壳聚糖铈配合物树脂在啤酒澄清中的应用研究
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摘要
啤酒是一种成分复杂、稳定性不强的胶体溶液,在贮存过程中易产生混浊沉淀现象。引发啤酒混浊失光的最常见的原因是蛋白质-多酚的复合。蛋白质-多酚混浊的出现,主要是由于敏感多酚及敏感蛋白的过量或不均衡引起的。在实际生产中,可通过去除敏感蛋白与敏感多酚来提高啤酒非生物稳定性。稀土元素铈在水解肽键方面有很好的活性;壳聚糖是一种天然多糖,其分子链上有大量活性基团,对金属离子有稳定的配位作用,对蛋白质和多酚也有吸附作用。
本文利用壳聚糖与金属元素铈络合反应,制备出啤酒专用壳聚糖树脂类产品,并将该树脂应用于啤酒澄清。主要研究结果如下:
1.采用反相悬浮交联法制备了壳聚糖铈配合物树脂。树脂微粒呈金黄色球状,粒径小于100μm。对壳聚糖铈配合物树脂进行紫外、红外光谱、XRD衍射分析确定壳聚糖铈配合物微粒中存在铈离子。壳聚糖铈配合物树脂在pH 1.0-12.0,温度0℃-60℃的溶液中性质稳定,一般的操作处理如有机溶剂处理,离心和超声离心也不会影响壳聚糖-铈配合物的稳定性。
2.将壳聚糖铈配合物树脂初步应用于啤酒澄清。结果显示,过滤流速(数值的范围)和层析柱径高比(数值的范围)对壳聚糖铈配合物树脂过滤效果无较大影响,壳聚糖铈配合物树脂的饱和处理量为自身体积的80倍,啤酒经澄清后敏感多酚含量下降99.92%,浊度下降97.10%,敏感蛋白下降48.56%,无机离子和风味物质含量没有发生明显变化,糖组分和有机酸也没有明显变化,氨基酸含量增加9.84%。因此,壳聚糖金属配合物树脂可作为一种新型的啤酒澄清剂。
3.比较了三种不同啤酒澄清工艺,对啤酒澄清后的浊度,多酚和蛋白含量进行了分析,确定壳聚糖铈配合物树脂和硅藻土过滤为一种较好的澄清工艺。应用此工艺进行中试试验,结果显示,啤酒过滤后色度为3.535EBC,属于淡色啤酒范畴,浊度为0.114EBC,泡沫洁白细腻,较持久挂杯,有明显酒花香气,酒体醇厚,总酸含量为1.58ml/100ml,双乙酰含量0.030mg/L,总多酚60.68mg/L,均符合国标对淡色啤酒的感官要求和理化要求。啤酒放置6个月后浊度为0.483 EBC,外观仍清澈透亮。
4.对壳聚糖铈配合物树脂的安全性的初步研究结果显示,经壳聚糖铈配合物树脂过滤的啤酒中铈含量低于清酒中铈含量,戊二醛未检出,说明壳聚糖铈配合物树脂对啤酒的安全性无影响。
5.对壳聚糖铈配合物树脂的再生剂研究表明,当再生剂为3%的盐酸和4% NaOH时,再生效果最好;对再生剂用量的研究结果显示,3%的盐酸用量为15倍树脂体积,4%的NaOH用量为20倍树脂体积。
本文将壳聚糖铈配合物树脂应用于啤酒澄清,效果良好,并优化了啤酒澄清工艺,提高了啤酒的非生物稳定性,保障了啤酒的质量安全以及营养,可提高啤酒在国际市场上科技竞争能力及保障啤酒生产技术的引领优势。本文制备的壳聚糖铈配合物树脂,为啤酒澄清提供了新的过滤介质,也为壳聚糖资源的利用提供新的方向。
The beer with complicated ingredients is not stable, and in storage process the precipitation will be produced easily. The main precipitation is the complex of protein and polyphenol, which is caused by the excessive sensitive-polyphenol and sensitive-protein. The beer stability can be improved by removing sensitive-polyphenol and sensitive-protein in industry. The rare-earth element cerium has a good activity in hydrolyzing protein. Chitosan is a nature polysaccharide, and on its molecular chain there are a number of active groups which can chelate metal ions, protein and polyphenols.
The objective of this study is application of resin made by the complex of chitosan and cerium to clarify beer. The research results are as follows:
1. The resins were made from complexes of chitosan and cerium (RCCM) prepared by opposite crosslinking method in this paper. The color of RCCM is golden, and the diameter of RCCM microsphere is less than 100μm. RCCM were analyzed by ultraviolet spectrum, infrared spectrum and XRD. The results prove that cerium was in RCCM. RCCM were stable in solution with pH 1.0 to 12.0, also RCCM were stable in solution of which the temperature is low than 60℃. Besides, RCCM handled by centrifuge or ultrasound were stable.
2. RCCM were applied in beer clarification. The results showed that filtering velocity and diameter length ratio of chromatographic column have little influence on the effect of beer clarification. RCCM can clarify beer which volume is 80 times of the volume of RCCM. The effects of RCCM on beer quality were determined and compared with the finished product beer. The sensitive polyphenols were nearly all adsorbed, the turbidity decreased 97.1%, and the sensitive proteins decreased 48.6%. Meanwhile, the inorganic ions, the flavor compounds, the saccharides and the organic acids had no obvious changes. The amino acids increased 9.84%. Thus the resins made from complexes of chitosan and metal can be used as a new beer clarifier.
3. Three process of beer clarification were compared, and the results indict that RCCM and diatomite clarification is better. The beer was clarified by RCCM and diatomite. The results showed that the chroma of beer was 3.535EBC, so the beer belongs to ale. The turbidity of beer was 0.114EBC. RCCM have no effect on the foam and pharmaceutical hops aroma. The contents of total acid, diacetyl and polyphenols reached the national standard on beer physical-chemical requirement. After six months, the turbidity of beer was 0.483EBC, and the beer was still limpid.
4. The safety of RCCM was studied, and the results showed that the contents of cerium in beer clarified by RCCM were lower than the contents of cerium in beer clarified by diatomite, and the glutaraldehyde was not detected. It proves that RCCM have no effect on beer safety. The regeneration of RCCM was studied and the effect was best when the regeneration reagent was hydrochloric acid with 3% concentration and NaOH with 4% concentration. The dosage of regeneration reagent was studied, and the results showed that the dosage of hydrochloric acid with 3% was 15 times the volume of RCCM, and the dosage of NaOH with 4% concentration was 20 times the volume of RCCM.
This research optimized the process of beer clarification, improved the beer stability, guaranteed the safety of beer, and enhanced the ability of beer competition in the international market. RCCM prepared in this research provide a new filter medium for beer clarification and also provide a new way for utilization of chitosan resource.
本文利用壳聚糖与金属元素铈络合反应,制备出啤酒专用壳聚糖树脂类产品,并将该树脂应用于啤酒澄清。主要研究结果如下:
1.采用反相悬浮交联法制备了壳聚糖铈配合物树脂。树脂微粒呈金黄色球状,粒径小于100μm。对壳聚糖铈配合物树脂进行紫外、红外光谱、XRD衍射分析确定壳聚糖铈配合物微粒中存在铈离子。壳聚糖铈配合物树脂在pH 1.0-12.0,温度0℃-60℃的溶液中性质稳定,一般的操作处理如有机溶剂处理,离心和超声离心也不会影响壳聚糖-铈配合物的稳定性。
2.将壳聚糖铈配合物树脂初步应用于啤酒澄清。结果显示,过滤流速(数值的范围)和层析柱径高比(数值的范围)对壳聚糖铈配合物树脂过滤效果无较大影响,壳聚糖铈配合物树脂的饱和处理量为自身体积的80倍,啤酒经澄清后敏感多酚含量下降99.92%,浊度下降97.10%,敏感蛋白下降48.56%,无机离子和风味物质含量没有发生明显变化,糖组分和有机酸也没有明显变化,氨基酸含量增加9.84%。因此,壳聚糖金属配合物树脂可作为一种新型的啤酒澄清剂。
3.比较了三种不同啤酒澄清工艺,对啤酒澄清后的浊度,多酚和蛋白含量进行了分析,确定壳聚糖铈配合物树脂和硅藻土过滤为一种较好的澄清工艺。应用此工艺进行中试试验,结果显示,啤酒过滤后色度为3.535EBC,属于淡色啤酒范畴,浊度为0.114EBC,泡沫洁白细腻,较持久挂杯,有明显酒花香气,酒体醇厚,总酸含量为1.58ml/100ml,双乙酰含量0.030mg/L,总多酚60.68mg/L,均符合国标对淡色啤酒的感官要求和理化要求。啤酒放置6个月后浊度为0.483 EBC,外观仍清澈透亮。
4.对壳聚糖铈配合物树脂的安全性的初步研究结果显示,经壳聚糖铈配合物树脂过滤的啤酒中铈含量低于清酒中铈含量,戊二醛未检出,说明壳聚糖铈配合物树脂对啤酒的安全性无影响。
5.对壳聚糖铈配合物树脂的再生剂研究表明,当再生剂为3%的盐酸和4% NaOH时,再生效果最好;对再生剂用量的研究结果显示,3%的盐酸用量为15倍树脂体积,4%的NaOH用量为20倍树脂体积。
本文将壳聚糖铈配合物树脂应用于啤酒澄清,效果良好,并优化了啤酒澄清工艺,提高了啤酒的非生物稳定性,保障了啤酒的质量安全以及营养,可提高啤酒在国际市场上科技竞争能力及保障啤酒生产技术的引领优势。本文制备的壳聚糖铈配合物树脂,为啤酒澄清提供了新的过滤介质,也为壳聚糖资源的利用提供新的方向。
The beer with complicated ingredients is not stable, and in storage process the precipitation will be produced easily. The main precipitation is the complex of protein and polyphenol, which is caused by the excessive sensitive-polyphenol and sensitive-protein. The beer stability can be improved by removing sensitive-polyphenol and sensitive-protein in industry. The rare-earth element cerium has a good activity in hydrolyzing protein. Chitosan is a nature polysaccharide, and on its molecular chain there are a number of active groups which can chelate metal ions, protein and polyphenols.
The objective of this study is application of resin made by the complex of chitosan and cerium to clarify beer. The research results are as follows:
1. The resins were made from complexes of chitosan and cerium (RCCM) prepared by opposite crosslinking method in this paper. The color of RCCM is golden, and the diameter of RCCM microsphere is less than 100μm. RCCM were analyzed by ultraviolet spectrum, infrared spectrum and XRD. The results prove that cerium was in RCCM. RCCM were stable in solution with pH 1.0 to 12.0, also RCCM were stable in solution of which the temperature is low than 60℃. Besides, RCCM handled by centrifuge or ultrasound were stable.
2. RCCM were applied in beer clarification. The results showed that filtering velocity and diameter length ratio of chromatographic column have little influence on the effect of beer clarification. RCCM can clarify beer which volume is 80 times of the volume of RCCM. The effects of RCCM on beer quality were determined and compared with the finished product beer. The sensitive polyphenols were nearly all adsorbed, the turbidity decreased 97.1%, and the sensitive proteins decreased 48.6%. Meanwhile, the inorganic ions, the flavor compounds, the saccharides and the organic acids had no obvious changes. The amino acids increased 9.84%. Thus the resins made from complexes of chitosan and metal can be used as a new beer clarifier.
3. Three process of beer clarification were compared, and the results indict that RCCM and diatomite clarification is better. The beer was clarified by RCCM and diatomite. The results showed that the chroma of beer was 3.535EBC, so the beer belongs to ale. The turbidity of beer was 0.114EBC. RCCM have no effect on the foam and pharmaceutical hops aroma. The contents of total acid, diacetyl and polyphenols reached the national standard on beer physical-chemical requirement. After six months, the turbidity of beer was 0.483EBC, and the beer was still limpid.
4. The safety of RCCM was studied, and the results showed that the contents of cerium in beer clarified by RCCM were lower than the contents of cerium in beer clarified by diatomite, and the glutaraldehyde was not detected. It proves that RCCM have no effect on beer safety. The regeneration of RCCM was studied and the effect was best when the regeneration reagent was hydrochloric acid with 3% concentration and NaOH with 4% concentration. The dosage of regeneration reagent was studied, and the results showed that the dosage of hydrochloric acid with 3% was 15 times the volume of RCCM, and the dosage of NaOH with 4% concentration was 20 times the volume of RCCM.
This research optimized the process of beer clarification, improved the beer stability, guaranteed the safety of beer, and enhanced the ability of beer competition in the international market. RCCM prepared in this research provide a new filter medium for beer clarification and also provide a new way for utilization of chitosan resource.
引文
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