CN102344499B - Method for preparing Iota-carrageenan - Google Patents

Method for preparing Iota-carrageenan Download PDF

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Publication number
CN102344499B
CN102344499B CN 201010243274 CN201010243274A CN102344499B CN 102344499 B CN102344499 B CN 102344499B CN 201010243274 CN201010243274 CN 201010243274 CN 201010243274 A CN201010243274 A CN 201010243274A CN 102344499 B CN102344499 B CN 102344499B
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iota
carrageenin
raw material
glue
water
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CN102344499A (en
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刘松
李鹏程
邢荣娥
李荣锋
李克成
冯金华
于华华
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Institute of Oceanology of CAS
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Abstract

The invention relates to a method for preparing Iota-carrageenan. The method comprises the following steps of: performing alkali modification on a raw material in 3-7 percent by mass percent of potassium hydroxide; neutralizing the modified raw material in a diluted acid solution till the pH is 7-8; washing the modified raw material liquid with water after neutralizing; performing microwave radiation treatment with the microwave radiation power of 180-450W for 5-20 minutes; boiling with water at high temperature for extracting colloid; and adding 0.01-0.1 percent of potassium permangenate aid during colloid extraction to obtain high-yield and high-jel-strength Iota-carrageenan. Due to the adoption of potassium hydroxide, the loss of colloid during alkali treatment can be reduced; the diluted acid is used for neutralizing, so that the water amount is greatly reduced; microwave radiation treatment is performed, and an aid is added for extracting colloid, so that the colloid can be dissolved out more easily, and the gel strength is increased; and the method has a wide application prospect.

Description

A kind of preparation method of Iota-carrageenin
Technical field
The present invention relates to marine chemical industry journey technical field, particularly relate to a kind of preparation method of Iota-carrageenin.
Background technology
Carrageenin (also claiming carrageenin or deer horn phycocolloid) is the hydrophilic polysaccharide of natural polymer that extracts from marine red alga.Its chemical structure is the linear compound of polysaccharide that is comprised of D-semi-lactosi and 3,6-dehydration-D-galactose residue.There is different fine structures in different sources, its colloidal property also is not quite similar, and named have kappa (card handkerchief), an iota (A Outa), lambda (lime reaches), mu (Miao), nu (knob), theta (plug tower), xi (west) type carrageenin etc., but what commercially produce mainly is that first three is planted, and what output was large is the kappa type, and Iota type and Lambda type output are less.
Carrageenin is in food, medicine, daily-use chemical industry, biological chemistry, and the purposes of the aspects such as building coating, textile printing and dyeing and food is very extensive.In foodstuffs industry, as jelling agent, thickening material, stablizer, suspension agent and finings, can be used in soft sweets, jelly, ham sausage, canned meat, ice-creams, beverage, seasonings, milk, bionic foods, jam, beer, bread and the pet food.Can be used as microbe carrier and fixed cell carrier etc. in biological chemistry.
The gel property of carrageenin depends on the type of carrageenin, and kappa-type and iota-type carrageenin can form heat reversible gel, and lambda-type carrageenin then can not gelling.The Iota-carrageenin mainly is present in the living Eucheuma muricatum (Gmel.) Web. Van Bos. of thorn and the aperture leaf Eucheuma muricatum (Gmel.) Web. Van Bos..The gel that the Iota-carrageenin forms is more soft than kappa-carrageenin, high resilience and transparent good, and has without character such as dewatering shrinkage and Nai Gao salt, is thixotropic fluid characteristics etc. in milk and water system.Because it is significantly different that many physics-chem characteristics of Iota-carrageenin and kappa-carrageenin and other colloids have, value and potentiality so that it has a wide range of applications in the industries such as food, makeup, medicine.In recent years, the Iota-carrageenin at home and abroad develops rapidly, and demand increases year by year.
The Iota-carrageenin derives from Philippines marine site Eucheuma Spinosum marine alga, and the kappa-carrageenin derives from Eucheuma cottonii marine alga, and the two materials variance is very large, and extraction process also should be different.But the gelatin extraction technique of existing Iota-carrageenin is still sodium hydroxide alkaline purification mostly, and a large amount of clear water soak and are washed till neutrality, and poach filters after carrying glue, obtains the Iota-carrageenin with alcohol precipitation process.Substantially continued to use kappa-type gelatin extraction technique, only done a small amount of improvement, caused that colloidal sol is serious, glue yield is low, gel-strength is not high.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists in order to overcome above-mentioned prior art, and a kind of preparation method of Iota-carrageenin is provided.
The technical solution used in the present invention is for achieving the above object:
A kind of preparation method of Iota-carrageenin: to sting living Eucheuma muricatum (Gmel.) Web. Van Bos. (Eucheuma Spinosum) as raw material, be to carry out alkali modification in the 3-7% potassium hydroxide with raw material in mass percent, it is 7-8 that raw material after the modification is neutralized to pH through dilute acid soln, stock liquid after the water cleaning modification after the neutralization, be microwave radiation processing 5-20min under the 180-450W in microwave irradiation power then, the high temperature poach is carried glue, the 0.01-0.1% potassium pyrophosphate auxiliary agent that adds when carrying glue namely obtains the Iota-carrageenin.
Described raw material frond and temperature be the potassium hydroxide solution of 50-70 degree with solid-to-liquid ratio 1: 5-10 mixes, and mixing post-modification, to process the treatment time be 1-4 hour, then takes out raw material and drain alkali lye.Described dilute acid soln is dilute hydrochloric acid, and concentration is 0.05-0.5M/L; Soak 2 times with clear water after the neutralization, each 1 hour, then take out raw material and drain.When described high temperature poach is carried glue, frond is dropped in its weight 20-30 water doubly, and in water, add volume mass than adding the 0.01-0.1% potassium pyrophosphate as carrying the glue auxiliary agent, carry glue temperature 95-100 degree.Described high temperature poach is carried behind the glue and being filtered in 300 eye mesh screens while hot, glue sabot, cooling be placed on-18 ℃ freezing 24 hours, thaw, dewater floating through water at low temperature, lyophilize namely gets the Iota-carrageenin after the drying treatment.
The advantage that the present invention has:
1. the present invention adopts potassium hydroxide to carry out alkaline purification, has kept the complete sum of frond to reduce the loss of carrageenin, and extraction yield and gel-strength are apparently higher than other reagent.
2. the present invention adopts Micro-wave pretreatment and interpolation to carry glue auxiliary agent potassium pyrophosphate, makes the smooth stripping of frond colloid, has improved the carrageenin productive rate.Microwave radiation processing makes the frond cell walls slight crack, fragmentation occur, is conducive to the stripping of colloid.Phosphoric acid salt is adsorbed in frond cellulosic and carrageenin surface easily, and self institute is electronegative more, has greatly increased interfacial potential, weaken the adhesive power between them, the a large amount of water molecules of Phosphate Adsorption makes cellulosic and carrageenin swelling simultaneously, makes it soluble in water easily under heating state.
3. the present invention adopts the diluted acid neutralizing treatment, has reduced washing times 2-3 time, reduces water loss 40-50%, and the water amount of blowdown minimizing, and in line acidity of water approaches neutral, and cost of water treatment greatly reduces.
4. after adopting method of the present invention, Iota-carrageenin productive rate is 24.6%, and gel-strength is 77g/cm 2
Embodiment
Embodiment 1
Take the Philippines marine red alga living Eucheuma muricatum (Gmel.) Web. Van Bos. of thorn (Eucheuma Spinosum) as raw material, to prepare mass percent 7% potassium hydroxide solution and be heated to 70 degree, take solid-to-liquid ratio as 1: 10, add the raw material frond, isothermal reaction 1 hour, 300 eye mesh screens filter, and take out frond and drain alkali lye, then soak with the 0.5M/L hydrochloric acid soln, transfer PH to 7-8, add again clear water and soak 2 times, each 1 hour, take out frond and drain.To drain frond and place microwave oven to process, microwave power 450w, reaction times 10min.Frond after microwave treatment drops in its frond weight 20-30 water doubly, and adds volume mass and carry the glue auxiliary agent than 0.05% potassium pyrophosphate conduct in water, carries glue temperature 100 degree, carries glue time 60min.Carry behind the glue while hot that 300 eye mesh screens filter, glue sabot, cooling be placed in the refrigerator-18 ℃ freezing 24 hours, low temperature (water temperature≤15 degree) water floats the dehydration of thawing, lyophilize namely obtains the Iota-carrageenin.
It is 21.0% that above-mentioned gained colloid is measured productive rate, and gel-strength is 66g/cm 2(productive rate Y (%)=product weight * (1-product moisture %)/raw material weight * (1-raw material moisture); The gel-strength measuring method: accurately prepare 1.5% carrageenan solutions (containing 2% calcium chloride), heat little boiling, the rear 20 degree constant temperature of the cup that falls 8-12 hour are measured than intensity measuring device with solidifying, average.)
Existing employing alkali modification is processed and can be removed most of sulfate, has reduced the electrostatic repulsion that causes because of sulfate, thereby improves gel-strength.Alkaline purification helps to remove impurity in addition, improves purity and the performance of carrageenin.But simultaneously alkali lye makes the frond tegumental cell impaired, and the part carrageenin also is subjected to heat of solution or decomposition and runs off in alkali lye, cause " race glue " phenomenon, so the extraction yield of carrageenin reduces.Adopt sodium hydroxide to carry out alkaline purification, cause the colloidal sol loss serious.And the present invention adopts potassium hydroxide to carry out alkaline purification, and potassium ion can promote crosslinked between carrageenan molecule.After potassium ion enters the frond tissue, be deposited in the intercellular substance, bridging has connect the double-spiral structure of carrageenan molecule as key, make it further be cross-linked into larger molecular grouping, be not easy to swelling and be dissolved in the water, kept the complete sum of frond to reduce the loss of carrageenin, extraction yield and gel-strength are apparently higher than other reagent.
Gelatin extraction technique is just in time opposite with alkali modification simultaneously.This is because will protect during alkaline purification frond not allow carrageenin run off in alkali lye, wishes but that in carrying glue carrageenin dissolves in the water as best one can, to improve extraction yield.Because it is higher to contain in the Iota-carrageenin Eucheuma Spinosum frond fibre-bearing matter, has hindered the smooth stripping of colloid.So improve extraction yield, just must manage to destroy cellulosic or colloid and cellulosic interaction and achieve the goal.Among the present invention, by carrying before the glue with the method for Micro-wave pretreatment frond and adding the smooth stripping that auxiliary agent has been realized colloid when carrying glue, improved productive rate.
In addition, the Iota-carrageenin dehydrates common employing alcohol precipitation process, and reagent dosage is large, and cost is higher, and the products obtained therefrom color is darker, and quality descends.After adopting freezing-freeze thawing dehydration among the present invention, cryodesiccated method has guaranteed the quality of product.
Embodiment 2
To sting living Eucheuma muricatum (Gmel.) Web. Van Bos. as raw material, will prepare mass percent 7% potassium hydroxide solution and be heated to 50 degree, take solid-to-liquid ratio as 1: 10, add the raw material frond, isothermal reaction 4 hours, 300 eye mesh screens filter, and take out frond and drain alkali lye.Then soak with the 0.5M/L hydrochloric acid soln, transfer PH to 7-8, add again clear water and soak 2 times, each 1 hour, take out frond and drain.To drain frond and place microwave oven to process, microwave power 180w, reaction times 20min.Frond after microwave treatment drops in its frond weight 20-30 water doubly, and adds 0.01% potassium pyrophosphate as carrying the glue auxiliary agent, carries glue temperature 100 degree, carries glue time 60min.Carry behind the glue while hot that 300 eye mesh screens filter, glue sabot, cooling be placed in the refrigerator-18 ℃ freezing 24 hours, water at low temperature is floated the dehydration of thawing, lyophilize namely obtains the Iota-carrageenin.
Measuring Iota-carrageenin productive rate is 19.3%, and gel-strength is 73g/cm 2
Embodiment 3
To sting living Eucheuma muricatum (Gmel.) Web. Van Bos. as raw material, will prepare mass percent 3% potassium hydroxide solution and be heated to 70 degree, take solid-to-liquid ratio as 1: 10, add the raw material frond, isothermal reaction 4 hours, 300 eye mesh screens filter, and take out frond and drain alkali lye.Then soak with the 0.1M/L hydrochloric acid soln, transfer PH to 7-8, add again clear water and soak 2 times, each 1 hour, take out frond and drain.To drain frond and place microwave oven to process, microwave power 300w, reaction times 15min.Frond after microwave treatment drops in its frond weight 20-30 water doubly, and adds 0.1% potassium pyrophosphate as carrying the glue auxiliary agent, carries glue temperature 100 degree, carries glue time 45min.Carry behind the glue while hot that 300 eye mesh screens filter, glue sabot, cooling be placed in the refrigerator-18 ℃ freezing 24 hours, water at low temperature is floated the dehydration of thawing, lyophilize namely obtains the Iota-carrageenin.
Measuring Iota-carrageenin productive rate is 23.8%, and gel-strength is 60g/cm 2
Embodiment 4
To sting living Eucheuma muricatum (Gmel.) Web. Van Bos. as raw material, will prepare mass percent 3% potassium hydroxide solution and be heated to 60 degree, take solid-to-liquid ratio as 1: 10, add the raw material frond, isothermal reaction 2 hours, 300 eye mesh screens filter, and take out frond and drain alkali lye.Then soak with the 0.1M/L hydrochloric acid soln, transfer PH to 7-8, add again clear water and soak 2 times, each 1 hour, take out frond and drain.To drain frond and place microwave oven to process, microwave power 300w, reaction times 15min.Frond after microwave treatment drops in its frond weight 20-30 water doubly, and adds 0.05% potassium pyrophosphate as carrying the glue auxiliary agent, carries glue temperature 100 degree, carries glue time 60min.Carry behind the glue while hot that 300 eye mesh screens filter, glue sabot, cooling be placed in the refrigerator-18 ℃ freezing 24 hours, water at low temperature is floated the dehydration of thawing, lyophilize namely obtains the Iota-carrageenin.
Measuring Iota-carrageenin productive rate is 22.7%, and gel-strength is 70g/cm 2
Embodiment 5
To sting living Eucheuma muricatum (Gmel.) Web. Van Bos. as raw material, will prepare mass percent 5% potassium hydroxide solution and be heated to 60 degree, take solid-to-liquid ratio as 1: 10, add the raw material frond, isothermal reaction 3 hours, 300 eye mesh screens filter, and take out frond and drain alkali lye.Then soak with the 0.1M/L hydrochloric acid soln, transfer PH to 7-8, add clear water again and soak 2 times, each 1 hour, taking-up drained.To drain frond and place microwave oven to process, microwave power 300w, reaction times 20min.Frond after microwave treatment drops in its frond weight 20-30 water doubly, adds 0.1% potassium pyrophosphate as carrying the glue auxiliary agent, carries glue temperature 100 degree, carries glue time 60min.Carry behind the glue while hot that 300 eye mesh screens filter, glue sabot, cooling be placed in the refrigerator-18 ℃ freezing 24 hours, water at low temperature is floated the dehydration of thawing, lyophilize namely obtains the Iota-carrageenin.
Measuring Iota-carrageenin productive rate is 24.6%, and gel-strength is 77g/cm 2
Comparative example
Take the Philippines marine red alga living Eucheuma muricatum (Gmel.) Web. Van Bos. of thorn (Eucheuma Spinosum) as raw material, to prepare mass percent 7% caustic lye of soda and be heated to 70 degree, take solid-to-liquid ratio as 1: 10, add the raw material frond, isothermal reaction 2 hours, 300 eye mesh screens filter, take out frond and drain alkali lye, add clear water and soak 5 times, each 1 hour, take out frond and drain.Drop in the water of 30 times of its frond weight draining frond, carry glue temperature 100 degree, carry glue time 60min.Carry behind the glue while hot that 300 eye mesh screens filter, glue adds 4 times of volume 95% ethanol precipitations after being cooled to the 40-45 degree, filters, and 60 ℃ of dryings of throw out namely obtain the Iota-carrageenin.
It is 13.6% that above-mentioned gained colloid is measured productive rate, and gel-strength is 36g/cm 2

Claims (4)

1. the preparation method of an Iota-carrageenin, it is characterized in that: to sting living Eucheuma muricatum (Gmel.) Web. Van Bos. (EucheumaSpinosum) as raw material, be to carry out alkali modification in the 3-7% potassium hydroxide with raw material in mass percent, it is 7-8 that raw material after the modification is neutralized to pH through dilute acid soln, raw material after the water cleaning modification after the neutralization, be microwave radiation processing 5-20min under the 180-450W in microwave irradiation power then, the high temperature poach is carried glue, add the potassium pyrophosphate auxiliary agent of 0.01-0.1% when carrying glue, namely obtain the Iota-carrageenin;
When described high temperature poach is carried glue, frond is dropped in its weight 20-30 water doubly, add the 0.01-0.1% potassium pyrophosphate as carrying the glue auxiliary agent, carry glue temperature 95-100 degree.
2. press the preparation method of Iota-carrageenin claimed in claim 1, it is characterized in that: the described raw material living Eucheuma muricatum (Gmel.) Web. Van Bos. of thorn (Eucheuma Spinosum) and temperature be the potassium hydroxide solution of 50-70 degree with solid-to-liquid ratio 1: 5-10 mixes, mixing the post-modification processing treatment time is 1-4 hour, then takes out raw material and drains alkali lye.
3. by the preparation method of Iota-carrageenin claimed in claim 1, it is characterized in that: described dilute acid soln is dilute hydrochloric acid, and concentration is 0.05-0.5M/L; Soak 2 times with clear water after the neutralization, each 1 hour, then take out raw material and drain.
4. press the preparation method of Iota-carrageenin claimed in claim 1, it is characterized in that: described high temperature poach filters in 300 eye mesh screens after carrying glue while hot, the glue sabot, the cooling be placed on-18 ℃ freezing 24 hours, thaw, dewater floating through water at low temperature, lyophilize namely gets the Iota-carrageenin after the drying treatment.
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CN102633902B (en) * 2012-05-03 2013-01-30 临沂艾德森生物科技有限公司 Carrageenan liquid/jelly, and preparation method and use method thereof
CN104844719A (en) * 2014-07-03 2015-08-19 福建省金燕海洋生物科技股份有限公司 Carrageenan preparation method
CN105029527A (en) * 2015-08-26 2015-11-11 集美大学 Method for crisping eucheuma
CN105104923A (en) * 2015-09-15 2015-12-02 常州市鼎日环保科技有限公司 Preparation method for preparing high-elasticity kappa-type carrageenan
CN105585640B (en) * 2016-03-15 2017-09-12 青岛聚大洋藻业集团有限公司 The method that microwave radiation technology alkali protease extracts carragheen
CN109705230B (en) * 2018-12-24 2021-04-09 江苏辰星药业股份有限公司 Method for extracting carrageenan from red algae and carrageenan
CN109824794A (en) * 2019-03-12 2019-05-31 集美大学 A kind of preparation method of carragheen
CN111700266A (en) * 2020-06-09 2020-09-25 邱涛 Refined carrageenan and preparation method and application thereof
CN111925902A (en) * 2020-08-27 2020-11-13 集美大学 Wine clarifying method
CN112663808B (en) * 2020-12-09 2022-05-06 安徽鼎元新材料有限公司 Rock wool heat preservation fire prevention composite sheet for outer wall cracking prevention
CN114702561B (en) * 2021-12-20 2023-05-26 中国科学院海洋研究所 Method for comprehensively extracting phycobiliprotein and carrageenan from weak and weak plumeria

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