从工业废液中提取巴豆醛氧化制备巴豆酸
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摘要
本文研究了从工业废液中分离提纯巴豆醛,并将分离提纯得到的巴豆醛用于氧化合成巴豆酸。提取巴豆酸之后的废液再进一步提取巴豆酸乙烯酯,该乙烯酯为可聚合单体。
常压精馏提纯含巴豆醛约30%的工业废液原料时约需要经过三次精馏可得到纯度98%的巴豆醛。常压加水共沸精馏较容易得到80%的巴豆醛,其中含水量约为10%,但将此共沸物再进行精馏得到的仍是含水共沸物,若要进一步提纯巴豆醛需采用其他方法。
无催化剂的条件下空气氧化约60g 90%巴豆醛原料制备巴豆酸的最佳反应条件是:空气流量200mL/min,反应时间12h,反应温度30℃,用气相色谱测(GC)产率为66.9%,初步回收产率为38.1%。
H_3PO_4催化氧化同样原料制备巴豆酸的最佳反应条件是:空气流量200mL/min,催化剂用量为反应物的4.5‰,反应时间12h,反应温度30℃,GC产率为67.9%,初步回收产率为39.5%。
Cu(Ac)_2催化氧化同样原料制备巴豆酸的最佳反应条件是:催化剂用量为5.84‰,空气流量200mL/min,反应时间16h,温度30℃,GC产率为63.4%,初步回收产率是28.2%。
Cu(Ac)_2/Co(Ac)_2催化氧化同样原料制备巴豆酸的最佳反应条件是:催化剂用量约为原料的5‰,且Cu(Ac)_2:Co(Ac)_2=30%:70%,空气流量200mL/min,反应时间16h,反应温度30℃,GC产率为62.4%,初步回收产率是25.2%。
比较几种催化剂及无催化剂的最佳反应产率,可以发现H_3PO_4催化反应效果最好,产率最高,所得粗产品的纯度也较高。
The method to extract and purify crotonaldehyde from the industrial waste liquid was studied in this paper.The obtained crotonaldehyde from the purification was used to oxidation synthesize crotonic acid.After extract crotonic acid,Vinyl Crotonate was extracted from industrial waste liquid,and can be polymerized as monomer.
To extract and purify crotonaldehyde from the industrial waste liquid which contents 30%of crotonaldehyde,after 3 times of batch distillation under normal pressure crotonaldehyde of 98%purity could be obtained.The azeotropic distillation with water under normal pressure was ready to obtained the distillate containing 80%of crotonaldehyde and about 10%of water.Further distillation of this crotonaldehyde could not increase the purity of the crotonaldehyde.If purer crotonaldehyde is wanted,other methods must be used.
The optimum reaction condition of synthesizing crotonic acid from 60g of 90%of crotonaldehyde without catalyst was the following:the flow rate of air was 200mL/min, reaction time～12 hours,temperature～30℃.The yield of crotonic acid was 66.9%mensurated with the gas chromatography,the primary recovery yield was 38.1%.
The optimum reaction condition of synthesizing crotonic acid from the same material with H_3PO_4 as catalyst was the following:the flow rate of air was 200mL/min,the dosage of catalyst was 4.5‰reaction time～12 hours,temperature～30℃.The yield of crotonic acid was 67.9%mensurated with the gas chromatography,the primary recovery yield was 39.5%.
The optimum reaction condition of synthesizing crotonic acid from same material with Cu(Ac)_2 as catalyst was the following:the flow rate of air was 200mL/min,the dosage of catalyst was 5.84‰reaction time～16 hours,temperature～30℃.The yield of crotonic acid was 63.4%mensurated with the gas chromatography,the primary recovery yield was 28.4%.
The optimum reaction condition of synthesizing crotonic acid from same material with Cu(Ac)_2/Co(Ac)_2 as catalyst was the following:the flow rate of air was 200mL/min,the dosage of catalyst was 5‰and the ratio of Cu(Ac)_2:Co(Ac)_2 was 30%:70%,reaction time～16 hours,temperature～30℃.The yield of crotonic acid was 62.4%mensurated with the gas chromatography,the primary recovery yield was 25.2%.
Comparing the yields of these catalysts and conditions,it could be found that the reactive effectiveness and the yield of H_3PO_4 as the catalyst was best,the purity of its crude products was also higher.
常压精馏提纯含巴豆醛约30%的工业废液原料时约需要经过三次精馏可得到纯度98%的巴豆醛。常压加水共沸精馏较容易得到80%的巴豆醛,其中含水量约为10%,但将此共沸物再进行精馏得到的仍是含水共沸物,若要进一步提纯巴豆醛需采用其他方法。
无催化剂的条件下空气氧化约60g 90%巴豆醛原料制备巴豆酸的最佳反应条件是:空气流量200mL/min,反应时间12h,反应温度30℃,用气相色谱测(GC)产率为66.9%,初步回收产率为38.1%。
H_3PO_4催化氧化同样原料制备巴豆酸的最佳反应条件是:空气流量200mL/min,催化剂用量为反应物的4.5‰,反应时间12h,反应温度30℃,GC产率为67.9%,初步回收产率为39.5%。
Cu(Ac)_2催化氧化同样原料制备巴豆酸的最佳反应条件是:催化剂用量为5.84‰,空气流量200mL/min,反应时间16h,温度30℃,GC产率为63.4%,初步回收产率是28.2%。
Cu(Ac)_2/Co(Ac)_2催化氧化同样原料制备巴豆酸的最佳反应条件是:催化剂用量约为原料的5‰,且Cu(Ac)_2:Co(Ac)_2=30%:70%,空气流量200mL/min,反应时间16h,反应温度30℃,GC产率为62.4%,初步回收产率是25.2%。
比较几种催化剂及无催化剂的最佳反应产率,可以发现H_3PO_4催化反应效果最好,产率最高,所得粗产品的纯度也较高。
The method to extract and purify crotonaldehyde from the industrial waste liquid was studied in this paper.The obtained crotonaldehyde from the purification was used to oxidation synthesize crotonic acid.After extract crotonic acid,Vinyl Crotonate was extracted from industrial waste liquid,and can be polymerized as monomer.
To extract and purify crotonaldehyde from the industrial waste liquid which contents 30%of crotonaldehyde,after 3 times of batch distillation under normal pressure crotonaldehyde of 98%purity could be obtained.The azeotropic distillation with water under normal pressure was ready to obtained the distillate containing 80%of crotonaldehyde and about 10%of water.Further distillation of this crotonaldehyde could not increase the purity of the crotonaldehyde.If purer crotonaldehyde is wanted,other methods must be used.
The optimum reaction condition of synthesizing crotonic acid from 60g of 90%of crotonaldehyde without catalyst was the following:the flow rate of air was 200mL/min, reaction time～12 hours,temperature～30℃.The yield of crotonic acid was 66.9%mensurated with the gas chromatography,the primary recovery yield was 38.1%.
The optimum reaction condition of synthesizing crotonic acid from the same material with H_3PO_4 as catalyst was the following:the flow rate of air was 200mL/min,the dosage of catalyst was 4.5‰reaction time～12 hours,temperature～30℃.The yield of crotonic acid was 67.9%mensurated with the gas chromatography,the primary recovery yield was 39.5%.
The optimum reaction condition of synthesizing crotonic acid from same material with Cu(Ac)_2 as catalyst was the following:the flow rate of air was 200mL/min,the dosage of catalyst was 5.84‰reaction time～16 hours,temperature～30℃.The yield of crotonic acid was 63.4%mensurated with the gas chromatography,the primary recovery yield was 28.4%.
The optimum reaction condition of synthesizing crotonic acid from same material with Cu(Ac)_2/Co(Ac)_2 as catalyst was the following:the flow rate of air was 200mL/min,the dosage of catalyst was 5‰and the ratio of Cu(Ac)_2:Co(Ac)_2 was 30%:70%,reaction time～16 hours,temperature～30℃.The yield of crotonic acid was 62.4%mensurated with the gas chromatography,the primary recovery yield was 25.2%.
Comparing the yields of these catalysts and conditions,it could be found that the reactive effectiveness and the yield of H_3PO_4 as the catalyst was best,the purity of its crude products was also higher.
引文
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[30]王贵,姚德.2-丁烯醛气相中无催化环氧化反应[J].山东理工大学学报(自然科学版),2003,17(2):1-4
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[33]Elektrizitatswerk L.A Process for the Production of Crotonic Acid from Croton Aldehyde[P].Germany,West:DE165728,1922.11.27
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[36]蔡哲斌,何佶,严赞开,等.金属氧化物/吸附树脂催化分子氧氧化巴豆醛的研究[J].湖北农学院学报,2000,20(4):334-337
[37]玄峰松,张大洋,吴丽.聚苯乙烯固载希夫碱钴金属配合物催化氧化制备巴豆酸和正丁酸[J].沈阳化工学院学报,2005,19(4):241-244
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