Article(id=1276190652853519113, tenantId=1146029695717560320, journalId=1235980609244409860, issueId=1276190518317023323, articleNumber=null, orderNo=null, doi=10.3969/j.issn.1000-2561.2024.05.015, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1683216000000, receivedDateStr=2023-05-05, revisedDate=1687622400000, revisedDateStr=2023-06-25, acceptedDate=null, acceptedDateStr=null, onlineDate=1782197162115, onlineDateStr=2026-06-23, pubDate=1716566400000, pubDateStr=2024-05-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1782197162115, onlineIssueDateStr=2026-06-23, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1782197162115, creator=13701087609, updateTime=1782197162115, updator=13701087609, issue=Issue{id=1276190518317023323, tenantId=1146029695717560320, journalId=1235980609244409860, year='2024', volume='45', issue='5', pageStart='873', pageEnd='1093', issueExtLink='null', onlineDate='null', pubDate='1716566400000', pubDateStr='2024-05-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1782197130040, creator='13701087609', updateTime=1782197317472, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1276191304694493587, tenantId=1146029695717560320, journalId=1235980609244409860, issueId=1276190518317023323, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1276191304694493588, tenantId=1146029695717560320, journalId=1235980609244409860, issueId=1276190518317023323, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1000, endPage=1006, ext={EN=ArticleExt(id=1276190653105177355, articleId=1276190652853519113, tenantId=1146029695717560320, journalId=1235980609244409860, language=EN, title=Separation and Purification of Ergothioneine from Natural Rubber Serum with Ion Exchange Resin, columnId=1236286112713470633, journalTitle=Chinese Journal of Tropical Crops, columnName=Post-harvest Treatment & Quality Safety, runingTitle=null, highlight=null, articleAbstract=

The adsorption and desorption rates of nine cationic exchange resins on ergothioneine (EGT) were investigated to screen out the ion exchange resin suitable for the separation and purification of EGT from natural rubber serum (NRS) and determine the optimum process parameters. The results showed that the SA-2 cation exchange resin was the most suitable for the separation and purification of EGT from NRS, and the optimum parameters were as follows: pH of sample loading 3.0-4.0, sample loading flow rate 2 BV/h, and eluted with 0.5% ammonium hydroxide at the flow rate of 1 BV/h. Furthermore, a higher sample loading concentration was more conducive to the adsorption capacity of resin. Under the conditions, the EGT elution rate could reach 97.83%. This research indicated that the SA-2 cation exchange resin is an ideal medium for the separation and purification of EGT from NRS, which would lay a theoretical foundation for the industrial production of EGT.

, authors=null, authorsList=Shikuan JIANG, Juan LI, Guimei ZHANG, Rong XU, Li DING, authorCompany=null, correspAuthors=null, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1276190658532606757, articleId=1276190652853519113, tenantId=1146029695717560320, journalId=1235980609244409860, language=CN, title=离子交换树脂分离纯化天然橡胶乳清中麦角硫因, columnId=1236286112877048492, journalTitle=热带作物学报, columnName=采后处理与质量安全, runingTitle=null, highlight=null, articleAbstract=

研究离子交换树脂对麦角硫因(EGT)的吸附分离性能,筛选出适合用于分离纯化天然橡胶乳清(NRS)中EGT的离子交换树脂,并确定最佳工艺参数。通过比较9种不同型号的阳离子交换树脂对EGT的吸附容量和解吸率,选出最优的离子交换树脂,并通过静态、动态吸附试验考察无机盐浓度、pH、上样液浓度、上样流速、洗脱液浓度、洗脱流速对树脂吸附、解吸效果的影响。结果表明,SA-2阳离子交换树脂最适合NRS中EGT的分离纯化,最佳工艺条件为:上样液pH为3.0~4.0,上样流速为2 BV/h,洗脱流速为1 BV/h,洗脱液氨水质量浓度为0.5%,提高上样液中EGT浓度更有利于树脂对EGT的吸附。验证试验表明,SA-2阳离子交换树脂是分离纯化NRS中EGT的理想介质,为工业化生产EGT奠定理论基础。

, authors=

姜士宽(1983—),男,学士,副研究员,研究方向:天然橡胶乳清的高值化利用。

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姜士宽(1983—),男,学士,副研究员,研究方向:天然橡胶乳清的高值化利用。

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姜士宽(1983—),男,学士,副研究员,研究方向:天然橡胶乳清的高值化利用。

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language=CN, label=图9, caption=验证试验的洗脱曲线, figureFileSmall=4fdulVYnoxSVFqcFpkHH8A==, figureFileBig=1RMxuViSLR5o2dNsTezShg==, tableContent=null), ArticleFig(id=1277241973136293939, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276190652853519113, language=EN, label=Tab. 1, caption=

Static adsorption property of different ion exchange resins on EGT

, figureFileSmall=null, figureFileBig=null, tableContent=
树脂型号Type of resin树脂极性Polarity of resin吸附量Adsorbing capacity/(mg×g-1)吸附率Adsorbing rate/%解吸率Desorption rate/%
001×7强酸性阳离子12.0450.7868.67
S1100强酸性阳离子12.9154.9766.57
SA-2强酸性阳离子21.6489.4066.36
D001大孔强酸性阳离子20.4884.8158.76
D61大孔强酸性阳离子20.5684.7164.38
D72大孔强酸性阳离子8.5536.6682.75
D81大孔强酸性阳离子16.0265.5470.05
JK008强酸性阳离子18.4376.3164.89
001×10强酸性阳离子18.1876.6561.97
), ArticleFig(id=1277241973207597108, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276190652853519113, language=CN, label=表1, caption=

不同离子交换树脂对EGT的静态吸附

, figureFileSmall=null, figureFileBig=null, tableContent=
树脂型号Type of resin树脂极性Polarity of resin吸附量Adsorbing capacity/(mg×g-1)吸附率Adsorbing rate/%解吸率Desorption rate/%
001×7强酸性阳离子12.0450.7868.67
S1100强酸性阳离子12.9154.9766.57
SA-2强酸性阳离子21.6489.4066.36
D001大孔强酸性阳离子20.4884.8158.76
D61大孔强酸性阳离子20.5684.7164.38
D72大孔强酸性阳离子8.5536.6682.75
D81大孔强酸性阳离子16.0265.5470.05
JK008强酸性阳离子18.4376.3164.89
001×10强酸性阳离子18.1876.6561.97
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离子交换树脂分离纯化天然橡胶乳清中麦角硫因
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姜士宽 1 , 李涓 2 , 张桂梅 1 , 徐荣 1 , 丁丽 3
热带作物学报 | 采后处理与质量安全 2024,45(5): 1000-1006
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热带作物学报 |采后处理与质量安全 2024 , 45 (5) : 1000 -1006
离子交换树脂分离纯化天然橡胶乳清中麦角硫因
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[Author(id=1277241963225153536, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276190652853519113, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=null, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1277241963539726339, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276190652853519113, authorId=1277241963225153536, language=EN, stringName=Shikuan JIANG, firstName=Shikuan, middleName=null, lastName=JIANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1.Yunnan Institute of Tropical Crops / Yunnan Key Laboratory of Sustainable Utilization Research on Rubber Tree / National and Local Joint Engineering Research Center of Breeding and Cultivation Technology of Rubber Tree, Jinghong, Yunnan 666100, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1277241963623612420, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276190652853519113, authorId=1277241963225153536, language=CN, stringName=姜士宽, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1.云南省热带作物科学研究所/云南省天然橡胶可持续利用研究重点实验室(筹)/天然橡胶良种选育与栽培技术国家地方联合工程研究中心,云南景洪 666100, bio={"content":"

姜士宽(1983—),男,学士,副研究员,研究方向:天然橡胶乳清的高值化利用。

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姜士宽(1983—),男,学士,副研究员,研究方向:天然橡胶乳清的高值化利用。

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姜士宽1, 李涓2, 张桂梅1, 徐荣1, 丁丽3
作者信息
  • 1.云南省热带作物科学研究所/云南省天然橡胶可持续利用研究重点实验室(筹)/天然橡胶良种选育与栽培技术国家地方联合工程研究中心,云南景洪 666100
  • 2.普洱学院生物与化学学院,云南普洱 665000
  • 3.中国热带农业科学院橡胶研究所,海南海口,571101
Separation and Purification of Ergothioneine from Natural Rubber Serum with Ion Exchange Resin
Shikuan JIANG1, Juan LI2, Guimei ZHANG1, Rong XU1, Li DING3
Affiliations
  • 1.Yunnan Institute of Tropical Crops / Yunnan Key Laboratory of Sustainable Utilization Research on Rubber Tree / National and Local Joint Engineering Research Center of Breeding and Cultivation Technology of Rubber Tree, Jinghong, Yunnan 666100, China
  • 2.School of Biological and Chemical Science, Puer University, Pu’er, Yunnan 665000, China
  • 3.Rubber Research Institute,Chinese Academy of Tropical Agricultural Sciences, Haikou, Hainan 571101, China
出版时间: 2024-05-25 doi: 10.3969/j.issn.1000-2561.2024.05.015
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研究离子交换树脂对麦角硫因(EGT)的吸附分离性能,筛选出适合用于分离纯化天然橡胶乳清(NRS)中EGT的离子交换树脂,并确定最佳工艺参数。通过比较9种不同型号的阳离子交换树脂对EGT的吸附容量和解吸率,选出最优的离子交换树脂,并通过静态、动态吸附试验考察无机盐浓度、pH、上样液浓度、上样流速、洗脱液浓度、洗脱流速对树脂吸附、解吸效果的影响。结果表明,SA-2阳离子交换树脂最适合NRS中EGT的分离纯化,最佳工艺条件为:上样液pH为3.0~4.0,上样流速为2 BV/h,洗脱流速为1 BV/h,洗脱液氨水质量浓度为0.5%,提高上样液中EGT浓度更有利于树脂对EGT的吸附。验证试验表明,SA-2阳离子交换树脂是分离纯化NRS中EGT的理想介质,为工业化生产EGT奠定理论基础。

天然橡胶乳清  /  麦角硫因  /  离子交换树脂

The adsorption and desorption rates of nine cationic exchange resins on ergothioneine (EGT) were investigated to screen out the ion exchange resin suitable for the separation and purification of EGT from natural rubber serum (NRS) and determine the optimum process parameters. The results showed that the SA-2 cation exchange resin was the most suitable for the separation and purification of EGT from NRS, and the optimum parameters were as follows: pH of sample loading 3.0-4.0, sample loading flow rate 2 BV/h, and eluted with 0.5% ammonium hydroxide at the flow rate of 1 BV/h. Furthermore, a higher sample loading concentration was more conducive to the adsorption capacity of resin. Under the conditions, the EGT elution rate could reach 97.83%. This research indicated that the SA-2 cation exchange resin is an ideal medium for the separation and purification of EGT from NRS, which would lay a theoretical foundation for the industrial production of EGT.

natural rubber serum (NRS)  /  ergothioneine  /  ion exchange resin
姜士宽, 李涓, 张桂梅, 徐荣, 丁丽. 离子交换树脂分离纯化天然橡胶乳清中麦角硫因. 热带作物学报, 2024 , 45 (5) : 1000 -1006 . DOI: 10.3969/j.issn.1000-2561.2024.05.015
Shikuan JIANG, Juan LI, Guimei ZHANG, Rong XU, Li DING. Separation and Purification of Ergothioneine from Natural Rubber Serum with Ion Exchange Resin[J]. Chinese Journal of Tropical Crops, 2024 , 45 (5) : 1000 -1006 . DOI: 10.3969/j.issn.1000-2561.2024.05.015
麦角硫因(L-ergothioneine,EGT)是一种天然氨基酸类强抗氧化剂,化学式为C9H15N3O2S,具有抗氧化、维持DNA的生物合成、细胞的正常生长和细胞免疫等多种生物活性[1],也因其具有抗辐射、美白和抗衰老等功效而应用于高端化妆品中[2]。自2005年发现EGT转运蛋白(ETT/OCTN1)以后,EGT逐渐成为研究的热点,与之相应的针对该化合物的报道也呈指数级增长[3]。自然界中,EGT主要由微生物合成,植物和动物自身不能合成,只能从外部摄取[4-5]。EGT的制备方法有天然生物提取法、化学合成法和生物合成法。天然生物提取法所用原料主要是蘑菇类真菌,但因其含量低,原料成本高,不具备工业化提取价值。化学合成法有溶剂残留和合成成本高的问题,采用此方法的生产厂家较少。目前工业化生产EGT主要采用生物合成法,随着生物合成学的快速发展,大大加快了微生物发酵生产EGT的研究[6]。目前公开报道制备EGT的最高水平为发酵220 h产量达到(1.63±0.04)g/L[7],但受发酵设备及发酵周期的制约,扩大生产规模的成本较高,至今EGT价格依然高达20万元/kg,生物合成法还有待更进一步的技术突破。
橡胶树(Hevea brasiliensis)是热带地区一种重要的经济林木,所产天然胶乳是一种乳状水分散体,由约35%的橡胶烃粒子和65%的乳清组成。1968年TAN等[8]首次在天然胶乳中发现有EGT,因其是由土壤中的微生物合成[9],所以受季节、植胶环境的影响较大。笔者对多个样品检测发现,EGT在西双版纳地区所取天然橡胶乳清(NRS)中的含量通常在10~15 mg/L,最高为113 mg/L,最低为2.7 mg/L。可能因为NRS中EGT含量过低,至今未见工业化提取的报道,但相较于生物合成法,NRS有着一项无可比拟的优势,我国天然橡胶种植面积为113.33余万hm2,干胶产量约为80万t[10],由此产生巨量的NRS,且属于零成本甚至负成本的EGT提取原料,因为在制胶厂,NRS作为高浓有机废水的处理成本高昂。
本研究通过对比9种离子交换树脂对EGT的吸附-解吸效果,筛选出了效果较好的树脂型号,并研究了该树脂的最佳吸附和洗脱条件,经试验验证,该树脂能很好地对NRS中的EGT进行分离纯化,为从NRS中工业化提取EGT提供了理论依据。
本研究供试材料为:乳清(天然胶乳加酸凝固后挤压获得);麦角硫因(上海麦角硫因生物科技集团有限公司);001×7、S1100离子交换树脂(西安蓝晓科技新材料股份有限公司);SA-2离子交换树脂(安徽三星树脂科技有限公司);D001、D61、D72、D81、JK008、001×10离子交换树脂(郑州和成新材料科技有限公司);超滤膜、纳滤膜(SUEZ环境集团)。
仪器设备:4040型、2540型膜分离设备(杭州道纳膜科技有限公司);UV-2700型紫外分光光度计(日本岛津制作所);CHA-SAS制冷气浴恒温振荡器(常州市金坛区指前镇旭日实验仪器厂)。
NRS过2500 Da超滤膜,滤过液过纳滤膜,收集截留液继续减压蒸馏至原NRS体积的1%~2%,浓缩液用1%活性炭70~ 80 ℃脱色30 min,得到无色乳清处理液,加入5倍体积的去离子水,并用EGT纯品调至所需浓度,备用。
新购树脂置于烧杯中,用饱和食盐水浸泡树脂24 h,然后用去离子水洗涤至上清液无色无异味。用4倍树脂体积的1 mol/L的HCl溶液浸泡4 h,去离子水洗涤至pH为5左右,再用4倍树脂体积的1 mol/L的NaOH溶液浸泡4 h,去离子水洗涤至中性,最后用4倍树脂体积的1 mol/L HCl溶液浸泡6 h,将树脂转换为H型,用去离子水洗涤至pH 5~6后备用。
取预处理过的树脂缓慢转移至层析柱内,柱床体积为50 mL,柱规格为200 mm×25 mm,柱内预先加入高度为4 cm的去离子水,液面上升至距管口2 cm处结束,待树脂完全沉下后用去离子水以2 BV/h速度平衡树脂柱,去离子水用量为2~3 BV。
精密称取EGT纯品10 mg,于100 mL容量瓶中加纯水配制成浓度为100 mg/L的标准品贮备液。分别吸取0.9、0.8、0.7、0.6、0.5、0.4 mL标准品溶液定容于10 mL容量瓶中,经0.22 μm微孔滤膜过滤,即得一系列浓度梯度的标准品溶液。在波长258 nm条件下用紫外分光光度计测出标准溶液的吸光度,绘制标准曲线。
称取2 g经预处理的湿树脂,置于150 mL具塞三角瓶中,加入EGT浓度为1.5 mg/mL,pH为4.0的上样液40 mL,在25 ℃,转速100 r/min的摇床中振荡24 h,使树脂吸附饱和,取上清液测定溶液中EGT的浓度,并按公式计算各树脂对EGT的静态吸附容量(Q)和吸附率(X)。
将吸附饱和的树脂滤去残液,用去离子水洗涤2次,加入质量浓度0.5%的氨水40 mL,在25 ℃,转速100 r/min的摇床中振荡解吸12 h,取上清液测定EGT含量,并计算解吸率(B)。
式中,Q为树脂对EGT的静态吸附容量,mg/g;X为树脂对EGT的吸附率,%;B为洗脱液对EGT的解吸率,%;C0为EGT的初始浓度,mg/mL;C1为吸附结束后溶液中EGT浓度,mg/mL;V1为所加入的上样液体积,mL;m为树脂的质量,g;C2为解吸液中EGT浓度,mg/mL;V2为所加入的解吸液体积,mL。
称取2.00 g预处理好的SA-2、D61树脂各4份,依次加入50 mL、pH 4.0浓度为2.5 mg/mL的EGT标准品配制液,其中NaCl浓度分别为0、0.1、0.5、1 mol/L,密封置于25 ℃水浴摇床上,100 r/min持续振荡6 h,测定上清液中的EGT含量,通过静态吸附容量考察无机盐对吸附的影响。
称取4 g经预处理的湿树脂,置于250 mL具塞三角瓶中,加入EGT浓度为2.5 mg/mL,pH 4.0的上样液100 mL,分别于吸附0.5、1、1.5、2、3、4、6、8、10、12、24 h时取0.5 mL上清液,测定吸光值,依据标准曲线计算上清液的EGT含量和吸附量,绘制SA-2树脂静态吸附曲线。
称取2.00 g预处理好的SA-2树脂6份,依次加入40 mL pH分别为2.5、3.0、3.5、4.0、4.5、5.0,浓度为1.5 mg/mL的上样液,密封置于25 ℃水浴摇床上,100 r/min持续振荡24 h,测定上清液中的EGT含量,通过静态吸附容量确定最佳pH。
称取2.00 g预处理好的SA-2树脂6份,依次加入50 mL pH 4.0浓度为2.5 mg/mL的上样液,密封置于25 ℃水浴摇床上,100 r/min持续振荡24 h,抽滤洗涤树脂,分别加入浓度为0.5%、1%、2%、3%、4%和5%的氨水溶液50 mL解吸12 h,测定上清液中的EGT含量,通过解吸率确定最佳氨水浓度。
配制pH为4.0,EGT浓度分别为2.5、5.0和10 mg/mL的上样液,以2 BV/h的流速进行上样吸附,当流出液中EGT浓度达到上样液浓度的10%时为EGT的穿透点,停止上样。用2 BV去离子水洗涤树脂,收集流出液和洗涤液,测量其体积和EGT浓度,计算树脂的吸附量,考察不同上样液浓度下树脂对EGT的吸附效果。
取3份处理好的SA-2树脂各50 mL装柱,将EGT浓度为5 mg/mL、pH 4.0的上样液上柱,分别控制上样液以1、2、3 BV/h的流速通过层析柱进行动态吸附,当流出液中EGT浓度达到上样液浓度的10%时,停止上样,测定流出液中EGT含量,通过吸附量确定最佳上样液流速。
SA-2树脂吸附完成后,用2 BV的去离子水洗柱,用浓度0.5%的氨水溶液分别以1、2、3 BV/h的流速对树脂柱进行洗脱,0.5 BV每管收集洗脱液,测定EGT浓度,绘制洗脱曲线,确定最佳洗脱流速。
试验选用了9个型号的离子交换树脂,不同离子交换树脂对EGT的吸附量、吸附率和解吸率如表1所示,SA-2阳离子交换树脂对EGT具有最高的吸附率,D001和D61树脂吸附率相当,但D61比D001有着更高的解吸率,综合考虑,初步选定凝胶型的SA-2和大孔型的D61两种树脂作为后续试验用树脂。
NRS中含有各种无机盐,能够被阳离子交换树脂吸附,对树脂吸附EGT具有较大影响。在EGT纯品配制的上样液中添加不同比例的NaCl,考察无机盐浓度对树脂吸附效果的影响,结果如图1所示。从图1可以看出,0.5 mol/L及以下的NaCl浓度对SA-2树脂吸附EGT几乎无影响,甚至0.1 mol/L的低浓度NaCl会提升SA-2树脂对EGT的吸附。当NaCl浓度继续增大时,树脂对EGT的吸附量呈下降趋势,NaCl浓度达到1 mol/L时,树脂对EGT的吸附量降至39.48 mg/g。而D61树脂则受NaCl的影响较大,当NaCl浓度由0增加至0.1 mol/L时,其对EGT的吸附量由28.70 mg/g陡降至16.13 mg/g,并随着NaCl浓度升高而逐步降低。试验最终确定SA-2阳离子交换树脂作为后续试验用树脂。
SA-2阳离子交换树脂的静态吸附过程如图2所示,在吸附开始的0.5 h内EGT快速吸附至SA-2树脂内部,吸附量达到31.63 mg/g,吸附率为56.39%,随后吸附速度明显降低。这是因为一方面随着吸附的进行,溶液中EGT浓度逐渐降低,其与树脂上的H+交换效率逐渐降低,吸附速度随之下降;而另一方面,在吸附初期,吸附过程处于液膜扩散阶段,溶液中的EGT被快速吸附至树脂表面,随着吸附时间的延长,吸附进入膜扩散和粒内扩散阶段,溶液中的EGT受到树脂表面以及树脂孔隙产生的阻力增加,扩散速度逐渐降低[11],24 h后吸附量最终达到54.88 mg/g,吸附率达到97.96%。
pH对离子交换平衡有着重要影响,其通过影响溶液中物质的带电性从而影响离子交换树脂的交换容量[12]。工厂内天然胶乳加酸凝固后获得的乳清pH一般在4~5之间,试验选定pH测试范围为2.5~5.0。如图3所示,SA-2树脂对EGT的吸附随pH的升高呈现先升高后降低的趋势,当pH在3.0~4.0之间时,SA-2树脂对EGT的吸附量较大,吸附量范围为19.77~20.00 mg/g,pH 2.5或4.8时吸附量相当,分别为18.60 mg/g和18.64 mg/g,整体而言,在试验范围内,pH对吸附效果有一定影响,但影响较小。
试验采用易于蒸馏去除的氨水作为洗脱剂,氨水浓度对解吸率的影响如图4所示。由图4可知,0.1%质量浓度的氨水溶液对EGT的解吸率较低,只有35.52%,当氨水质量浓度达到0.5%时,解吸率达到最高72.92%,随着氨水浓度的继续升高,解吸率呈逐渐下降趋势,这是因为洗脱液中的NH4+对离子交换树脂表面的双电层不仅有交换作用,还有压缩作用,随着洗脱液浓度的增大,树脂反离子的扩散层被压缩,扩散层中部分反离子变成固定层中的反离子,扩散层的活动范围变小,从而影响了洗脱效果。当氨水质量浓度达到5%时,解吸率降至63.27%,试验最终确定最佳洗脱液的氨水质量浓度为0.5%。
NRS中的EGT非由橡胶树合成,不同季节、不同植胶环境都有可能导致EGT含量的差别,这也导致制备的乳清处理液中EGT的浓度会有较大差异。试验初期,实验室内制备的乳清处理液中EGT浓度仅为1.5 mg/mL左右,后提高到2.5 mg/mL,目前可以达到5 mg/mL,随着技术成熟,会进一步提高乳清处理液中的EGT浓度,所以,本试验配制的上样液最高浓度到10 mg/mL,考察EGT浓度对吸附效果的影响。
以流出液中EGT质量浓度达到上样液质量浓度的10%时,为停止上样点[13-14]。EGT浓度分别为2.5、5.0、10 mg/mL的上样液的上样体积分别为32.5、20.5、19.5 BV。浓度为10 mg/mL的上样液上样体积大大低于浓度为2.5 mg/mL的上样液,可大幅缩减上样时间。由图5可知,上样液浓度为10 mg/mL时,SA-2树脂对EGT的吸附量高达214.51 mg/g,远大于上样液浓度为2.5 mg/mL的68.49 mg/g和浓度为5.0 mg/mL的83.84 mg/g的吸附量,这可能是因为较高浓度的上样液变相降低了溶液中无机盐、氨基酸类物质的相对浓度,高浓度上样液10%停止上样点的浓度较高也是一个重要原因。综上可知,在制备乳清上样液时,应尽量提高EGT浓度。
上样液流速对树脂动态吸附的影响如图6所示,从图6可以看出,上样流速越快,流出液浓度上升越快,越早达到上样液浓度的10%,即停止上样点,这就意味着树脂对EGT的吸附量也越少,上样液流速为1、2、3 BV/h对应的上样体积分别为10、9.5、8.5 BV,对应的上样时间分别为10、4.75、2.83 h,兼顾吸附量和生产效率,确定2 BV/h为最佳上样流速。
不同洗脱流速下的洗脱曲线如图7所示,从图7可以看出,洗脱流速越低,峰型越集中,峰宽也更窄,当洗脱流出液中EGT浓度降至5 mg/L左右时,1、2、3 BV/h的洗脱流速分别需要6、9.5、16 BV的洗脱液,对应的洗脱时间分别为6、4.75、5.3 h。3个流速下所需洗脱时间差别不大但洗脱液用量差异较大,这是因为洗脱流速越快,洗脱液在树脂内的停留时间越短,洗脱液还未充分交换树脂吸附的EGT就已经穿透流出,洗脱流速越快所需洗脱液的量也就越大。综合考虑洗脱时间以及洗脱液用量,确定最佳洗脱流速为1 BV/h。
验证试验不仅是对筛选出的SA-2树脂进行验证,其目的也包括利用所选树脂对乳清处理方法进行调整、优化。前4次验证试验中,采用完全由NRS制备的上样液,上样体积在1 BV时流出液中EGT浓度即超过了上样液浓度的10%,甚至达到30%的浓度,树脂对EGT的吸附量最低仅为4 mg/g,经过不断调整乳清处理方法,最终得到吸附洗脱效果都较好的乳清处理液。
采用完全由NRS制备的上样液,充分去除无机盐等杂质,测得上样液中EGT浓度为2780.12 mg/L,pH为2.5,考虑到无机盐比pH对SA-2树脂吸附EGT的影响更大,验证试验未调节上样液pH,以免引入更多的无机盐。由图8可以看出,当上样体积达到14.5 BV时,流出液的EGT浓度达到280.01 mg/L,达到上样液浓度的10%,用2 BV的去离子水洗涤树脂,计算得到树脂对EGT的吸附量为40.18 mg/g,吸附情况良好。
用0.5%质量浓度的氨水溶液以1 BV/h流速对树脂柱进行洗脱,由图9可以看出,当洗脱体积达到5.5 BV时,EGT浓度达到最高,为16.93 mg/mL,洗脱至流出液中EGT含量约5 mg/L时需要10 BV的洗脱液,计算得到EGT洗脱率为95.83%,洗脱情况良好,洗脱液经减压蒸馏除氨后能顺利结晶,经高效液相色谱检测,结晶样品纯度达到99.98%。验证试验表明,SA-2阳离子交换树脂对NRS中EGT分离纯化性能较好。
NRS中含有各种无机盐、氨基酸等成分[15],这些离子成分能够被阳离子交换树脂交换吸附,对树脂吸附目标产物EGT具有较大影响。试验中,采用完全由NRS制备的上样液,9种离子交换树脂吸附效果都极差,无法区分出优劣,所以,本实验将NRS处理液用5倍去离子水进行稀释,降低各种干扰成分的浓度,再添加EGT纯品配制所需浓度,在此条件下筛选出吸附效果较好的树脂,最后用完全由NRS制备的上样液进行验证试验,验证试验结果表明该方法合理、可行,筛选出的树脂可以用于NRS中EGT的分离纯化。
自天然橡胶产业形成以来,国内外学者对NRS开展了多种用途的利用研究,但结果都停留于实验室阶段,目前没有一个产业真正建立起来,NRS在制胶厂依然是高浓有机废水的角色,在实现NRS的产业化应用之前还需更广泛深入的研究并建立应用示范[16],本研究的目的即为NRS的资源化、高值化利用开发一条可行的技术途径。
  • 云南省热带作物科技创新体系建设专项资金项目(RF2023-13)
  • 云南省现代农业橡胶产业技术体系建设专项(2023KJTX008-06)
  • 中国热带农业科学院基本科研业务费专项资金项目(1630022020029)
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2024年第45卷第5期
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doi: 10.3969/j.issn.1000-2561.2024.05.015
  • 接收时间:2023-05-05
  • 首发时间:2026-06-23
  • 出版时间:2024-05-25
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  • 收稿日期:2023-05-05
  • 修回日期:2023-06-25
基金
云南省热带作物科技创新体系建设专项资金项目(RF2023-13)
云南省现代农业橡胶产业技术体系建设专项(2023KJTX008-06)
中国热带农业科学院基本科研业务费专项资金项目(1630022020029)
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    1.云南省热带作物科学研究所/云南省天然橡胶可持续利用研究重点实验室(筹)/天然橡胶良种选育与栽培技术国家地方联合工程研究中心,云南景洪 666100
    2.普洱学院生物与化学学院,云南普洱 665000
    3.中国热带农业科学院橡胶研究所,海南海口,571101
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
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Genus
种数
Number of
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Percentage of total
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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