CN114957350A - Method for producing galactose by using carrageenan as raw material - Google Patents

Method for producing galactose by using carrageenan as raw material Download PDF

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Publication number
CN114957350A
CN114957350A CN202210739118.0A CN202210739118A CN114957350A CN 114957350 A CN114957350 A CN 114957350A CN 202210739118 A CN202210739118 A CN 202210739118A CN 114957350 A CN114957350 A CN 114957350A
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carrageenan
galactose
solution
raw material
material according
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徐以泓
张宝园
卢丽丽
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Anhui Hegeng Bio Tech Co ltd
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Anhui Hegeng Bio Tech Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02Monosaccharides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00Processes for the preparation of sugar derivatives
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00Processes for the preparation of sugar derivatives
    • C07H1/06Separation; Purification
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

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  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention discloses a method for producing galactose by using carrageenan as a raw material, which comprises the following steps of (1) putting the carrageenan into a dissolving kettle, introducing purified water for dissolving, filtering after dissolving, and removing insoluble physical impurities such as broken stones, seaweed and the like in the carrageenan to obtain a carrageenan solution; (2) introducing the carrageenin solution into a hydrolysis kettle, adding acid, heating, preserving heat, and adding alkali for neutralization; (3) carrying out decoloration, filtration and desalting treatment on the solution after hydrolysis; (4) concentrating and carrying out chromatographic separation on the desalted solution to obtain a galactose enrichment solution; (5) concentrating and crystallizing the galactose enrichment solution; (6) and centrifuging, drying, crushing and packaging the crystallized galactose crude product to finally obtain the high-quality galactose with the purity of more than 99%. The method provided by the invention is simple to operate, does not use an organic solvent, and does not have the food safety problem of organic solvent residue.

Description

Method for producing galactose by using carrageenan as raw material
Technical Field
The invention relates to the technical field of galactose production, in particular to a method for producing galactose by taking carrageenan as a raw material.
Background
Carrageenan, also known as carrageenin, carrageenan and carrageenin, is a general name of polysaccharide extracted from marine red algae (including carrageenin, Eucheuma, Gigartina, Hypnea, etc.), is a mixture of various substances, and has four kinds of Iota (Iota), Kappa (Kappa), lambda (Lamda) and mu (mu). The name carrageenan comes from the species carrageenin (Chondrus crispus, also known as carrageenin), which is known in Ireland as carraigen. In 1844, carrageenan was first isolated from seaweed. When used for food products, carrageenan is indicated in the E code E407 (alginate) of the european union on the packaging of the food product. Although the commercial production of carrageenan began in the 1930's, carrageenan (Gigartina) was used in China as early as 600 b.c., and Ireland used it approximately 400 b.c.
The extraction of k-carrageenan is carried out by taking Eucheuma algae as main raw material, drying in the sun, alkali treating, washing, acidifying and bleaching, washing, boiling, filtering, cooling, squeezing, dewatering, drying, grinding and the like to obtain k-carrageenan powder. The coagulability of K-carrageenan is the best of the various types of carrageenan. k-carrageenan consists of repeating a (1 → 3) -D-galactose-4 sulfate and B (1 → 4) -3, 6-anhydro-D-galactose disaccharide units.
The method for producing galactose by using k carrageenan as a raw material has few literature reports, and the common extraction method of the plant oligosaccharide adopts hot water, ethanol, alkaline water and the like as solvents, and adopts reflux extraction, ultrasonic extraction and microwave extraction to carry out crude extraction, the obtained crude extract is subjected to ethanol fractional precipitation of polysaccharide, so that the polysaccharide and the oligosaccharide are separated to obtain a crude product, and the crude product is extracted by an organic solvent to remove low-polarity organic matters. However, the conventional extraction method obtains crude products, the content of the products is not high, the efficiency is low, and the produced products have the food safety problem of organic solvent residue.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a method for producing galactose by using carrageenan as a raw material, the production method of the galactose has the advantages that the product purification process relates to chromatographic separation and crystallization, the method is advanced, the purity of the produced galactose reaches more than 99 percent, the solvent used in the production method is purified water, other organic solvents are not added in the whole process, and the problem of food safety risk caused by organic solvent residue is effectively avoided.
In order to realize the purpose of the invention, the invention is realized by the following technical scheme: a method for producing galactose by using carrageenan as a raw material comprises the following steps:
(1) putting carrageenan into a dissolution kettle, introducing purified water for dissolution, filtering after dissolution is finished, and removing insoluble physical impurities such as broken stones, seaweed and the like in the carrageenan to obtain a carrageenan solution;
(2) introducing the carrageenin solution obtained in the step (1) into a hydrolysis kettle, adding acid, heating and preserving heat, and adding alkali for neutralization;
(3) carrying out decoloration, filtration and desalting treatment on the solution obtained in the step (2);
(4) concentrating and carrying out chromatographic separation on the solution obtained in the step (3) to obtain a galactose enrichment solution;
(5) concentrating and crystallizing the galactose enrichment solution obtained in the step (4);
(6) and (4) centrifuging, drying, crushing and packaging the galactose crude product obtained in the step (5) to finally obtain high-quality galactose with the purity of more than 99%.
The further improvement lies in that: the type of the carrageenan in the step (1) is kappa-carrageenan.
The further improvement lies in that: the ratio of the carrageenan to the purified water in the step (1) is 1: 1-4.
The further improvement lies in that: the acid in the step (2) is dilute sulfuric acid, the concentration of the dilute sulfuric acid is 5% -30%, and the pH value of the solution after the acid is added is 2-4.
The further improvement lies in that: the temperature after the temperature rise in the step (2) is 90-130 ℃, and the heat preservation time is 2-6 hours.
The further improvement lies in that: the alkali in the step (2) is calcium hydroxide suspension, the mass fraction of the calcium hydroxide suspension is 10-40%, and the pH value of a solution neutralized by the calcium hydroxide suspension is 4.5-6.
The further improvement lies in that: and (4) filtering and intercepting pigment macromolecules by a membrane filtering device by using a membrane decoloring device used for decoloring in the step (3).
The further improvement lies in that: and (4) concentrating the solution, wherein the concentration of the concentrated solution is controlled to be 30-50%.
The further improvement lies in that: in the step (4), four chromatographic separation columns connected in series are adopted for chromatographic separation, the adsorption medium filled in the chromatographic separation columns is calcium type cation adsorption resin, and the used eluent is purified water.
The further improvement lies in that: in the step (5), the galactose enrichment solution is concentrated, and the concentration of the concentrated galactose solution is 65-75%.
The further improvement is that: the drying temperature in the step (6) is 85-95 ℃, the drying time is 2-5 hours, and the moisture of the semi-lactose after drying is controlled below 1.0 percent.
The invention has the beneficial effects that: the carrageenan is dissolved and then filtered, so that the adverse effect of impurities on equipment in a production system is avoided, meanwhile, the content of a final product is effectively improved by adopting a chromatographic separation technology, the carrageenan used as a raw material in the method is from marine natural crops and is a plant source, and the risks of mad cow disease and transgenosis are effectively avoided.
Drawings
FIG. 1 is a flow chart of the production method of the present invention.
FIG. 2 is a HPLC chart of a mixture after hydrolysis of carrageenan of the present invention.
FIG. 3 is an HPLC chart of D-galactose as a final product of the present invention.
Detailed Description
In order to further understand the present invention, the following detailed description will be made with reference to the following examples, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
According to the drawings of fig. 1, 2 and 3, the embodiment provides a method for producing galactose by using carrageenan as a raw material, which comprises the following steps:
(1) putting carrageenan into a dissolution kettle, introducing purified water for dissolution, filtering after dissolution is finished, and removing insoluble physical impurities such as broken stones, seaweed and the like in the carrageenan to obtain a carrageenan solution;
(2) introducing the carrageenin solution obtained in the step (1) into a hydrolysis kettle, adding acid, heating and preserving heat, and adding alkali for neutralization;
(3) carrying out decoloring, filtering and desalting treatment on the solution obtained in the step (2);
(4) concentrating and carrying out chromatographic separation on the solution obtained in the step (3) to obtain a galactose enrichment solution;
(5) concentrating and crystallizing the galactose enrichment solution obtained in the step (4);
(6) and (4) centrifuging, drying, crushing and packaging the galactose crude product obtained in the step (5) to finally obtain the high-quality galactose with the purity of more than 99%.
Examples
Dissolving carrageenan in purified water by using Arabic gum, and controlling the mass percentage concentration to be 30%;
adding dilute sulfuric acid with the mass fraction of 10%, adjusting the pH value of the solution to 2.5, hydrolyzing at the temperature of 102 ℃ for 5 hours, cooling to 80 ℃, adding calcium hydroxide suspension with the mass fraction of 20%, adjusting the pH value to 5.0, and adjusting the content of the hydrolyzed carrageenan solution galactose to 56.461%;
introducing the neutralized solution into a membrane decolorization device, and determining the decolorization effect by testing the light transmittance of the decolorized solution;
the decolored solution enters an ion exchange column for desalting, two ion exchange columns are provided, one is a positive column, the positive column is filled with cation exchange resin, the other is a negative column, the negative column is filled with anion exchange resin, and the conductivity of the desalted solution is tested and is required to be 20 mu s/cm smaller;
evaporating and concentrating the decolorized solution, wherein the concentration of the concentrated solution is 35%, then separating and removing impurities by using a program simulated moving bed chromatographic separation device to obtain a galactose enrichment solution, wherein the chromatographic separation adopts four chromatographic separation columns and a program control system which are connected in series, an adsorption medium filled in the chromatographic separation columns is calcium type cation adsorption resin, and an eluant is purified water;
evaporating and concentrating the galactose enrichment solution obtained after chromatographic separation, wherein the concentration of the concentrated solution is 68%, and crystallizing the concentrated galactose by adopting a crystallizing tank;
after the galactose crystallization is finished, the material is centrifugally dried by a centrifugal machine, the moisture of the dried material is 11.2%, and then the dried material is dried at the drying temperature of 92 ℃ for 4 hours, and the moisture of the half-lactose after drying is 0.03%. The dried product has particles and a small amount of powder, and a pulverizer is adopted to pulverize the materials;
the purity of the packaged galactose product is 99.697%.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (11)

1. A method for producing galactose by using carrageenan as a raw material is characterized by comprising the following steps:
putting carrageenan into a dissolution kettle, introducing purified water for dissolution, filtering after dissolution is finished, and removing insoluble physical impurities such as broken stones, seaweed and the like in the carrageenan to obtain a carrageenan solution;
introducing the carrageenin solution obtained in the step (1) into a hydrolysis kettle, adding acid, heating and preserving heat, and adding alkali for neutralization;
carrying out decoloration, filtration and desalting treatment on the solution obtained in the step (2);
concentrating and carrying out chromatographic separation on the solution obtained in the step (3) to obtain a galactose enrichment solution;
concentrating and crystallizing the galactose enrichment solution obtained in the step (4);
and (4) centrifuging, drying, crushing and packaging the galactose crude product obtained in the step (5) to finally obtain high-quality galactose with the purity of more than 99%.
2. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein the type of the carrageenan in the step (1) is kappa-carrageenan.
3. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein the ratio of the carrageenan in the step (1) and the purified water is 1: 1-4.
4. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein the acid in the step (2) is dilute sulfuric acid, the concentration of the dilute sulfuric acid is 5% -30%, and the pH value of the solution after adding the acid is 2-4.
5. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein the temperature after the temperature rise in the step (2) is 90-130 ℃, and the holding time is 2-6 hours.
6. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein the base in the step (2) is a calcium hydroxide suspension, the mass fraction of the calcium hydroxide suspension is 10% -40%, and the pH value of a solution neutralized by the calcium hydroxide suspension is 4.5-6.
7. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein the membrane decolorization device used for decolorization in step (3) filters and retains pigment macromolecules by a membrane filtration device.
8. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein the solution is concentrated in the step (4), and the concentration of the concentrated solution is controlled to be 30% -50%.
9. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein four chromatographic separation columns connected in series are used for the chromatographic separation in step (4), the adsorption medium filled in the chromatographic separation columns is calcium type cation adsorption resin, and the eluent used is purified water.
10. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein in the step (5), the galactose concentrated solution is concentrated, and the concentration of the concentrated galactose solution is 65% -75%.
11. The method for producing galactose by using carrageenan as a raw material according to claim 1, wherein the drying temperature in the step (6) is 85 ℃ to 95 ℃, the drying time is 2 to 5 hours, and the moisture of the lactose after drying is controlled to be less than 1.0%.
CN202210739118.0A 2022-06-28 2022-06-28 Method for producing galactose by using carrageenan as raw material Pending CN114957350A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106318994A (en) * 2015-07-01 2017-01-11 现代自动车株式会社 Method of preparing seaweed-derived galactose using agarase
CN108026554A (en) * 2015-09-11 2018-05-11 科莱恩国际有限公司 Method for purifying biological matter hydrolysate
CN112458126A (en) * 2020-11-26 2021-03-09 中国海洋大学 Preparation method and application of galactose sulfate compound with anti-inflammatory activity
CN112708702A (en) * 2021-02-07 2021-04-27 安徽禾庚生物技术有限公司 Method for producing plant source D-tagatose
CN112876520A (en) * 2021-02-07 2021-06-01 安徽禾庚生物技术有限公司 Preparation method of high-quality arabinose, galactose, rhamnose and glucuronic acid

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106318994A (en) * 2015-07-01 2017-01-11 现代自动车株式会社 Method of preparing seaweed-derived galactose using agarase
CN108026554A (en) * 2015-09-11 2018-05-11 科莱恩国际有限公司 Method for purifying biological matter hydrolysate
CN112458126A (en) * 2020-11-26 2021-03-09 中国海洋大学 Preparation method and application of galactose sulfate compound with anti-inflammatory activity
CN112708702A (en) * 2021-02-07 2021-04-27 安徽禾庚生物技术有限公司 Method for producing plant source D-tagatose
CN112876520A (en) * 2021-02-07 2021-06-01 安徽禾庚生物技术有限公司 Preparation method of high-quality arabinose, galactose, rhamnose and glucuronic acid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JEONG AH KIM,等: "Production of 3, 6-Anhydro-D-galactose from κ-Carrageenan Using Acid Catalysts", 《BIOTECHNOLOGY AND BIOPROCESS ENGINEERING》, vol. 21, pages 79 - 86, XP035648542, DOI: 10.1007/s12257-015-0636-5 *
郭世伟: "糖蜜纳滤脱色过程机理及高性能脱色膜制备的研究", 《中国科学院大学博士学位论文》, pages 11 - 13 *

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