沉淀法回收生物油高温馏分中的酚类物质

赵欣; 李凯; 李明; 马善为; 朱锡锋

沉淀法回收生物油高温馏分中的酚类物质

基金项目:

国家重点基础研究发展规划 973计划, 2013CB228103

中国科学院重点部署项目 KGZD-EW-304-3

详细信息

中图分类号: TK6
计量
- 文章访问数: 87
- HTML全文浏览量: 115
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2015-09-18
- 修回日期: 2015-11-19

Separating phenols from high-temperature fraction of bio-oil by precipitation

More Information

Corresponding author: Tel: 0551-63600040, E-mail: xfzhu@ustc.edu.cn

摘要

摘要: 为了研究金属离子沉淀法对生物油高温馏分中酚类物质的回收, 提高生物油中化学物质的利用率, 利用气相色谱-质谱联用仪 (GC-MS) 从NaOH试剂浓度、反应温度和反应时间三个方面研究了镁离子对生物油中酚类物质的回收效果。结果表明, 镁离子与酚类物质形成了不溶物, 而且不同浓度的氢氧化钠溶液 (1.0-4.0 mol/L)、不同的反应温度 (25-85℃) 以及不同的反应时间 (5-35 min) 对实验结果有着不同程度的影响。结果表明, 在反应温度为25℃、氢氧化钠浓度为2.5 mol/L, 反应时间在20 min时为最佳反应条件。在此条件下, 对生物油高温馏分中对乙基苯酚的回收率可达34.97%。
- 生物油 /
- 酚类 /
- 镁离子 /
- 沉淀法 /
- 回收
Abstract: To improve the utilization of chemicals in bio-oil, recovery of phenolic compounds from high temperature bio-oil fractions by metal ion precipitation was studied.The effects of concentration of sodium hydroxide solution, reaction temperature and reaction time on the recovery of phenolic compounds by magnesium ion were examined using gas chromatography-mass spectrometry (GC-MS).The results demonstrate that the precipitation was formed instead of a salt of magnesium phenols.The optimum reaction conditions are reaction temperature of 25℃, 2.5 mol/L of sodium hydroxide solution, and reaction time of 20 min.In this case, the recovery of 4-ethylphenol from high temperature bio-oil fractions reaches 34.97%.
- bio-oil /
- phenol /
- magnesium ion /
- precipitation /
- recovery

HTML全文

图 1 沉淀法回收生物油中酚类物质的工艺路线示意图

Figure 1. Extraction procedure of phenolic compounds from bio-oil

下载: 全尺寸图片幻灯片

图 2 不溶物的红外光谱谱图

Figure 2. FT-IR spectrum of the complex

下载: 全尺寸图片幻灯片

图 3 乙酸乙酯层的总离子色谱图

Figure 3. Total ion chromatogram of ethyl acetate layer

下载: 全尺寸图片幻灯片

图 4 在不同NaOH浓度下对乙基苯酚的萃取率和pH值

Figure 4. 4-ethylphenol extraction rate and pH value at various concentrations of sodium hydroxide solution

下载: 全尺寸图片幻灯片

图 5 在不同温度下对乙基苯酚的萃取率和pH值

Figure 5. 4-ethylphenol extraction rate and pH value at various temperatures

下载: 全尺寸图片幻灯片

图 6 在不同时间下对乙基苯酚的萃取率和pH值

Figure 6. 4-ethylphenol extraction rate and pH value at various reaction times

下载: 全尺寸图片幻灯片

表 1 生物油高温馏分中酚类物质的化学成分

Table 1. Chemical compositions of phenolic compounds from high temperature fractions of bio-oil

No.	Chemical compound	Molecular formula	Molecular weight /(g·mol^-1)	Structure	Peak area /%
1	phenol	C₆H₆O	94		4.47
2	phenol, 2-methyl-	C₇H₈O	108		5.67
3	phenol, 3-methyl-	C₇H₈O	108		6.56
4	phenol, 2-methoxy-	C₇H₈O₂	124		3.35
5	2, 5-xylenol	C₈H₁₀O	122		1.88
6	phenol, 4-ethyl-	C₈H₁₀O	122		21.5
7	phenol, 2-methoxy-4-methyl-	C₈H₁₀O₂	138		2.86
8	1, 2-benzenediol	C₆H₆O₂	110		3.41
9	phenol, 3-(1-methylethyl)-	C₉H₁₀O	134		3.05
10	phenol, 3-methyl-4-ethyl-	C₉H₁₀O	134		1.58
11	phenol, 4-isopropyl-	C₉H₁₂O	136		3.89
12	guaiacol, 4-ethyl-	C₉H₁₀O₂	150		3.75
13	1, 2-benzenediol, 4-methyl-	C₇H₈O₂	124		2.1
14	phenol, 4-sec-butyl-	C₁₀H₁₄O	150		2.37
15	phenol, 2, 6-dimethoxy-	C₈H₁₀O₃	154		3.15
16	guaiacol, 5-allyl-	C₁₀H₁₂O₂	164		2.51
17	phenol, 2-methoxy-4-propyl-	C₁₀H₁₄O₂	166		2.94
18	catechol, 4-ethyl-	C₈H₁₀O₂	138		2.2
19	guaiacol, 4-propenyl-	C₁₀H₁₂O₂	164		2.04

下载: 导出CSV

表 2 乙酸乙酯层中的酚类化合物

Table 2. Phenolic compounds identified in the ethyl acetate layer

No.	Chemical compound	Molecular formula	Molecular weight /(g·mol^-1)	Structure	Peak area /%
1	phenol	C₆H₆O	94		5.48
2	phenol, 3-methyl-	C₇H₈O	108		6.47
3	guaiacol	C₇H₈O₂	124		4.03
4	phenol, 4-ethyl-	C₈H₁₀O	122		21.75
5	guaiacol, 4-methyl	C₈H₁₀O₂	138		3.74
6	catechol	C₆H₆O₂	110		3.19
7	phenol, 3-(1-methylethyl)-	C₉H₁₀O	134		3.95
8	phenol, 2-ethyl-5-methyl-	C₉H₁₂O	136		2.09
9	phenol, 4-propyl-	C₉H₁₂O	136		4.01
10	guaiacol, 4-ethyl-	C₉H₁₀O₂	150		5.6
11	catechol, 4-methyl-	C₈H₁₀O₂	138		1.77
12	phenol, 4-sec-butyl-	C₁₀H₁₄O	150		1.48
13	phenol, 2, 6-dimethoxy-	C₈H₁₀O₃	154		2.78
14	guaiacol, 5-allyl-	C₁₀H₁₂O₂	156		1.85
15	phenol, 2-methoxy-4-propyl-	C₁₀H₁₄O₂	166		3.96
16	catechol, 4-ethyl-	C₈H₁₀O₂	138		1.56
17	guaiacol, 4-propenyl-	C₉H₁₂O	136		2.1

下载: 导出CSV

参考文献(17)

[1]	朱锡锋.生物油制备技术[M].北京:化学工业出版社, 2013. ZHU Xi-feng.Preparation and application of bio-oil[M].Beijing:Chemical Industry Presss, 2013.
[2]	OASMAA A, CZERNIK S.Fuel oil quality of biomass pyrolysis oils-state of the art for the end user[J].Energy Fuels, 1999, 13:914-921. doi: 10.1021/ef980272b
[3]	BRIDGWATER A V, PEACOCKE G V C.Fast pyrolysis processes for biomass[J].Renew Sust Energy Rev, 2000, 4:1-73. doi: 10.1016/S1364-0321(99)00007-6
[4]	AMEN-CHEN C, PAKDEL H, ROY C.Separation of phenols from Eucalyptus wood tar[J].Biomass Bioenergy, 1997, 13(1/2):25-37.
[5]	MAHFUD F H, VAN GEEL F P, VENDERBOSCH R H, HEERES H J.Acetic acid recovery from fast pyrolysis oil:An exploratory study on liquid-liquid reactive extraction using aliphatic tertiary amines[J].Sep Sci Technol, 2008, 43(11/12):3056-3074.
[6]	GANDER M, RAPP K M, SCHIWECK H.Process for preparing 1, 6-β-anhydroglucopyranose (levoglucosan) in high purity:US, 5023330[P].1991-06-11.
[7]	STRADAL J A, UNDERWOOD G L.Process for producing hydroxyacetaldehyde:US, 5252188[P].1993-10-12.
[8]	STRADAL J A, UNDERWOOD G L.Process for producing hydroxyacetaldehyde:US, 5393542[P].1995-02-28.
[9]	DINESH M, CHARLES U P, PHILIP H S.Pyrolysis of wood/biomass for bio-oil:A critical review[J].Energy Fuels, 2006, 20:848-889. doi: 10.1021/ef0502397
[10]	EFFENDI A, GERHAUSER H, BRIDGWATER A V.Production of renewable phenolic resins by thermochemical conversion of biomass:A review[J].Renew Sust Energy Rev, 2008, 12:2092-2116. doi: 10.1016/j.rser.2007.04.008
[11]	LI J, WANG C, YANG Z.Production and separation of phenols from biomass-derived bio-petroleum[J].J Anal Appl Pyrolysis, 2010, 89(2):218-224. doi: 10.1016/j.jaap.2010.08.004
[12]	GE Y Z, JIN H.Recovery process for phenolic compounds from coal-derived oils by ions of solublemetal salts[J].Fuel, 1996, 75:1681-1683. doi: 10.1016/0016-2361(95)00276-6
[13]	WANG D, LI D B, LIU Y Q, LV D C, YE Y Y, ZHU S J, ZHANG B B.Study of a new complex method for extraction of phenolic compounds from bio-oils[J].Sep Purif Technol, 2014, 134:132-138. doi: 10.1016/j.seppur.2014.07.033
[14]	葛宜掌, 金红, 李斌.Ba²⁺离子沉淀法回收酚类化学过程的研究[J].燃料化学学报, 1996, 24(3):266-270. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX603.014.htm GE Yi-zhang, JIN Hong, LI Bin.Study on recovery of phenolic compounds using Ba²⁺ as precipitant[J].J Fuel Chem Technol, 1996, 24(3):266-270. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX603.014.htm
[15]	JEWEL A.CAPUNITAN, SERGIO C.CAPAREDA.Characterization and separation of corn stover bio-oil by fractional distillation[J].Fuel, 2013, 112:60-73. doi: 10.1016/j.fuel.2013.04.079
[16]	明珠, 吴云海, 阿依妮尕尔·艾尔肯.茶汤与金属离子络合反应的研究[J].环境科技, 2015, 28(4):5-11. http://youxian.cnki.com.cn/yxdetail.aspx?filename=JSHJ2015072100F&dbname=CAPJ2015 MING Zhu, WU Yun-hai, ARKEN·AYINIGAR.Study on complexation reaction of tea infusion with metal ions[J].Environ Sci Technol, 2015, 28(4):5-11. http://youxian.cnki.com.cn/yxdetail.aspx?filename=JSHJ2015072100F&dbname=CAPJ2015
[17]	GE Y, JIN H.Recovery of phenols from coal tar and waste water by precipitation[J].J China Coal Soc, 1995, 20:545-548.