the effects of applying the ZrO_2 ceramic membrane on NMMO recovery in lyocell fiber process were further investigated. The effects of operating conditions on removing the colored impurity, metal ions and morpholine (M) by ion exchange resin were investigated and the mechanism of this process was also studied. In addition, the processing conditions and mechanism of the discoloring oxidation reaction and how to oxidize the N-methylmorpholine to N-methylmorpholine-N-oxide were also discussed. The main results obtained are as follows:
1. The study of the degradation and stabilization in cellulose/NMMO/H_2O mixtures indicates that the acid environment and the elevated temperature increases the instability of NMMO, the degradations of NMMO and cellulose increase with heating time, the decompositions of NMMO and cellulose are further accelerated by metal ions. If the concentration of metal ions reaches 600 ppm in the system of NMMO·H_2O /cellulose, more than 30% of NMMO will be decomposed, while cellulose is degraded severely. It is shown that the thermal instability of NMMO/cellulose system in the presence of metal ions would be increased remarkably, even an uncontrollable decomposition process could occur. Propyl gallate could stabilize the NMMO/cellulose system better than hydroquinone and ellagic acid. The mechanism of stabilization using propyl gallate is that it acts as a free radical scavenger agent and inhibits the degradation of cellulose by preventing free radicals to attack cellulose. On the other hand, propyl gallate can be oxidated into highly conjugated bis(ortho-quinone) which is deeply colored. It represents one major reason for the discoloration of concentrating NMMO in the presence of propyl gallate. The optimum concentration of propyl gallate is 0.4wt% in order to stabilize NMMO/cellulose system, propyl gallate in combination with NaOH can not only counteract the degradation of NMMO and cellulose but also considerably increase the thermal stability of NMMO-cellulose-water solution.
2. A HPLC method for the separation and quantitative determination of NMMO,NMM and M from the coagulation bath has been established. The separation is carried out on a Xterra~(TM) C_(18) column. A standard method is employed to optimize the mobile phase, the mobile phase composition is V (0.02mol/L sodium carbonate and sodium bicarbonate buffer containing 0.55% triethylamine, pH10.54) :V (acetonitrile) =97:3. The detection is performed at 218nm and the injection volume is 10μl. A baseline separation is achieved within 4 min and the retention times for NMMO, M and NMM are 1.231 min, 1.924 min and 2.726 min respectively. NMMO,NMM and M show good linearity in the ranges of 50 mg/L to 300 mg/L, 20 mg/L to300 mg/L and 20 mg/L to300 mg/L respectively. The average recoveries is 96.85±0.48% for NMMO, 98.41±0.45% for NMM, and 98.61+0.40% for M. The detection limits for NMM0,NMM and M are 50 mg/L, 20mg/L and 20mg/L, RSD is less than 3.6%, 3.4% and 3.1% respectively. HPLC method is rapid and accurate, and suitable for control of the recovery of NMMO.
3. The composition and structure of the deformable floccule particles in coagulation bath and the effect of water quality on fiber properties are investigated, and the sizes of the deformable floccule particles are also determined. The deformable floccule particles in the coagulation bath show a main characteristic of cellulose from IR spectrum. The deformable particles average size in coagulation bath is bigger than 1μm whatever the coagulation bath is tap water or distilled water. Compared with the distilled water, the whiteness, tenacity and elongation at break of the fiber made from using tap water as coagulation bath decrease 15.5%, 9.5% and 7.4% respectively.
4. The preparation and application of ZrO_2 ceramic membrane in NMMO recycle process. The results show that ZrO_2 powder with size bigger than 5μm and too high or too low concentration of ZrO_2 powder are not suitable to for membrane. The best concentration for ZrO_2 membrane is 0.7-0.8g/l. The permeation flux increases with the cross-flow velocity, and the optimum cross-flow velocity for forming membrane is 0.2m/s. It is found permeation flux will be stable 30 minutes after forming membrane, so the time of forming dynamic membrane should be 30 minutes. The deformable particle sizes are big if the coagulation bath is filtrated through a membrane by using the ZrO_2 powder whose average size is 4.98μm. On the other hand, if the coagulation bath is filtrated through a membrane made by ZrO_2 powder with average size of 1.90μm or 1.15μm, the deformable particle sizes are small and can meet the demand of the recycle process. In addition, with the applied pressure increasing, the permeation flux increases rapidly at first, increases slightly and finally the applied pressure reaches 150kPa.
5. The anion exchange resin X can not only remove the deformable floccule particles in the coagulation bath but also decolorize the coagulation bath, while the cation exchange resin Y can selectively remove morpholine(M) as NMMO degradation product and eliminate metal ions like iron, copper etc, at the same time the cation exchange resin Y has a good fatigue resistance. The regeneration process of the aqueous solutions of NMMO is developed, that is, the coagulation bath to be recycled is treated by the anion exchange resin X firstly, then is treated by the cation exchange resin, the above process discolors the coagulation bath, removes morpholine(M) and eliminates metal ions, and is easy to operate, can be used repeatedly. The recycled NMMO aqueous solution can completely meets the demand of the industrial production for lyocell fibers. In addition, the properties of fiber which is made by recycled NMMO are almost equal to the fibers which are made by virgin NMMO.
6. The factors which influence the discoloring oxidation reaction of the coagulation bath are investigated. The optimum processing condition for the discoloring oxidation reaction is obtained. The results indicate that the regenerating temperature strongly affects the rate and extent of the oxidation reaction and it is found that the optimum regenerating temperature is 70℃. The amount of H_2O_2 mainly affects the remains of H_2O_2 besides influencing the rate and extent of the discoloring oxidation reaction. On the other hand, the NMMO concentration of the coagulation bath is not the main factor which influences the discoloring oxidation reaction. Finally the optimum processing conditions of the discoloring oxidation reaction are that, the regenerating temperature is 70℃, hydrogen peroxide added is 1.0% by weight of the total solution, the pH value of the coagulation bath is 8, and the NMMO concentration of the coagulation bath is 12.2%. The final processing condition of oxidizing N-methylmorpholine to N-methylmorpholine-N-oxide are that, the pH value of the coagulation bath is 8, the oxidation reaction temperature is 70℃, the oxidation reaction time is 5 hours, and hydrogen peroxide employed is 1.2 mole per mole of N-methylmorpholine. In addition, approximately 85% N-methylmorpholine can be converted into N-methylmorpholine-N-oxide.
7. The final recycle process of solvent NMMO for the lyocell fibers production has been established:
Coagulation bath(concentration of NMMO is 10%(w/w))→rough filtrated→fine filtrated (processed by ZrO_2 ceramic membrane)→treated with anion exchange resin→treated with cation exchange resin→oxidized by H_2O_2→concentrated into 50% NMMO aqueous solution (w/w) .
引文
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