Thermal Dissociation of Trioctylamine Hydrochloride Catalyzed by 5A Molecular Sieve
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摘要: 制碱含钙废液与CO2反应-萃取-结晶耦合工艺低成本运行的关键在于有机胺有效再生。以5A分子筛为有机胺盐酸盐热解催化剂，考察有机胺盐酸盐热解过程的影响参数并对其进行优化。结果表明：提高热解温度、载气流量、增大稀释剂和催化剂用量，热解反应速率加快，转化率提高。综合考虑转化率和能耗，选择的优化工艺参数为：反应温度180 ℃，载气流量300 mL/min，转速150 r/min，三辛胺盐酸盐与十氢萘和5A分子筛的质量比分别为1∶4和10∶1。在此最优工艺下，反应4 h时的转化率达95%、8 h转化率为99%。5次循环实验的结果表明：5A分子筛具有良好的催化活性。Abstract: Coupled process of mineralization of CaCl2 waste by reaction extraction crystallization would be beneficial for waste recycling and mineralization of CO2, which has a broad application prospect. The key to low cost operation of reaction extraction crystallization coupling mineralization process is the effective regeneration of organic amine extractant. Solid acid catalyst was used to strengthen the pyrolysis regeneration process to realize the regeneration of organic amine.At the same time, the coupled process also producedvaluable HCl gas, improving the economyof the process. The effect of heating temperature, carrier gas flow, stirring speed, diluent amount and catalyst amount on the thermal dissociation of trioctylamine hydrochloride by 5A molecular sieve were investigated. The results showed that the pyrolysis of trioctylamine hydrochloride catalyzed by 5A molecular sieve conformed to the first-order kinetic model. The thermal dissociation reaction rate was accelerated and the conversion rate increased with thermal dissociation temperature, carrier gas flow, diluent naphthalene and catalyst amount, and the effect of rotational speed on the thermal dissociation reaction was not obvious. Considering the conversion rate and energy consumption, the optimized pyrolysis conditions were as follows: reaction temperature 180 ℃, carrier gas flow 300 mL/min, rotating speed 150 r/min, mass ratio of triactylamine hydrochloride to naphthalene 1∶4, mass ratio to 5A molecular sieve 10∶1, 4-hour conversion rate is 95%, and 8 h conversion rate is 99%. The 5 cycles experiments showed that 5A zeolite still had good catalytic activity.
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Key words:
- trioctylamine hydrochloride /
- 5A molecular sieve /
- thermal dissociation /
- solid acid
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图 2 不同温度下5A分子筛催化三辛胺盐酸盐热解曲线
Figure 2. Thermal dissociation curves of TOAHCl catalyzed by 5A molecular sieve at different temperatures
图 5 不同反应温度下5A分子筛催化三辛胺盐酸盐热解能耗计算
Figure 5. Energy consumption of TOAHCl pyrolysis catalyzed by 5A molecular sieve at different reaction temperatures
图 6 载气流量对5A分子筛催化三辛胺盐酸盐热解过程的影响
Figure 6. Effect of carrier gas flow on thermal dissociation of TOAHCl catalyzed by 5A molecular sieve
图 7 转速对5A分子筛催化三辛胺盐酸盐热解的影响
Figure 7. Effect of rotate speed on thermal dissociation of TOAHCl catalyzed by 5A molecular sieve
图 8 十氢萘用量对5A分子筛催化三辛胺盐酸盐热解效果的影响
Figure 8. Effect of decalin content on thermal dissociation of TOAHCl catalyzed by 5A molecular sieve
图 9 不同十氢萘用量下5A分子筛催化三辛胺盐酸盐热解能耗
Figure 9. Energy consumption of TOAHCl pyrolysis catalyzed by 5A molecular sieve at different decalin content
图 10 5A分子筛用量对三辛胺盐酸盐热解反应的影响
Figure 10. Effect of 5A molecular sieve dosage on thermal dissociation of TOAHCl
表 1 不同温度下达到不同转化率所用反应时间
Table 1. Reaction time for different conversion at different temperatures
T/℃ t/h 90% 95% 98% 99% 180 2.8 3.6 4.7 5.6 170 5.9 7.7 10.0 11.8 160 13.5 17.6 23.0 27.0 150 18.8 24.5 32.0 37.6 
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表 2 不同十氢萘用量达到不同转化率所用反应时间
Table 2. Reaction time for different conversion rate at different decalin content
mTOAHCI∶${ {m} }_{{{\rm{C}}_{10}{\rm{H}}_{18}}}$ t/h 90% 95% 98% 99% 1∶5 2.6 3.4 4.5 5.2 1∶4 2.9 3.8 5.0 5.9 1∶3 5.7 7.4 9.7 11.4 1∶2 6.2 8.1 10.5 12.4 1∶1 18.5 24.0 31.3 36.9
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