CN1273494C - Production of K-kala glue - Google Patents
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Abstract
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技术领域technical field
本发明涉及一种从海藻中分离提取卡拉胶的方法,更具体地说是从卡拉胶混合物中制备K-卡拉胶的方法。The invention relates to a method for separating and extracting carrageenan from seaweed, more specifically a method for preparing K-carrageenan from a carrageenan mixture.
背景技术Background technique
多糖是地球上最丰富的生物大分子,而卡拉胶是多糖家族中的重要一员,卡拉胶(Carrageenan),又名角叉菜胶,它是一种由1,3键合的β-D-半乳糖基和1,4键合的α-D-半乳糖基重复交叉连结而成的硫酸化胞壁多糖。它是从角叉菜(Chondrus)、麒麟菜(Eucheuma)、杉藻(Gigartina)及沙菜(Hypena)等多种红藻中提取出来的。这些物质来源丰富,无污染,具有众多的应用领域,早在600多年前就有应用,20世纪50年代就有研究,至今仍有许多研究工作者进行这方面的研究。Polysaccharides are the most abundant biological macromolecules on earth, and carrageenan is an important member of the polysaccharide family. Carrageenan (Carrageenan), also known as carrageenan, is a β-D bonded by 1,3 -Sulfated cell wall polysaccharide formed by repeated cross-linking of galactosyl and 1,4-bonded α-D-galactosyl. It is extracted from various red algae such as Chondrus, Eucheuma, Gigartina and Hypena. These substances are rich in sources, non-polluting, and have many application fields. They were used more than 600 years ago, and they were studied in the 1950s. There are still many researchers conducting research in this area.
(1→3)与(1→4)交叉连接的D-半乳糖是卡拉胶的共同结构,因取代基等的不同而分为众多类型。根据是否含有3,6-内醚半乳糖以及硫酸基的含量和在分子中连接的位置,将卡拉胶分为K族和λ族。K-卡拉胶(KC)是K族其中的一种,它是由β-(1→3)-D-半乳糖-4-硫酸基和α-(1→4)-3,6-内醚-D-半乳糖形成的交替共聚物。因为它具有优良的热可逆凝胶化,抗蛋白凝结、亲水无毒性等独特性能,成为卡拉胶中的佼佼者而备受关注,在食品、化工和包装等方面应用广泛。特别是近年来在医药和生物工程领域的应用,更引起人们广泛的研究兴趣。(1→3) and (1→4) cross-linked D-galactose is the common structure of carrageenan, which can be divided into many types due to different substituents. Carrageenan is divided into K group and λ group according to whether it contains 3,6-inner ether galactose and the content of sulfate group and the position of connection in the molecule. K-carrageenan (KC) is one of the K family, which is composed of β-(1→3)-D-galactose-4-sulfate group and α-(1→4)-3,6-inside ether Alternating copolymers of -D-galactose. Because of its unique properties such as excellent thermoreversible gelation, anti-protein coagulation, hydrophilic and non-toxic, it has become the leader in carrageenan and has attracted much attention. It is widely used in food, chemical and packaging. Especially in recent years, the application in the fields of medicine and bioengineering has aroused people's extensive research interest.
不同类型的卡拉胶,由于其特性不同,其用途亦有较大的区别。K-卡拉胶,其凝固性能最好,粘度较低,适合于做果冻、固定化酶载体、药用胶囊原料等;λ-卡拉胶,粘度最高,但不能凝固,主要作为增稠剂使用;ι-卡拉胶,粘度介于K-卡拉胶、λ-卡拉胶之间,通常利用其与蛋白质反应的特性,适合于制造乳制品。K-卡拉胶能形成坚硬的凝胶,符合药用辅料的要求,在医药工业中又可以作为乳化剂、混悬剂、成膜剂、凝胶济、缓释剂等,用途广泛。Different types of carrageenan have different uses due to their different properties. K-carrageenan has the best coagulation performance and low viscosity, which is suitable for making jelly, immobilized enzyme carrier, pharmaceutical capsule raw materials, etc.; λ-carrageenan has the highest viscosity, but cannot solidify, and is mainly used as a thickener; ι-carrageenan, whose viscosity is between K-carrageenan and λ-carrageenan, is usually used to react with protein and is suitable for making dairy products. K-carrageenan can form a hard gel, which meets the requirements of pharmaceutical excipients. In the pharmaceutical industry, it can also be used as an emulsifier, suspending agent, film-forming agent, gel agent, slow-release agent, etc., and has a wide range of uses.
红藻藻体中不存在理想的重复二糖连接的卡拉胶,是多种卡拉胶结构的混合体。由于K-卡拉胶具有良好的性能,尤其是它具有高的凝胶强度,是制备药用硬胶囊原料之一。因此从卡拉胶混合体中分离制取K-卡拉胶成了研究者们关注的焦点。There is no ideal repeating disaccharide-linked carrageenan in red algal phyllases, and it is a mixture of various carrageenan structures. Because K-carrageenan has good properties, especially its high gel strength, it is one of the raw materials for preparing pharmaceutical hard capsules. Therefore, the separation and preparation of K-carrageenan from carrageenan mixture has become the focus of researchers.
中国专利文献专利号为94112179.8(授权公告号CN1037067C)的专利文献报导了从卡拉胶混合体中提纯K-卡拉胶的方法。The Chinese Patent Document Patent No. 94112179.8 (Authorized Notification No. CN1037067C) reports a method for purifying K-carrageenan from a carrageenan mixture.
该制取的方法是以麒麟藻及卡拉胶半成品为原料用氯化钠水溶液作为浸取剂浸取卡拉胶混合物,其条件为:The preparation method is to use the kylin algae and the carrageenan semi-finished product as raw materials and use the sodium chloride aqueous solution as the leaching agent to leach the carrageenan mixture, and the conditions are as follows:
氯化钠的浓度 0.6-1.0%(wt);The concentration of sodium chloride is 0.6-1.0% (wt);
溶液的pH值 7.0-8.0;The pH value of the solution is 7.0-8.0;
操作温度 75-85℃;Operating temperature 75-85°C;
保温时间 0.2-0.7hr;Holding time 0.2-0.7hr;
粘度 35-45厘泊;Viscosity 35-45 centipoise;
将浸液过滤除去浸取液的杂质,得到滤液;filtering the leaching solution to remove impurities in the leaching solution to obtain a filtrate;
用氯化钾作为盐析剂,对滤液进行盐析沉淀,其条件为:Potassium chloride is used as the salting-out agent to carry out salting-out precipitation to the filtrate, and its condition is:
氯化钾的浓度 3.6-4.6%(wt);The concentration of potassium chloride is 3.6-4.6% (wt);
操作温度 0-40℃;Operating temperature 0-40°C;
过滤出盐析沉淀;Filter out the salt precipitation;
用乙醇、异丙醇或它们的混合物作为挤水剂,对滤饼进行挤水,其条件为:挤水剂(v)∶投料量(干基,wt)=3-8∶1。Using ethanol, isopropanol or their mixture as a water-squeezing agent to squeeze the filter cake, the condition is: water-squeezing agent (v):feeding amount (dry basis, wt)=3-8:1.
该专利方法所制备出来的K-卡拉胶,其凝胶强度高,可达800-1100g/cm2,K-卡拉胶的提取率为75%,但是其不足之处是该方法要用氯化钾作为盐析剂,所生成的K-卡拉胶是K-卡拉胶的钾盐。由于K-卡拉胶的钾盐在水中只能吸水膨胀,不溶于水,λ-卡拉胶、ι-卡拉胶、K-卡拉胶的钠盐能溶于水,当用于药用硬胶囊的原料时,还要将K-卡拉胶的钾盐转换成K-卡拉胶的钠盐。而且其工艺流程仍较长,成本高。The K-carrageenan prepared by this patent method has a high gel strength, which can reach 800-1100g/cm 2 , and the extraction rate of K-carrageenan is 75%. Potassium is used as a salting-out agent, and the generated K-carrageenan is the potassium salt of K-carrageenan. Because the potassium salt of K-carrageenan can only absorb water and swell in water, it is insoluble in water, and the sodium salt of λ-carrageenan, iota-carrageenan, and K-carrageenan can be dissolved in water. At the same time, the potassium salt of K-carrageenan should also be converted into the sodium salt of K-carrageenan. And its technological process is still long, and the cost is high.
发明内容Contents of the invention
本发明的目的就在于研究出一种新的制备K-卡拉胶的方法,克服现有技术中存在的不足,避免生成K-卡拉胶的钾盐,而又使其所生成的K-卡拉胶具有高的凝胶强度。The purpose of the present invention is to develop a new method for preparing K-carrageenan, overcome the deficiencies in the prior art, avoid generating the potassium salt of K-carrageenan, and make the produced K-carrageenan Has high gel strength.
为了达到发明目的,本发明的研究者进行了许多研究工作。曾以粗藻为原料,用热水提取,将所用的热水调至PH5.0-6.5,再用含有与水混溶的有机溶剂例如甲醇、乙醇、异丙醇等,加入到所得的溶液中沉淀K-卡拉胶。实验结果表明,所得产品的凝胶强度低,这可能是由于在酸性介质中K-卡拉胶容易发生酸水解作用,加热使水解更快,大分子降解为小分子,粘度下降,凝胶强度下降。为了查明凝胶强度下降的原因,用各种方法进行了试验。经过多次的研究结果表明,在弱碱条件下可以得到满意的结果。研究出了一种K-卡拉胶的制备方法,用这种方法制备出的K-卡拉胶凝胶强度高。In order to achieve the purpose of the invention, the researchers of the present invention have carried out a lot of research work. Algae was used as raw material, extracted with hot water, the hot water used was adjusted to PH5.0-6.5, and then water-miscible organic solvents such as methanol, ethanol, isopropanol, etc. were added to the resulting solution Precipitate K-carrageenan. The experimental results show that the gel strength of the obtained product is low, which may be due to the fact that K-carrageenan is prone to acid hydrolysis in acidic medium, heating makes the hydrolysis faster, the large molecules are degraded into small molecules, the viscosity decreases, and the gel strength decreases . In order to find out the cause of the decrease in gel strength, experiments were carried out by various methods. The results of many studies show that satisfactory results can be obtained under weak alkaline conditions. A preparation method of K-carrageenan has been studied, and the K-carrageenan gel prepared by this method has high gel strength.
实验表明在弱碱性条件下,K-卡拉胶在一定乙醇的浓度的范围内,其溶解度比λ-卡拉胶、ι-卡拉胶的溶解度更小,利用K-卡拉胶的这种性质从卡拉胶的混合物中制备出K-卡拉胶。Experiment shows that under weakly alkaline conditions, K-carrageenan has a solubility smaller than that of lambda-carrageenan and iota-carrageenan in the range of a certain concentration of ethanol. Utilize this property of K-carrageenan from carrageenan K-carrageenan was prepared from a mixture of gums.
本发明的一种K-卡拉胶的制备方法,以卡拉胶的混合物为原料,在卡拉胶的混合物中加入pH7.5~9的浓度10-60%体积百分数的乙醇水溶液,形成混合物,于55-85℃的温度下回流0.5-2.5小时,放置至室温,过滤,得到K-卡拉胶。A kind of preparation method of K-carrageenan of the present invention, take the mixture of carrageenan as raw material, add the ethanol aqueous solution of the concentration 10-60% volume percent of pH7.5~9 in the mixture of carrageenan, form mixture, at 55 Reflux at -85°C for 0.5-2.5 hours, place to room temperature, and filter to obtain K-carrageenan.
所用原料卡拉胶混合物为市售食品添加剂级的卡拉胶,它是含有K-卡拉胶、λ-卡拉胶、ι-卡拉胶的混合物;也可以用含有K-卡拉胶、λ-卡拉胶、ι-卡拉胶的菲律宾产的卡拉胶半成品作为原料。The raw material carrageenan mixture used is the carrageenan of commercially available food additive grade, and it is the mixture containing K-carrageenan, λ-carrageenan, and ι-carrageenan; - Carrageenan semi-finished carrageenan produced in the Philippines is used as a raw material.
在原料卡拉胶的混合物中,所加入的pH7.5~9浓度10-60%体积百分数的乙醇水溶液的量为原料卡拉胶混合物的量与pH7.5~9浓度10-60%体积百分数的量的重量比为1∶0.5~6,又以1∶1~6为好。所用的乙醇可以是工业级乙醇、化学纯、分析纯乙醇、医药级乙醇。用氢氧化钠水溶液、盐酸来调节乙醇水溶液的pH值。若用pH7.5~8的浓度为10-60%体积百分数的乙醇水溶液,可以生产出K-卡拉胶。但是,这样生产出的K-卡拉胶的凝胶强度比加入pH8.2~9的浓度10-60%体积百分数的乙醇水溶液生产出的的凝胶强度稍低,以pH8.2~9的浓度10-60%体积百分数的乙醇水溶液为佳。In the mixture of raw carrageenan, the amount of the added ethanol aqueous solution with a concentration of 10-60% by volume at pH 7.5 to 9 is the amount of the mixture of raw carrageenan and the amount of 10-60% by volume at pH 7.5 to 9 The weight ratio is 1:0.5-6, preferably 1:1-6. The ethanol used can be technical grade ethanol, chemical pure ethanol, analytical pure ethanol, pharmaceutical grade ethanol. The pH value of the ethanol aqueous solution was adjusted with sodium hydroxide aqueous solution and hydrochloric acid. K-carrageenan can be produced by using ethanol aqueous solution with a pH of 7.5-8 and a concentration of 10-60% by volume. However, the gel strength of the K-carrageenan produced in this way is slightly lower than the gel strength produced by adding a pH 8.2-9 concentration of 10-60% ethanol aqueous solution. 10-60% by volume ethanol aqueous solution is preferred.
加入pH7.5~9的10-60%体积百分数的乙醇水溶液或加入pH8.2~9的10-60%体积百分数的乙醇水溶液后,于55-85℃的温度下回流,其回流温度>85℃使大分子降解为小分子,使其凝胶强度变小,所以回流温度又以60-80℃为宜。回流的时间为0.5-2.5小时,又以1-2小时为好。After adding 10-60% ethanol aqueous solution with pH 7.5-9 or 10-60% ethanol aqueous solution with pH 8.2-9, reflux at a temperature of 55-85°C, and the reflux temperature>85 °C degrades macromolecules into small molecules and reduces the gel strength, so the reflux temperature is preferably 60-80 °C. The time of reflux is 0.5-2.5 hours, preferably 1-2 hours.
所说的室温为15-25℃。过滤时,在实验室可以用滤纸过滤,工业上可用板框压滤机进行。Said room temperature is 15-25 ℃. When filtering, filter paper can be used in the laboratory, and a plate and frame filter press can be used in industry.
为了使过滤后的K-卡拉胶杂质的含量减小,过滤后可以用pH7.5~9的10-60%体积百分数的乙醇水溶液或用pH8.2~9的10-60%体积百分数的乙醇水溶液洗涤2-5次更好。In order to reduce the impurity content of K-carrageenan after filtration, the ethanol aqueous solution of 10-60% volume percentage of pH7.5~9 or the ethanol of 10-60% volume percentage of pH8.2~9 can be used after filtration It is better to wash with aqueous solution 2-5 times.
为了使过滤后的K-卡拉胶干燥,可以将过滤后的K-卡拉胶或经过滤洗涤后的K-卡拉胶于45-85℃的温度下干燥,又以45-65℃的温度下干燥为好,至K-卡拉胶中的水分含量<12%(重量百分数)。In order to dry the filtered K-carrageenan, the filtered K-carrageenan or the filtered and washed K-carrageenan can be dried at a temperature of 45-85°C, and then dried at a temperature of 45-65°C For better, to the moisture content in K-carrageenan<12% (percentage by weight).
在进行实验研究中,一个偶然的机会发现,在原料卡拉胶混合物中,加入pH7.5~9的浓度10-60%体积百分数的乙醇水溶液,更好加入pH8.2~9的浓度10-60%体积百分数的乙醇水溶液后,用超声波发生器进行超声处理后,制备出来了凝胶强度更好的K-卡拉胶,形成本发明的另一种K-卡拉胶的制备方法。In the experimental research, an accidental opportunity found that in the raw material carrageenan mixture, add ethanol aqueous solution with a concentration of 10-60% by volume at a pH of 7.5 to 9, and preferably add a concentration of 10-60 at a pH of 8.2 to 9. % volume percentage of ethanol aqueous solution, after ultrasonic treatment with an ultrasonic generator, K-carrageenan with better gel strength is prepared, forming another preparation method of K-carrageenan of the present invention.
本发明的另一种K-卡拉胶的制备方法,以卡拉胶混合物为原料,在原料卡拉胶混合物中加入pH7.5~9的浓度10-60%体积百分数的乙醇水溶液,形成混合物,以频率20-60千赫(KHz)的超声波处理所形成的混合物10-100分钟,在超声波处理过程中,所被超声波处理的混合物的温度控制在20-40℃,经超声波处理10-100分钟后,过滤,得到K-卡拉胶。The preparation method of another kind of K-carrageenan of the present invention, take the carrageenan mixture as raw material, add the ethanol aqueous solution of the concentration 10-60% volume percent of pH7.5~9 in raw material carrageenan mixture, form mixture, with frequency 20-60 kilohertz (KHz) ultrasonic treatment of the formed mixture for 10-100 minutes, during the ultrasonic treatment process, the temperature of the ultrasonic-treated mixture is controlled at 20-40 ° C, after ultrasonic treatment for 10-100 minutes, Filter to obtain K-carrageenan.
所用的原料卡拉胶混合物也是市售食品添加剂级卡拉胶及菲律宾产的卡拉胶半成品。The raw carrageenan mixture used is also commercially available food additive grade carrageenan and semi-finished carrageenan produced in the Philippines.
在原料卡拉胶的混合物中,所加入的pH7.5~9的浓度10-60%体积百分数的乙醇的量为原料卡拉胶混合物的量与pH7.5~9的浓度10-60%体积百分数梁的重量比为1∶0.5~6,又以1∶1~6为好。所用的乙醇可以是工业级乙醇、化学纯、分析纯乙醇、医药级乙醇。用氢氧化钠水溶液、盐酸来调节乙醇水溶液的pH值,用pH7.5~8的浓度10-60%体积百分数的乙醇水溶液,可以生产出K-卡拉胶。但是,这样生产出的K-卡拉胶的凝胶强度比用pH8.2~9的浓度10-60%体积百分数的乙醇水溶液生产出的K-卡拉胶的凝胶强度稍低。以pH8.2~9的浓度10-60%体积百分数的乙醇水溶液为佳。In the mixture of raw material carrageenan, the amount of ethanol with a concentration of 10-60% volume percentage of pH 7.5~9 added is the amount of raw material carrageenan mixture and a concentration of 10-60% volume percentage of pH 7.5~9. The weight ratio is 1:0.5-6, preferably 1:1-6. The ethanol used can be technical grade ethanol, chemical pure ethanol, analytical pure ethanol, pharmaceutical grade ethanol. Sodium hydroxide aqueous solution and hydrochloric acid are used to adjust the pH value of ethanol aqueous solution, and K-carrageenan can be produced by using ethanol aqueous solution with a concentration of 10-60% volume percentage of pH 7.5-8. However, the gel strength of the K-carrageenan produced in this way is slightly lower than that of the K-carrageenan produced with a pH 8.2-9 concentration of 10-60% ethanol aqueous solution. It is preferably an aqueous ethanol solution with a concentration of 10-60% by volume at a pH of 8.2-9.
加入pH7.5~9的10-60%体积百分数的乙醇水溶液或加入pH8.2~9的10-60%体积百分数的乙醇水溶液后,用20-60千赫(KHz)的超声波处理10-100分钟,又以处理10-60分钟为佳。After adding 10-60% volume percent ethanol aqueous solution of pH 7.5~9 or adding 10-60% volume percent ethanol aqueous solution of pH 8.2~9, use 20-60 kilohertz (KHz) ultrasonic treatment 10-100 Minutes, preferably 10-60 minutes.
所说的室温为15-25℃。过滤时,在实验室可以用滤纸过滤,工业上可用板框压滤机进行。Said room temperature is 15-25 ℃. When filtering, filter paper can be used in the laboratory, and a plate and frame filter press can be used in industry.
为了使过滤后的K-卡拉胶杂质的含量减小,可以用pH7.5~9的10-60%体积百分数的乙醇水溶液或用pH8.2~9的10-60%体积百分数的乙醇水溶液洗涤2-5次更好。In order to reduce the impurity content of K-carrageenan after filtration, it can be washed with 10-60% ethanol aqueous solution of pH 7.5~9 or with 10-60% ethanol aqueous solution of pH 8.2~9 2-5 times is better.
为了使过滤后的K-卡拉胶干燥,可以将过滤后的K-卡拉胶或经过滤洗涤后的K-卡拉胶于45-85℃的温度下干燥,又以45-65℃的温度下干燥为好,至K-卡拉胶中的水分含量<12%(重量百分数)。In order to dry the filtered K-carrageenan, the filtered K-carrageenan or the filtered and washed K-carrageenan can be dried at a temperature of 45-85°C, and then dried at a temperature of 45-65°C For better, to the moisture content in K-carrageenan<12% (percentage by weight).
本发明的上述二种制备方法制出来的K-卡拉胶又叫做海藻多糖胶,生产出的K-卡拉胶用美国药典26版的红外光谱法进行测试。The K-carrageenan produced by the above two preparation methods of the present invention is also called seaweed polysaccharide gum, and the produced K-carrageenan is tested by the infrared spectroscopy method of the 26th edition of the United States Pharmacopoeia.
本发明的K-卡拉胶的制备方法的优良效果为:The excellent effect of the preparation method of K-carrageenan of the present invention is:
(1)用本发明的方法制备出来的K-卡拉胶的凝胶强度高,有的可高达1100g/cm2以上。(1) The gel strength of the K-carrageenan prepared by the method of the present invention is high, some can be as high as 1100g/cm 2 or more.
(2)用本发明的方法对K-卡拉胶的提取率可达80%以上,所说的提取率为产品的产量与原料量的比,以百分数表示。(2) the extraction rate of K-carrageenan can reach more than 80% with the method of the present invention, and said extraction rate is the ratio of the output of product and raw material amount, expresses with percentage.
(3)用本发明的方法制出的K-卡拉胶的运动粘度>80mm2/s(秒)(用平氏粘度计测定),其粘度一般在80-110mm2/s之间,用本发明的方法制备出的K-卡拉胶用以制备出的医药用胶囊完全符合现行中国药典的质量要求。(3) the kinematic viscosity of the K-carrageenan produced by the method of the present invention>80mm 2 /s (second) (measured with flat viscometer), its viscosity is generally between 80-110mm 2 /s, with this The K-carrageenan prepared by the inventive method is used to prepare medicinal capsules which fully meet the quality requirements of the current Chinese Pharmacopoeia.
(4)本发明的方法工艺简短,节能,不用氯化钾,不形成卡拉胶的钾盐,降低了产品的成本。(4) The method technology of the present invention is brief, energy-conserving, does not need Potassium Chloride, does not form the potassium salt of carrageenan, reduces the cost of product.
具体实施方式Detailed ways
以下用实施例对本发明的方法作进一步的说明,有助于对本发明的K-卡拉胶制备方法的进一步的理解,实施例不限定本发明的保护范围,其保护范围由权利要求来决定。The method of the present invention is further described below with embodiment, contributes to the further understanding of K-carrageenan preparation method of the present invention, embodiment does not limit protection scope of the present invention, and its protection scope is determined by claims.
实施例1Example 1
在市售回流罐(ZN型,医药化工容器制造厂出品)中加入1公斤市售食品添加剂卡拉胶混合物作为原料,在卡拉胶混合物中加入pH8.5的浓度35%体积百分数的乙醇水溶液,形成混合物。原料卡拉胶的量与pH8.5的浓度35%体积百分数的乙醇水溶液量的重量比为1∶2,于80℃的温度下回流1.5小时,放置至室温25℃,用滤纸过滤后,用pH8.5的浓度35%体积百分数的乙醇水溶液洗涤3次,洗涤后于70℃的温度下用市售实验室用的恒温箱(DHP-420型,北京市光明医疗仪器厂)中干燥至水分含量为11%重量百分数,其提取率为88%重量百分数。经美国药典26版所述的红外光谱法测试合格,经测试其凝胶强度为1200g/cm2,其运动粘度为90mm2/s(用平氏粘度计测定)。Add 1 kilogram of commercially available food additive carrageenan mixture as raw material in the commercially available reflux tank (ZN type, produced by the pharmaceutical chemical container manufacturer), add the ethanol aqueous solution of the concentration 35% volume percentage of pH8.5 in the carrageenan mixture, form mixture. The weight ratio of the amount of raw material carrageenan to the amount of ethanol aqueous solution with a concentration of 35% volume percentage of pH8.5 is 1:2, reflux at a temperature of 80°C for 1.5 hours, place it at room temperature at 25°C, filter with filter paper, and filter with pH8 The ethanol aqueous solution of the concentration 35% volume percent of .5 is washed 3 times, and is dried to moisture content in the constant temperature box (DHP-420 type, Beijing Guangming Medical Instrument Factory) with commercially available laboratory at the temperature of 70 ℃ after washing. It is 11% by weight, and its extraction rate is 88% by weight. It passed the infrared spectrometry test described in the 26th edition of the United States Pharmacopoeia, and its gel strength was tested to be 1200g/cm 2 , and its kinematic viscosity was 90mm 2 /s (measured with a Pinnacle viscometer).
实施例2Example 2
其所用的设备及其操作方法基本同实施例1,唯有不同的是,1公斤菲律宾产卡拉胶半成品,即卡拉胶混合物中,加入pH9的浓度60%体积百分数的乙醇水溶液,形成混合物。原料量与pH9的浓度60%体积百分数的乙醇水溶液量的重量比为1∶6,于55℃的温度下回流2.5小时,放置至室温25℃,用滤纸过滤后,用pH 9的浓度60%体积百分数的乙醇水溶液洗涤5次,于85℃的温度下干燥至水分含量为10%重量百分数,其提取率为81%重量百分数,其凝胶强度为1150g/cm2,其运动粘度为95mm2/s(用平氏粘度计测定)。Its used equipment and operation method thereof are basically the same as embodiment 1, only difference is, 1 kilogram of Philippines produces carrageenan semi-finished product, i.e. in the carrageenan mixture, adds the ethanol aqueous solution of the concentration 60% volume percent of pH9, forms mixture. The weight ratio of the amount of raw material to the amount of ethanol aqueous solution with a concentration of pH9 of 60% volume percentage is 1:6, reflux at a temperature of 55°C for 2.5 hours, place it at room temperature at 25°C, filter with filter paper, and then filter with a concentration of pH9 of 60%. The volume percent ethanol aqueous solution was washed 5 times, dried at a temperature of 85°C until the water content was 10% by weight, the extraction rate was 81% by weight, the gel strength was 1150g/cm 2 , and the kinematic viscosity was 95mm 2 /s (determined with Ping's viscometer).
实施例3Example 3
其所用的设备及其操作方法基本同实施例1,唯有不同的是,在原料卡拉胶混合物中加入pH7.5的浓度35%体积百分数的乙醇水溶液,所得产品K-卡拉胶的凝胶强度为930g/cm2。Its used equipment and operating method thereof are basically the same as in Example 1, only difference is, in the raw material carrageenan mixture, add the ethanol aqueous solution of the concentration 35% volume percent of pH7.5, the gel strength of gained product K-carrageenan It is 930g/cm 2 .
实施例4Example 4
其所用的设备及其操作方法基本同实施例1,唯有不同的是过滤后不洗涤,其产品K-卡拉胶的凝胶强度为1050g/cm2。The equipment used and its operating method are basically the same as in Example 1, except that it is not washed after filtration, and the gel strength of its product K-carrageenan is 1050 g/cm 2 .
实施例5Example 5
其所用的设备及其操作方法基本同实施例1,唯有不同的是,以1公斤市售的食品添加剂级卡拉胶混合物为原料,在原料中加入pH8.2的浓度45%体积百分数的乙醇水溶液,形成混合物。原料量与pH8.2的浓度45%体积百分数的乙醇水溶液量的重量比为1∶4,于65℃的温度下回流1小时,放置至室温15℃,用滤纸过滤后,用pH8.2的浓度45%体积百分数的乙醇水溶液洗涤3次,于65℃的温度下干燥至水分含量为11.5%重量百分数,其提取率为85%重量百分数,其凝胶强度为1180g/cm2,其运动粘度为85mm2/s(用平氏粘度计测定)。Its used equipment and operation method thereof are basically the same as in Example 1, only difference is that, with 1 kilogram of commercially available food additive grade carrageenan mixture as raw material, add the ethanol of the concentration 45% volume percent of pH8.2 in raw material aqueous solution to form a mixture. The weight ratio of the amount of raw material to the amount of ethanol aqueous solution with a concentration of 45% volume percentage of pH8.2 is 1:4, reflux at a temperature of 65°C for 1 hour, place it at room temperature at 15°C, filter with filter paper, and use pH8.2 Concentration of 45% volume percentage ethanol aqueous solution washed 3 times, dried at a temperature of 65°C until the water content was 11.5% by weight, the extraction rate was 85% by weight, the gel strength was 1180g/cm 2 , and the kinematic viscosity It is 85mm 2 /s (determined by Ping's viscometer).
实施例6Example 6
其所用的设备及其操作方法基本同实施例1,唯有不同的是,以1公斤市售的食品添加剂级卡拉胶混合物为原料,在原料中加入pH8.7的浓度25%体积百分数的乙醇水溶液,形成混合物。原料量与pH8.7的浓度25%体积百分数的乙醇水溶液量的重量比为1∶3,于75℃的温度下回流0.8小时,放置至室温25℃,用滤纸过滤后,用pH8.7的浓度25%体积百分数的乙醇水溶液洗涤2次,于45℃的温度下干燥至水分含量为10.5%重量百分数,其提取率为81%重量百分数,其凝胶强度为1200g/cm2,其运动粘度为82mm2/s(用平氏粘度计测定)。Its used equipment and operation method thereof are basically the same as in Example 1, only difference is, with 1 kilogram of commercially available food additive grade carrageenan mixture as raw material, add the ethanol of the concentration 25% volume percentage of pH8.7 in raw material aqueous solution to form a mixture. The weight ratio of the amount of raw material to the amount of ethanol aqueous solution with a concentration of 25% volume percentage of pH8.7 is 1:3, reflux at a temperature of 75°C for 0.8 hours, place it at room temperature at 25°C, filter with filter paper, and use pH8.7 Wash twice with an aqueous ethanol solution with a concentration of 25% by volume, dry at a temperature of 45°C until the water content is 10.5% by weight, the extraction rate is 81% by weight, the gel strength is 1200g/cm 2 , and the kinematic viscosity It is 82mm 2 /s (determined by Ping's viscometer).
实施例7Example 7
其所用的设备及其操作方法基本同实施例1,唯有不同的是,以1公斤市售的食品添加剂级卡拉胶为原料,在原料中加入pH8.5的浓度10%体积百分数的乙醇水溶液,形成混合物。原料量与pH8.5的浓度10%体积百分数的乙醇水溶液的重量比为1∶0.5,其凝胶强度为1000g/cm2。Its used equipment and operation method thereof are basically the same as embodiment 1, only difference is, with 1 kilogram of commercially available food additive grade carrageenan as raw material, add the ethanol aqueous solution of the concentration 10% volume percent of pH8.5 in raw material , forming a mixture. The weight ratio of raw material amount to 10% by volume ethanol aqueous solution at pH 8.5 is 1:0.5, and its gel strength is 1000 g/cm 2 .
实施例8Example 8
在容器中加入市售的食品添加剂级卡拉胶混合物作为原料,在卡拉胶混合物中加入pH8.5的浓度35%体积百分数的乙醇水溶液,形成混合物。原料量与pH8.5的浓度35%体积百分数的乙醇水溶液量的重量比为1∶2,以频率40千赫(KHz)的超声波处理所形成的混合物(超声波发生器为JU-6212型,上海杰恩普超声设备有限公司出品)55分钟。在超声波处理过程中,所被超声波处理的混合物的温度控制在30℃,经超声波处理55分钟后,用滤纸过滤,用pH 8.5的浓度35%体积百分数的乙醇水溶液洗涤3次,洗涤后于70℃的温度下用市售实验室用的恒温箱干燥至水分含量为10.9%重量百分数,其提取率为88.5%重量百分数,经美国药典26版所述的红外光谱法测试合格,经测试其凝胶强度为1250g/cm2,其运动粘度为91mm2/s(用平氏粘度计测定)。A commercially available food additive grade carrageenan mixture is added in the container as a raw material, and an aqueous ethanol solution with a concentration of 35% by volume of pH 8.5 is added to the carrageenan mixture to form a mixture. The weight ratio of the ethanol aqueous solution amount of the concentration 35% volume percent of raw material amount and pH8.5 is 1: 2, with the mixture (ultrasonic generator is the JU-6212 type of JU-6212 type, Shanghai Produced by JP Ultrasound Equipment Co., Ltd.) 55 minutes. During the ultrasonic treatment process, the temperature of the ultrasonically treated mixture was controlled at 30°C. After ultrasonic treatment for 55 minutes, it was filtered with filter paper, washed 3 times with an aqueous ethanol solution with a concentration of 35% volume percentage of pH 8.5, and washed at 70°C. Under the temperature of ℃, it is 10.9% by weight to dry to moisture content with the constant temperature box that commercially available laboratory is used, and its extraction rate is 88.5% by weight, is qualified through the infrared spectrometry test described in 26th edition of United States Pharmacopoeia, after testing its condensation The glue strength is 1250g/cm 2 , and its kinematic viscosity is 91mm 2 /s (determined by Ping's viscometer).
实施例9Example 9
其所用的设备及其操作方法基本同实施例8,唯有不同的是,1公斤菲律宾产卡拉胶半成品,即卡拉胶混合物中,加入pH9的浓度60%体积百分数的乙醇水溶液,形成混合物。原料量与pH9的浓度60%体积百分数的乙醇水溶液量的重量比为1∶6,以频率20千赫(KHz)的超声波处理100分钟,被超声波处理的混合物的温度控制在40℃,经超声波处理100分钟后,用滤纸过滤,用pH9的浓度60%体积百分数的乙醇水溶液洗涤3次,洗涤后于85℃的温度下干燥至水分含量为9.9%重量百分数,其提取率为83%重量百分数,其凝胶强度为1180g/cm2,其运动粘度为96mm2/s(用平氏粘度计测定)。Its used equipment and operation method thereof are basically the same as embodiment 8, only difference is, 1 kilogram of Philippines produces carrageenan semi-finished product, i.e. in the carrageenan mixture, adds the ethanol aqueous solution of the concentration 60% volume percent of pH9, forms mixture. The weight ratio of raw material amount and the ethanol aqueous solution amount of the concentration 60% volume percent of pH9 is 1: 6, with the ultrasonic treatment of frequency 20 kilohertz (KHz) 100 minutes, the temperature of the mixture by ultrasonic treatment is controlled at 40 ℃, after ultrasonic treatment After processing for 100 minutes, filter with filter paper, wash 3 times with an aqueous ethanol solution with a concentration of 60% by volume of pH9, and dry at a temperature of 85° C. to a moisture content of 9.9% by weight after washing, and the extraction rate is 83% by weight , its gel strength is 1180g/cm 2 , and its kinematic viscosity is 96mm 2 /s (determined by Ping's viscometer).
实施例10Example 10
其所用的设备及其操作方法基本同实施例8,唯有不同的是,在原料卡拉胶混合物中加入pH7.5的浓度35%体积百分数的乙醇水溶液,所得产品K-卡拉胶的凝胶强度为950g/cm2。Its used equipment and operation method thereof are basically the same as embodiment 8, only difference is, in the raw material carrageenan mixture, add the ethanol aqueous solution of the concentration 35% volume percent of pH7.5, the gel strength of gained product K-carrageenan It is 950g/cm 2 .
实施例11Example 11
其所用的设备及其操作方法基本同实施例8,唯有不同的是过滤后不洗涤,其产品K-卡拉胶的凝胶强度为1100g/cm2。The equipment used and its operating method are basically the same as in Example 8, except that it is not washed after filtration, and the gel strength of its product K-carrageenan is 1100 g/cm 2 .
实施例12Example 12
其所用的设备及其操作方法基本同实施例8,唯有不同的是,以1公斤市售的食品添加剂级卡拉胶混合物为原料,在原料中加入pH8.2的浓度45%体积百分数的乙醇水溶液,形成混合物。原料量与pH8.2的浓度45%体积百分数的乙醇水溶液量的重量比为1∶4,以频率60千赫(KHz)的超声波处理10分钟,被超声波处理的混合物的温度控制在20℃,经超声波处理10分钟后,用滤纸过滤,用pH8.2的浓度45%体积百分数的乙醇水溶液洗涤3次,于65℃的温度下干燥至水分含量为11%重量百分数,其提取率为86.5%重量百分数,其凝胶强度为1200g/cm2,其运动粘度为87mm2/s(用平氏粘度计测定)。Its used equipment and its operating method are basically the same as in Example 8, except that 1 kilogram of commercially available food additive grade carrageenan mixture is used as raw material, and ethanol with a concentration of 45% by volume of pH 8.2 is added to the raw material aqueous solution to form a mixture. The weight ratio of the ethanol aqueous solution amount of the concentration 45% volume percent of raw material amount and pH8.2 is 1: 4, with the ultrasonic treatment of frequency 60 kilohertz (KHz) 10 minutes, the temperature of the mixture of ultrasonic treatment is controlled at 20 ℃, After ultrasonic treatment for 10 minutes, filter with filter paper, wash 3 times with ethanol aqueous solution with a concentration of 45% by volume at pH 8.2, and dry at a temperature of 65°C until the moisture content is 11% by weight, and the extraction rate is 86.5%. Percentage by weight, its gel strength is 1200g/cm 2 , and its kinematic viscosity is 87mm 2 /s (measured by Ping's viscometer).
实施例13Example 13
其所用的设备及其操作方法基本同实施例8,唯有不同的是,以1公斤市售的食品添加剂级卡拉胶混合物为原料,在原料中加入pH8.7的浓度25%体积百分数的乙醇水溶液,形成混合物。原料量与pH8.7的浓度25%体积百分数的乙醇水溶液量的重量比为1∶3,以频率30千赫(KHz)的超声波处理20分钟,被超声波处理的混合物的温度控制在30℃,经超声波处理20分钟后,用滤纸过滤,用pH8.7的浓度25%体积百分数的乙醇水溶液洗涤2次,于45℃的温度下干燥至水分含量为10.1%重量百分数,其提取率为82%重量百分数,其凝胶强度为1210g/cm2,其运动粘度为83mm2/s(用平氏粘度计测定)。The equipment used and its operation method are basically the same as in Example 8, except that 1 kg of commercially available food additive grade carrageenan mixture is used as raw material, and ethanol with a concentration of 25% by volume of pH 8.7 is added to the raw material aqueous solution to form a mixture. The weight ratio of the ethanol aqueous solution amount of the concentration 25% volume percentage of raw material amount and pH8.7 is 1: 3, with the ultrasonic treatment of frequency 30 kilohertz (KHz) 20 minutes, the temperature of the mixture by ultrasonic treatment is controlled at 30 ℃, After ultrasonic treatment for 20 minutes, filter with filter paper, wash twice with ethanol aqueous solution with a concentration of 25% by volume at pH 8.7, and dry at a temperature of 45°C until the moisture content is 10.1% by weight, and the extraction rate is 82%. Percentage by weight, its gel strength is 1210g/cm 2 , and its kinematic viscosity is 83mm 2 /s (measured by Ping's viscometer).
实施例14Example 14
其所用的设备及其操作方法基本同实施例8,唯有不同的是,以1公斤市售的食品添加剂级卡拉胶为原料,原料中加入pH8.5的浓度10%体积百分数的乙醇水溶液,形成混合物。原料量与pH8.5的浓度10%体积百分数的乙醇水溶液的重量比为1∶0.5,其凝胶强度为1050g/cm2。Its used equipment and operation method thereof are basically the same as embodiment 8, only difference is, with 1 kilogram of commercially available food additive grade carrageenan as raw material, add the ethanol aqueous solution of the concentration 10% volume percent of pH8.5 in the raw material, A mixture is formed. The weight ratio of raw material amount to 10% by volume ethanol aqueous solution at pH 8.5 is 1:0.5, and its gel strength is 1050 g/cm 2 .
Claims (18)
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