CN117430728B - 一种高纯度硒化浒苔多糖的制备方法 - Google Patents
一种高纯度硒化浒苔多糖的制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
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- A—HUMAN NECESSITIES
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- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/125—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives containing carbohydrate syrups; containing sugars; containing sugar alcohols; containing starch hydrolysates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
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Abstract
本发明提供了一种高纯度硒化浒苔多糖的制备方法,具体步骤包括:以新鲜浒苔为原料进行多糖提取,在浒苔提取液中加入二氧化硒进行多糖降解;加入氧化钡或氢氧化钡进行硒化反应;再加入氧化钡或氢氧化钡调节pH值,使亚硒酸形成沉淀物过滤除去,滤液经离子交换柱进一步脱去残留的无机盐杂质,浓缩后进行喷雾干燥,即得硒化浒苔多糖。本发明以二氧化硒为多糖降解催化剂,氧化钡或氢氧化钡为硒化反应催化剂,制备过程中未添加硝酸根离子、氯离子等,添加的钡离子和亚硒酸根离子在后期中性溶液中形成沉淀被除去,再经离子交换树脂柱进一步纯化,多糖中硒含量在20~80mg/g之间,有机硒含量占总硒比达到95%以上,保证了在应用时的安全性和功效性。
Description
技术领域
本发明涉及一种绿色、环保、经济的硒化浒苔多糖的制备方法,其属于海洋生物技术领域。
背景技术
硒是人和动物必需的微量营养元素之一,具有清除自由基、抗氧化、增强免疫功能等多种生物活性。中国国土面积属低硒或缺硒土壤,加之农作物对存在于土壤中硒的吸收程度取决于硒的形态及其有效性,大多数硒是以矿物结晶形态存在,难以被作物吸收利用,这就制约着中国食物中硒的营养状况。而硒营养元素缺乏将导致人和动物许多疾病的发生。
硒化卡拉胶是一种以卡拉胶、亚硒酸或其盐等为原料,经反应并精制得到的食品营养强化剂,目前在食品和保健食品领域应用广泛,由于其优异的物化性质和疗效,在农业、饲料领域也有良好的发展前景。
研究安全健康的有机硒源,以补充人体对硒的摄入量,对于提高生活在缺硒地区居民的健康水平具有十分重大的意义。
目前,关于硒化浒苔多糖的生产方法的专利还不是很多,由于多糖结构的相似性,可参考的多为硒化卡拉胶生产方法。例如申请号为CN88103347的中国专利公开了一种硒化卡拉胶的制备方法:先用浓硝酸溶解硒粉后,再将卡拉胶加入氯化钠水溶液中加热搅拌,形成均一的卡拉胶溶胶;将上述两种溶液在一定条件下反应,将反应液用乙醇沉析,再干燥粉碎。公开号为CN1288899A的中国专利公开了一种硒化多糖化合物及其制备方法:将多糖类化合物、亚硒酸或其盐、钡离子、氢离子一起在一定条件下反应,得到硒化多糖化合物;再加入硫酸溶液除去钡离子,加入氯化铁溶液、NH3-NH4HCl溶液除去未反应的亚硒酸根离子;用醋酸钠调节pH后,用乙醇分级沉淀,抽滤烘干精制。公开号为CN108299567A的中国专利公开了一种利用浒苔制取海藻硒多糖的方法:将浒苔进行预处理,加入浒苔粉质量30-50倍的去离子水,通过超声波破壁仪辅助进行浒苔粗多糖的提取,通过过滤、醇沉将粗多糖纯化,通过加酸、微波辅助进行浒苔粗多糖降解,降解后的浒苔粗多糖片段,进行硒化反应,经冻干制得的浒苔海藻硒多糖,硒含量在20~120mg/g之间。以上三种方法在制备过程中引入了过多的其他元素和基团,可能使得到的产品中含有有害元素,分离纯化工艺都采用了乙醇沉淀的处理方式,导致有机硒与无机硒分离不彻底,既不利于环境保护,又使得产品中“有机硒占总硒质量百分比”不高,技术上存在一定缺陷。
无机硒毒性大,而且中毒量与需要量之闾范围小,使用量需要严格控制。有机硒毒副作用远比无机硒低。例如,硒化卡拉胶LD50为4.92g/kg,同类亚硒酸钠LD50为7mg/kg,其毒性降低700多倍,其毒性最大耐受量(MIC)为16g/kg,属无毒级。同时使用剂量容易控制,可缓慢释放、吸收,生物利用率高。
因为在制备硒化卡拉胶过程中,是应用卡拉胶和无机硒反应,为使反应完全,要适当过量加入无机亚硒酸,以保证亚硒酸充分置换多糖分子中的硫酸酯。未置换的游离无机硒虽然通过提纯工艺绝大部分被除去,但产晶中还有残留一些无机硒。也就是说有机硒含量愈高,游离无机硒含量愈低,有机硒比率就愈高,产品质量愈好。事实上市场上已经有了食品营养强化剂富硒酵母产品,其有机硒占总硒质量百分比达到97%以上。但其缺点是总硒含量只有0.2%。
为了解决现有的技术的不足之处,本发明的目的是提供一种绿色、环保、经济的硒化浒苔多糖的制备方法,同时所制备的产品有机硒纯度高,质量好。
发明内容
本发明的目的是提供一种绿色、环保、经济的硒化浒苔多糖的制备方法,同时所制备的产品有机硒纯度高,质量好。
为达到上述目的,本发明采用的技术方案是:首先以新鲜浒苔为原料进行多糖提取,在浒苔提取液中加入二氧化硒进行浒苔多糖降解;加入氧化钡(或氢氧化钡),进行硒化反应;再加入氧化钡(或氢氧化钡)调节pH,值形成亚硒酸钡沉淀,所得沉淀物过滤除去,再经离子交换树脂柱进一步脱去残留的无机盐等杂质;浓缩后进行喷雾干燥,即得硒化浒苔多糖。
一种高纯度硒化浒苔多糖的制备方法,其特征具体包括下列步骤:
(1)浒苔的预处理:取鲜浒苔加水清洗后,进行挤压脱水。脱水后浒苔(或清洗脱水后冷冻保存浒苔)按2-3倍重量加水,经胶体磨进行破碎、匀浆;
(2)浒苔多糖的提取:取经过步骤(1)处理的浒苔匀浆液,加入浒苔干品量的0.2-1.0%纤维素酶,升温至50-60℃,提取浒苔多糖,过滤得提取液;
(3)浒苔多糖降解:提取液中缓慢加入二氧化硒(或溶液,以下同),至总体系浓度为0.05M-0.1M,加热至50-70℃进行浒苔多糖降解,控制降解多糖平均分子量为1000-10000Da;
(4)浒苔粗多糖硒化反应:在浒苔多糖降解液中加入氧化钡(或氢氧化钡)作为催化剂,至总体系浓度为0.02M-0.05M,保持温度25-35℃,进行硒化反应;
(5)中和:加氧化钡(氢氧化钡)中和反应溶液中未反应的亚硒酸,至pH值6.0-8.0,形成亚硒酸钡沉淀,过滤除去亚硒酸钡沉淀;
(6)滤液过强酸性阳离子交换树脂柱:除去溶液中残留的钡、钠、钾等金属离子;
(7)承接液过弱碱性阴离子交换树脂柱:吸附除去溶液中的亚硒酸;
(8)浓缩:将步骤(7)中的硒化浒苔多糖液体浓缩,至固形物15-25%
(9)喷雾干燥:将步骤(8)中的硒化浒苔多糖浓缩液,进行喷雾干燥,制成高纯度硒化多糖固体产品。
上述高纯度硒化浒苔多糖的制备方法,其特征在于:所述步骤(3)中的浒苔多糖的降解催化剂为二氧化硒,用量至总体系浓度为0.05M-0.1M。
上述高纯度硒化浒苔多糖的制备方法,其特征在于:所述步骤(4)中硒化反应催化剂为氧化钡(或氢氧化钡),用量达到总体系浓度为0.02M-0.05M。
上述高纯度硒化浒苔多糖的制备方法,其特征在于:所述步骤(5)中的中和试剂为氧化钡(或氢氧化钡),调节pH值至6.0-8.0,形成亚硒酸钡沉淀。
上述高纯度硒化浒苔多糖的制备方法,其特征在于:所述步骤(6)中的滤液过强酸阳离子交换树脂柱,除去溶液中残留的钡、钠、钾等金属离子。
上述高纯度硒化浒苔多糖的制备方法,其特征在于:所述步骤(7)中的承接液过弱碱阴离子交换树脂柱,吸附除去溶液中的亚硒酸,形成硒化浒苔多糖溶液。
本发明高纯度硒化浒苔多糖具有以下优点:
(1)本发明的高纯度硒化浒苔多糖的制备方法原料为鲜浒苔(或清洗脱水后冷冻保存浒苔),资源丰富,成本低廉。提取液经亚硒酸催化降解后,平均分子量在1000-10000道尔顿;而且其少量硫酸酯降解时可被亚硒酸置换;本工艺未涉及浒苔干燥、粉碎步骤,以硒化剂兼做降解催化剂,进行了制备过程的优化集成,具有绿色化工理念;
(2)本发明的高纯度硒化浒苔多糖的制备方法对传统工艺进行了源消减,在多糖降解和硒化过程中,未使用硝酸,未引入新的氯离子、钠离子、硫酸根离子;而制备过程中引入的钡离子和亚硒酸根离子,会在后期中性溶液中形成沉淀,被巧妙地过滤除去。这就降低了后期离子交换树脂的处理负担,有利于产品进一步纯化。
(3)本发明的高纯度硒化浒苔多糖的制备方法采用离子交换树脂进行纯化,可再生重复使用,具备环保和经济特性;脱盐的同时,也起到了脱色作用,改善了产品的外观。实验结果表明将阳离子柱和阴离子柱直接串联使用,会进一步提高生产效率。
(4)本发明的高纯度硒化浒苔多糖硒的制备方法,其产品含量为20~80mg/g,较传统的方法制得硒化卡拉胶产品硒含量相当,但按食品安全国家标准GB1903.23-2016中方法进行检测,“有机硒占总硒质量百分比”达到95%以上;
(5)本发明的高纯度硒化浒苔多糖的制备方法,其产品可进一步开发为食品营养添加剂,应用于食品营养补充,添加于保健食品、功能性食品中;
(6)本发明的高纯度硒化浒苔多糖,其产品也可进一步开发为肥料,应用于作物喷施,生产富硒大米、富硒水果、富硒蔬菜等富硒农产品,对环境不会造成无机硒污染;
(7)本发明的高纯度硒化浒苔多糖,其产品也可进一步开发为饲料添加剂,应用于畜禽饲料中生产富硒蛋、富硒肉等富硒畜禽产品,食用安全性高。
具体实施方式
为了使本发明实现的技术手段易于理解,下面通过具体实施例,进一步详细阐述本发明。
实施例1
(1)浒苔的预处理:取鲜浒苔加水清洗后,进行挤压脱水。称取1000g脱水浒苔,加水3000g,经胶体磨进行破碎、匀浆;
(2)浒苔多糖的提取:浒苔匀浆液,加入1.2g纤维素酶,升温至55℃,进行浒苔多糖提取4小时,趁热过滤得提取液;
(3)浒苔多糖降解:提取液中缓慢加入二氧化硒33g。加热至70℃,进行浒苔多糖降解4小时;
(4)浒苔粗多糖硒化反应:在浒苔多糖降解液中加入氧化钡22g(或氢氧化钡24.6g),保持温度30℃,进行硒化置换反应24小时;
(5)中和:分次加入氧化钡(或氢氧化钡),中和反应溶液中未置换的亚硒酸,至反应液pH值7.0,形成亚硒酸钡沉淀,过滤除去亚硒酸钡沉淀;
(6)滤液过强酸性阳离子交换树脂柱:D001型大孔树脂300g,清洗后装柱后进行预处理。将滤液加入柱中,调整流速2.5BV/h,收集糖液,用去离子水顶出所有糖度液,停止收集;
(7)承接液过弱碱性阴离子交换树脂柱:D301型大孔树脂500g,清洗后装柱后进行预处理。将滤液加入柱中,调整流速2.5BV/h,收集硒化浒苔多糖溶液。用去离子水顶出所有糖度液,停止收集;
(8)浓缩:将硒化浒苔多糖溶液减压浓缩,至固形物25%;
(9)喷雾干燥:硒化浒苔多糖浓缩液,进行喷雾干燥,制成高纯度硒化多糖固体产品50g。
实施例2
(1)浒苔的预处理:称取冷冻保存浒苔2000g,加水4000g,经胶体磨进行破碎、匀浆。
(2)浒苔多糖的提取:浒苔匀浆液,加入1.6g纤维素酶,升温至55℃,进行浒苔多糖提取4小时,趁热过滤得提取液;
(3)浒苔多糖降解:提取液中缓慢加入二氧化硒25g。加热至60℃,进行浒苔多糖降解4小时;
(4)浒苔粗多糖硒化反应:在浒苔多糖降解液中加入氧化钡16g(或氢氧化钡17.9g),保持温度30℃,进行硒化置换反应48小时;
(5)中和:分次加入氧化钡(或氢氧化钡),中和反应溶液中未置换的亚硒酸,至反应液pH值7.5,形成亚硒酸钡沉淀,过滤除去亚硒酸钡沉淀;
(6)滤液过强酸性阳离子交换树脂柱:D001型大孔树脂500g,清洗后装柱后进行预处理。将滤液加入柱中,调整流速2.5BV/h,收集糖液。用去离子水顶出所有糖度液,停止收集;
(7)承接液过弱碱性阴离子交换树脂柱:D301型大孔树脂800g,清洗后装柱后进行预处理;将滤液加入柱中,调整流速为2.5BV/h,收集糖液。用去离子水顶出所有糖度液,停止收集;
(8)浓缩:将硒化浒苔多糖溶液减压浓缩,至固形物20%;
(9)喷雾干燥:硒化浒苔多糖浓缩液,进行喷雾干燥,制成高纯度硒化多糖固体产品110g。
对比实施例3:
采用实施例1-2的方法制备获得相应的高纯度硒化浒苔多糖样品,按食品安全国家标准GB1903.23-2016中方法进行检测,并与市场上购买的硒化卡拉胶的市售品(市售品1,青岛鹏洋生物工程有限公司;市售品2,无锡健特药业有限公司产品)进行对比,具体如表1所示。
表1高纯度硒化浒苔多糖与市售硒化卡拉胶商品对比
样品来源 | 总硒含量 | 无机硒含量 | 有机硒占总硒质量百分比 |
实施例1 | 4.2% | 0.12% | 97.1% |
实施例2 | 3.5% | 0.15% | 95.7% |
市售品1 | 4.5% | 0.40% | 91.1% |
市售品2 | 3.8% | 0.33% | 93.3% |
由表1所示,与传统硒化卡拉胶市售品进行对比可以发现,本技术得到的硒化浒苔多糖样品,有机硒占总硒质量百分比明显高于硒化卡拉胶市售品,产品更具食用安全性。
最后,还需要注意的是,以上所列举的仅是本发明的若干具体实施例。本领域的普通技术人员都会理解。在本发明的保护范围内,对于上述实施例进行修改,添加和替换都是可能的,其都没有超出本发明的保护范围。同时,本发明提供的高纯度硒化浒苔多糖的制备方法不仅仅局限于对硒化浒苔多糖的制备,也同样适用于硒化卡拉胶等产品的制备。
Claims (1)
1.一种高纯度硒化浒苔多糖的制备方法,其特征在于它包括下列步骤:
(1)浒苔的预处理;取鲜浒苔加水清洗后,进行挤压脱水,取脱水后浒苔或清洗脱水后冷冻保存浒苔,按浒苔2-3倍重量加水,经胶体磨进行破碎、匀浆;
(2)浒苔多糖的提取:取经过步骤(1)处理的浒苔匀浆液,加入浒苔干品量的0.2-1.0%纤维素酶,升温至50-60℃,提取浒苔多糖,过滤得提取液;
(3)浒苔多糖降解:提取液中缓慢加入二氧化硒,至总体系浓度为0.05M-0.1M,加热至50-70℃进行浒苔多糖降解,控制降解多糖平均分子量为1000-10000Da;
(4)浒苔多糖硒化反应:在浒苔多糖降解液中加入氧化钡或氢氧化钡作为催化剂,至总体系浓度为0.02M-0.05M,保持温度25-35℃,进行硒化反应;
(5)中和,除去亚硒酸钡沉淀:继续加入氧化钡或氢氧化钡,进一步中和反应溶液中未反应的亚硒酸,至pH值6.0-8.0,形成亚硒酸钡沉淀,过滤除去亚硒酸钡沉淀;
(6)过强酸性阳离子交换树脂柱:滤液过强酸性阳离子交换树脂柱,除去溶液中残留的金属阳离子;
(7)过弱碱性阴离子交换树脂柱:承接液过弱碱性阴离子交换树脂柱,吸附除去溶液中的亚硒酸;
(8)浓缩:将步骤(7)中的硒化浒苔多糖液体浓缩,至固形物15-25%;
(9)喷雾干燥:将步骤(8)中的硒化浒苔多糖浓缩液,进行喷雾干燥,制成高纯度硒化多糖固体产品。
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