Study on 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,考察有机胺盐酸盐的热解过程影响,优化工艺参数。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。考虑转化率和能耗,优化的工艺参数为: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质量比为1∶4、与5A分子筛质量比为10∶1,反应4 h转化率达95%,8 h为99%。通过5次循环实验,结果表明5A分子筛保持良好催化活性。Abstract: Coupled process of CaCl2 waste mineralization by reaction extraction crystallization has the function of 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,, which improved 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 was increased with the increase of thermal dissociation temperature, carrier gas flow, the increase of 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 follws: reaction temperature 180 ℃, carrier gas flow 300 mL/min, rotating speed 150 rpm, 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-hour 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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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 temperature
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 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 at different decalin content
mTOAHCI∶${\rm{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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