Study on thermal dissociation of trioctylamine hydrochloride catalyzed by 5A molecular sieve
-
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.
-
Key words:
- trioctylamine hydrochloride /
- 5A molecular sieve /
- thermal dissociation /
- solid acid
-
图 2 不同温度下5A分子筛催化TOAHCI热解曲线
Figure 2. Thermal dissociation curves of TOAHCI catalyzed by 5A at different temperature
图 5 不同反应温度下5A分子筛催化TOAHCl热解能耗计算
Figure 5. Energy consumption of TOAHCl pyrolysis catalyzed by 5A at different reaction temperature
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
图 7 转速对5A分子筛催化TOAHCl热解影响
Figure 7. Effect of speed on thermal dissociation of TOAHCl catalyzed by 5A molecular
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
图 9 不同十氢萘用量下5A分子筛催化TOAHCl热解能耗计算
Figure 9. Energy consumption of TOAHCl pyrolysis catalyzed by 5A at different decalin content
图 10 5A分子筛用量对TOAHCl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 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 
下载: 导出CSV
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
下载: 导出CSV
-
[1] XU Y, ZHU L, CHANG D, et al. International chains of CO2 capture, utilization and storage (CCUS) in a carbon-neutral world[J]. Resources, Conservation & Recycling, 2021, 167: 105433. doi: 10.1016/j.resconrec.2021.105433 [2] SINGH U, COLOSI L M. The case for estimating carbon return on investment (CROI) for CCUS platforms[J]. Applied Energy, 2021, 285: 1116394. doi: 10.1016/J.APENERGY.2020.116394 [3] JIANG K, ASHWORTH P. The development of Carbon Capture Utilization and Storage (CCUS) research in China: A bibliometric perspective[J]. Renewable and Sustainable Energy Reviews, 2021, 138: 110521. doi: 10.1016/J.RSER.2020.110521 [4] ZHOU Z, LIANG F, QIN W, et al. Coupled reaction and solvent extraction process to form Li2CO3: Mechanism and product characterization[J]. AIChE Journal, 2014, 60(1): 282-288. doi: 10.1002/aic.14243 [5] 许振良, 黄颂安, 施亚钧. 有机胺制碱碳化过程的热力学[J]. 华东化工学院学报, 1988(5): 605-613. [6] 黄钦佩, 靳凤民, 康仕芳. 有机胺萃取法制备碳酸钾[J]. 化学工业与工程, 2007(4): 304-308. doi: 10.3969/j.issn.1004-9533.2007.04.006 [7] WANG W, LIU X, WANG P, et al. Enhancement of CO2 Mineralization in Ca2+-/Mg2+-rich aqueous solutions using insoluble amine[J]. Industrial & Engineering Chemistry Research, 2013, 52(23): 8028-8033. [8] CHEN G, SONG X, DONG C, et al. Mineralizing CO2 as MgCO3 center dot 3H2O using abandoned MgCl2 based on a coupled reaction-extraction-alcohol precipitation process[J]. Energy & Fuels, 2016, 30(9): 7551-7559. [9] LI Y, SONG X, SUN S, et al. Extraction equilibrium of hydrochloric acid at low concentrations between water and N235 in isoamyl alcohol solution: Experiments and simulation[J]. Journal of Chemical and Engineering Data, 2015, 60(10): 3000-3008. doi: 10.1021/acs.jced.5b00409 [10] LI Y, SONG X, CHEN G, et al. Preparation of calcium carbonate and hydrogen chloride from distiller waste based on reactive extraction-crystallization process[J]. Chemical Engineering Journal, 2015, 278: 55-61. doi: 10.1016/j.cej.2014.12.058 [11] DAI C, CHEN H, SONG X, et al. Coupled reaction and solvent extraction process to utilize distiller waste using N235-isoamylol system[J]. Energy Sources Part a-Recovery Utilization and Environmental Effects. 10.1080/15567036.2020.1781299:14. [12] CHEN M, LI J, JIN Y, et al. Efficient solvent extraction of phosphoric acid with dibutyl sulfoxide[J]. Journal of Chemical Technology & Biotechnology, 2018, 93(2): 467-475. [13] 张少杰, 唐盛伟, 王杨, 等. 盐酸法磷酸萃取相的洗涤和磷酸反萃取过程初探[J/OL]. 无机盐工业: 2020年12月, 网络首发, 1-13. http://kns.cnki.net/kcms/detail/12.1069.tq.20201207.1218.004.html. [14] LIU X, WANG W, WANG M, et al. Experimental Study of CO2 Mineralization in Ca2+-rich aqueous solutions using tributylamine as an enhancing medium[J]. Energy & Fuels, 2014, 28(3): 2047-2053. [15] 叶龙泼, 李爽, 岳海荣, 等. 富钙溶液中萃取与反应耦合强化CO2矿化过程[J]. 化工学报, 2015, 66(9): 3511-3517. [16] CHEMARIN F, MOUSSA M, ALLAIS F, et al. Recovery of 3-hydroxypropionic acid from organic phases after reactive extraction with amines in an alcohol-type solvent[J]. Separation and Purification Technology, 2019, 219: 260-267. doi: 10.1016/j.seppur.2019.02.026 [17] DONG C, SONG X, MEIJER E J, et al. Mechanism studies on thermal dissociation of tri-n-octylamine hydrochloride with FTIR, TG, DSC and quantum chemical methods[J]. Journal of Chemical Sciences, 2017, 129(9): 1431-1440. doi: 10.1007/s12039-017-1357-4 [18] DONG C, SONG X, ZHANG J, et al. Insight into thermal dissociation of tri-n-octylamine hydrochloride: The key to realizing CO2 mineralization with waste calcium/magnesium chloride liquids[J]. Energy Science & Engineering, 2018, 6(5): 437-447. [19] DONG C, SONG X, ZHANG J, et al. Thermodynamics and kinetics analysis of thermal dissociation of tri-n-octylamine hydrochloride in open system: A DFT and TGA study[J]. Thermochimica Acta, 2018, 670: 35-43. doi: 10.1016/j.tca.2018.05.017 [20] GIBSON E K. Amine Hydrochloride Salts: A Problem in Polyurethane Synthesis[D]. [s.n.] University of Glasgow, 2007. -
点击查看大图
计量
- 文章访问数: 96
- HTML全文浏览量: 28
- PDF下载量: 6
- 被引次数: 0
