提高乙二醇紫外透过率的研究
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摘要
乙二醇是一种重要的化工原料，它目前最大的用途是用于生产聚酯。当它作为聚酯原料时，对其纯度要求很高，紫外透过率须达到一定的标准。本课题用离子交换树脂对乙二醇杂质进行富集，用盐酸甲醇液洗脱，然后用色质联用仪器进行分析，检测出了十几种杂质。本论文研究表明：造成乙二醇紫外透过率低的原因在于它含有两大类吸收紫外光的杂质，一类是含一或多个碳原子的有机羧酸及其衍生物，另一大类是含一到两个羰基的醛和酮。要有效提高乙二醇的紫外透过率，必须同时去除这两类杂质。
本课题用阴离子交换树脂和阳离子交换树脂串联吸附催化乙二醇含水样，即含约15％质量分数水的粗乙二醇，之后再进行精制得到的乙二醇成品紫外透过率在220nm、275nm和350nm处分别高于90％、95％和98％。
Ethylene glycol is an important chemical product. Now a particularly important use of ethylene glycol is in the production of polyester fibers. Ethylene glycol used in the manufacture of polyester fibers generally must be of exceptionally high purity and has to meet a rigid UV transmittance specification. In this paper, impurities were concentrated on an ion-exchange resin, then eluted by hydrochloric acid-methanol solution, and detected by gas chromatography-mass spectrometry. More than ten impurities were detected. The paper pointed out: there are two kinds of impurities which affect commercial ethylene glycol UV transmittance. One kind is organic acids, which contain one or more carbon atoms, and their derivates, the other is aldehyde and ketone which contain one or two carbonyls. In order to improve the UV transmittance of the ethylene glycol, these two kinds of impurities must be removed at the same time.In this paper, a bed of anion exchange resin followed by a bed of cation exchange resin was used to absorbed and catalyzed the aqueous mixture of ethylene glycols, which contain about 15 wt% water, then the product stream which has a reduced UV light absorbance was sent to be distilled. The final monoethylene glycol product has a UV transmittance over 90% at 220nm, 95% at 275nm and 98% at 350nm.
本课题用阴离子交换树脂和阳离子交换树脂串联吸附催化乙二醇含水样，即含约15％质量分数水的粗乙二醇，之后再进行精制得到的乙二醇成品紫外透过率在220nm、275nm和350nm处分别高于90％、95％和98％。
Ethylene glycol is an important chemical product. Now a particularly important use of ethylene glycol is in the production of polyester fibers. Ethylene glycol used in the manufacture of polyester fibers generally must be of exceptionally high purity and has to meet a rigid UV transmittance specification. In this paper, impurities were concentrated on an ion-exchange resin, then eluted by hydrochloric acid-methanol solution, and detected by gas chromatography-mass spectrometry. More than ten impurities were detected. The paper pointed out: there are two kinds of impurities which affect commercial ethylene glycol UV transmittance. One kind is organic acids, which contain one or more carbon atoms, and their derivates, the other is aldehyde and ketone which contain one or two carbonyls. In order to improve the UV transmittance of the ethylene glycol, these two kinds of impurities must be removed at the same time.In this paper, a bed of anion exchange resin followed by a bed of cation exchange resin was used to absorbed and catalyzed the aqueous mixture of ethylene glycols, which contain about 15 wt% water, then the product stream which has a reduced UV light absorbance was sent to be distilled. The final monoethylene glycol product has a UV transmittance over 90% at 220nm, 95% at 275nm and 98% at 350nm.
引文
1 刘定华，刘晓勤，华强等．乙二醇合成技术进展及应用前景[J]．南京工业大学学报，2002，24(6)：95-98．
2 沈景馀．国外环氧乙烷／乙二醇技术进展[J]．石油化工，2001，30(5)：404-409．
3 沈吕宁．影响乙二醇中紫外透过率组分的测定[J]．色谱，1994，12(5)：330-332．
4 平德来，王玉春．高效液相色谱法／二极管阵列检测器分析乙二醇中的未知痕量杂质[J]．石油化工，2000，29(12)：942-945．
5 YuHong Zhang, YuAn Feng, WenKui Lu. Identification of impurities affecting cimmercial ethylene glycol UV transmittance[J]. Journal of Chromatography A, 904(2000):87-97
6 陈红．对乙二醇成品UV值影响因素的探讨[J]．金山油化纤．1997(3)：30-32．
7 张勇斌，刘定华，马正飞等．NY型均相催化剂对乙二醇产品UV值影响的研究[J]．石油化工，2004，33(5)：460-463．
8 Reiche Charles Ronald, Heckman Jerry A. Method of producing glycols [P].US3970711,1976.
9 Davis Pauls, Allen George M, Schmitt Thomas. Method for purification of ethylene glycols[P].CA1330350,1994.
10 Schmitt Tomas M, Allen George M, et al. Process for improving the ultraviolet light transmittance of ethylene glycol [P]. US4647705 ,1985.
11 Briody Robert G, Cummings Frances M. Method for increasing the ultra-violet light transmittances of ethylene glycol[P]. US4289593, 1981.
12 Dietz Edward A, Albright David E. Method for producing UV absorption. in ethylene glycols, water, and mixtures[P]. CA2203485 ,1997.
13 Husain Mansoor. Glycol purification [P]. US6187973, 2001.
14 George Kathleen Frances, Dahuron Lise, Robson John Howrd, et al. Treatment of impurity-containing liquid streams in ethylene oxide/glycol processes with semi-permeable membranes[P]. W09109828, 1991.
15 Marquis Edward T, Sanderson John R. Improved glycol purification[P]. W09958483, 1999.
16 Rebsdat, Siegfried, Mayer, et al. Process for the manufacture of extremeiy pure monoethylene glycol[P]. US4349417, 1982.
17 Paggini, Alberto, Romano, et al. method for the production of high-purity ethylene glycols[P]. US4358625,1982.
18
18 Hoffman, William C.,Dever, John P.. Method for separating compounds in process streams[P]. US5440058, 1995.
19 Kasyanov Anatolij G, Kolesnikov Valerij Ya, Bodrikov Ivan V, et al. Method for cleaning ethylene glycol[P]. SU1498752, 1989.
20 Crandall John Worth, Ream Bernard Claude. Process for refining ethylene glycol[P]. EP0310189,1989.
21 徐克勋主编．精细有机化工原料及中间体手册．北京：化学工业出版社，1998．
22 司航主编．化工产品手册 有机化工原料．第3版．北京：化学工业出版社，1999．
23 陈冠荣等编辑．化工百科全书第2卷．北京：化学工业出版社，1991．
24 陈冠荣等编辑．化工百科全书第7卷．北京：化学工业出版社，1994．
25 陈冠荣等编辑．化工百科全书 第18卷．北京：化学工业出版社，1998．
26 周名成，俞洁勤．紫外与可见分光光度分析法．北京：化学工业出版社，1986．
27 谈天．谱学方法在有机化学中的应用．北京：高等教育出版社，1985．
28 陈洁，宋启泽．有机波谱分析．北京：北京理工大学出版社，2000．
29 陈耀祖，涂亚平．有机质谱及应用．北京：科学出版社，2001．
30 汪正范，杨树民，吴伴天．色谱联用技术．北京：化学工业出版社，2001．
31 汪正范．色谱定性与定量．北京：化学工业出版社，2000．
32 赵瑶兴，孙祥玉．有机分子结构光谱鉴定．北京：科学出版社，2003．
33 何炳林，黄文强．离子交换与吸附树脂．上海：上海科技教育出版社，1995．
34 王方．离子交换树脂．北京：北京科学技术出版社，1989．
35 钱旭红，高建宝，焦家俊等．有机化学．北京：化学工业出版社，1999．
36 GB6682-86实验室用水规格．
2 沈景馀．国外环氧乙烷／乙二醇技术进展[J]．石油化工，2001，30(5)：404-409．
3 沈吕宁．影响乙二醇中紫外透过率组分的测定[J]．色谱，1994，12(5)：330-332．
4 平德来，王玉春．高效液相色谱法／二极管阵列检测器分析乙二醇中的未知痕量杂质[J]．石油化工，2000，29(12)：942-945．
5 YuHong Zhang, YuAn Feng, WenKui Lu. Identification of impurities affecting cimmercial ethylene glycol UV transmittance[J]. Journal of Chromatography A, 904(2000):87-97
6 陈红．对乙二醇成品UV值影响因素的探讨[J]．金山油化纤．1997(3)：30-32．
7 张勇斌，刘定华，马正飞等．NY型均相催化剂对乙二醇产品UV值影响的研究[J]．石油化工，2004，33(5)：460-463．
8 Reiche Charles Ronald, Heckman Jerry A. Method of producing glycols [P].US3970711,1976.
9 Davis Pauls, Allen George M, Schmitt Thomas. Method for purification of ethylene glycols[P].CA1330350,1994.
10 Schmitt Tomas M, Allen George M, et al. Process for improving the ultraviolet light transmittance of ethylene glycol [P]. US4647705 ,1985.
11 Briody Robert G, Cummings Frances M. Method for increasing the ultra-violet light transmittances of ethylene glycol[P]. US4289593, 1981.
12 Dietz Edward A, Albright David E. Method for producing UV absorption. in ethylene glycols, water, and mixtures[P]. CA2203485 ,1997.
13 Husain Mansoor. Glycol purification [P]. US6187973, 2001.
14 George Kathleen Frances, Dahuron Lise, Robson John Howrd, et al. Treatment of impurity-containing liquid streams in ethylene oxide/glycol processes with semi-permeable membranes[P]. W09109828, 1991.
15 Marquis Edward T, Sanderson John R. Improved glycol purification[P]. W09958483, 1999.
16 Rebsdat, Siegfried, Mayer, et al. Process for the manufacture of extremeiy pure monoethylene glycol[P]. US4349417, 1982.
17 Paggini, Alberto, Romano, et al. method for the production of high-purity ethylene glycols[P]. US4358625,1982.
18
18 Hoffman, William C.,Dever, John P.. Method for separating compounds in process streams[P]. US5440058, 1995.
19 Kasyanov Anatolij G, Kolesnikov Valerij Ya, Bodrikov Ivan V, et al. Method for cleaning ethylene glycol[P]. SU1498752, 1989.
20 Crandall John Worth, Ream Bernard Claude. Process for refining ethylene glycol[P]. EP0310189,1989.
21 徐克勋主编．精细有机化工原料及中间体手册．北京：化学工业出版社，1998．
22 司航主编．化工产品手册 有机化工原料．第3版．北京：化学工业出版社，1999．
23 陈冠荣等编辑．化工百科全书第2卷．北京：化学工业出版社，1991．
24 陈冠荣等编辑．化工百科全书第7卷．北京：化学工业出版社，1994．
25 陈冠荣等编辑．化工百科全书 第18卷．北京：化学工业出版社，1998．
26 周名成，俞洁勤．紫外与可见分光光度分析法．北京：化学工业出版社，1986．
27 谈天．谱学方法在有机化学中的应用．北京：高等教育出版社，1985．
28 陈洁，宋启泽．有机波谱分析．北京：北京理工大学出版社，2000．
29 陈耀祖，涂亚平．有机质谱及应用．北京：科学出版社，2001．
30 汪正范，杨树民，吴伴天．色谱联用技术．北京：化学工业出版社，2001．
31 汪正范．色谱定性与定量．北京：化学工业出版社，2000．
32 赵瑶兴，孙祥玉．有机分子结构光谱鉴定．北京：科学出版社，2003．
33 何炳林，黄文强．离子交换与吸附树脂．上海：上海科技教育出版社，1995．
34 王方．离子交换树脂．北京：北京科学技术出版社，1989．
35 钱旭红，高建宝，焦家俊等．有机化学．北京：化学工业出版社，1999．
36 GB6682-86实验室用水规格．