CN109384820B - Method for preparing arabinose, galactose, rhamnose and glucuronic acid - Google Patents
Method for preparing arabinose, galactose, rhamnose and glucuronic acid Download PDFInfo
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- CN109384820B CN109384820B CN201710677852.8A CN201710677852A CN109384820B CN 109384820 B CN109384820 B CN 109384820B CN 201710677852 A CN201710677852 A CN 201710677852A CN 109384820 B CN109384820 B CN 109384820B
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- 229930182830 galactose Natural products 0.000 title claims abstract description 74
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229940097043 glucuronic acid Drugs 0.000 title claims abstract description 64
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 title claims abstract description 48
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 title claims abstract description 46
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 title claims abstract description 39
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 61
- AEMOLEFTQBMNLQ-AQKNRBDQSA-N D-glucopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-AQKNRBDQSA-N 0.000 title abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 70
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- 239000001785 acacia senegal l. willd gum Substances 0.000 claims abstract description 16
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- 238000001914 filtration Methods 0.000 claims abstract description 10
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- 239000010413 mother solution Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 184
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 claims description 61
- 239000000049 pigment Substances 0.000 claims description 48
- 230000008569 process Effects 0.000 claims description 42
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 claims description 38
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- 238000000605 extraction Methods 0.000 claims description 35
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- 239000000463 material Substances 0.000 claims description 33
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- SRBFZHDQGSBBOR-HWQSCIPKSA-N L-arabinopyranose Chemical compound O[C@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-HWQSCIPKSA-N 0.000 claims description 23
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- 238000001179 sorption measurement Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000000284 extract Substances 0.000 claims description 9
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 8
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- AEMOLEFTQBMNLQ-WAXACMCWSA-N alpha-D-glucuronic acid Chemical compound O[C@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-WAXACMCWSA-N 0.000 claims description 7
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
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- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
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- DWCSNWXARWMZTG-UHFFFAOYSA-N Trigonegenin A Natural products CC1C(C2(CCC3C4(C)CCC(O)C=C4CCC3C2C2)C)C2OC11CCC(C)CO1 DWCSNWXARWMZTG-UHFFFAOYSA-N 0.000 description 2
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- WQLVFSAGQJTQCK-VKROHFNGSA-N diosgenin Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)CC4=CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 WQLVFSAGQJTQCK-VKROHFNGSA-N 0.000 description 2
- WQLVFSAGQJTQCK-UHFFFAOYSA-N diosgenin Natural products CC1C(C2(CCC3C4(C)CCC(O)CC4=CCC3C2C2)C)C2OC11CCC(C)CO1 WQLVFSAGQJTQCK-UHFFFAOYSA-N 0.000 description 2
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- 206010016952 Food poisoning Diseases 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 description 1
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- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 description 1
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- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 description 1
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 description 1
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- 235000013976 turmeric Nutrition 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H7/00—Compounds containing non-saccharide radicals linked to saccharide radicals by a carbon-to-carbon bond
- C07H7/02—Acyclic radicals
- C07H7/033—Uronic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Saccharide Compounds (AREA)
Abstract
Hydrolyzing Arabic gum under acidic condition to obtain mixed solution of arabinose, galactose, rhamnose and glucuronic acid, neutralizing, filtering, concentrating to obtain concentrated solution, decolorizing, deionizing, and separating to obtain: (1) Concentrating and crystallizing the arabinose-rich solution to obtain crystallized arabinose; (2) Concentrating and crystallizing the galactose-rich solution to obtain crystalline galactose; (3) Mixing the mixed sugar solution rich in galactose and rhamnose with a crystallization mother solution of galactose, performing chromatographic separation to obtain a solution rich in rhamnose, and then concentrating and crystallizing to obtain crystallized rhamnose; (4) Removing ions from the solution rich in glucuronic acid, and then concentrating and crystallizing to obtain the crystalline glucuronic acid.
Description
Technical Field
The invention relates to a production technology of L-arabinose, D-galactose, L-rhamnose and D-glucuronic acid. In particular to the technical field of production for simultaneously preparing arabinose, galactose, rhamnose and glucuronic acid by taking Arabic gum as a raw material.
Background
Arabic gum is a thickener which is widely available, safe and harmless and can be partially degraded by human bodies. Gum arabic has two components, a polysaccharide and a small portion of protein covalently bound to the polysaccharide. The polysaccharide in the Arabic gum can be subjected to acidolysis to obtain a mixture of L-arabinose, D-galactose, L-rhamnose, D-glucuronic acid, oligosaccharides and other heterosugars.
L-Arabinose (L-arabinosine), also called L-Arabinose, is a sweetener with extremely low calorie, can effectively inhibit and block the metabolic transformation of human body to sucrose, thereby inhibiting obesity, and preventing and treating diseases related to hyperglycemia; the L-arabinose can also be used as a medical intermediate for preparing antiviral and anticancer drugs, and also can be used for preparing bacteria culture medium in the biochemical field, synthesizing spices and the like. L-arabinose rarely occurs in nature in the free form, usually in combination with other monosaccharides, in colloids, hemicelluloses, bacterial polysaccharides and certain glycosides in the form of heteropolysaccharides or L-arabinan-D-galactose. At present, most of the L-arabinose is prepared by extracting from some natural or semi-natural raw materials, including some plant fibers or semi-fibers (such as corn, bagasse, straws and the like), beet pulp, arabic gum and the like.
D-galactose is an important drug intermediate. The Arabic gum acidolysis solution contains L-arabinose and also has higher content of D-galactose, and in order to improve the utilization rate of raw materials and economic benefit, the L-arabinose and the D-galactose in the acidolysis solution need to be separated and extracted. The prior patents in China mainly focus on the separation and extraction of L-arabinose, and D-galactose is rarely mentioned.
Rhamnose is widely distributed in plants as a trace sugar, but the content is not high. Rhamnose can be used for measuring intestinal permeability, and can be used as sweetener for producing essence and flavor, and can also be used as pharmaceutical raw material, etc. CN103755776B discloses a method for extracting diosgenin from turmeric and then converting the diosgenin into rhamnose; CN103937854A discloses a method for preparing rhamnose by utilizing rutin.
Glucuronic acid (Glucuronic acid), abbreviated as Glucuronic acid, is a compound formed by oxidizing primary alcohol hydroxyl of glucose into carboxyl, and is widely distributed in animals and plants. In thatThe plant exists in the form of uronic acid in gum such as acacia gum and tragacanth gum, and is important component for pectin, mucus and high-grade polysaccharide. In animals, glucuronic acid forms complexes with glucuronic acid that are stored in tissues. Glucuronic acid molecular formula is C 6 H 10 O 7 Relative molecular weight 194.14, powder or white needle crystals. The glucuronic acid aqueous solution is unstable, is easy to form 3,6-glucuronolactone to be in a interconversion equilibrium state, and is easy to generate decarboxylation to generate CO when the D-glucuronic acid is heated and a strong acid exists 2 Furan and other cracking products. Glucuronic acid can combine with toxic substances in vivo to form nontoxic glucuronic acid conjugate, and can be discharged, and has effects of protecting liver and removing toxic substance, and can be used for treating hepatitis, liver cirrhosis, and food and drug poisoning. Glucuronic acid is also an important component constituting connective tissue, and can be used for treating arthritis and collagenous diseases.
At present, gum arabic is adopted as a raw material in most of L-arabinose and D-galactose produced by the traditional process, mixed liquor of the L-arabinose and the D-galactose is obtained by hydrolyzing the gum arabic under an acidic condition and controlling different hydrolysis conditions, after impurities such as decolorization, desalination and the like of the mixed liquor are removed, the L-arabinose is extracted and precipitated by an organic solvent, then the concentrated L-arabinose and the D-galactose are purified, and the crude products of the L-arabinose and the D-galactose are obtained by primary crystallization and centrifugal dehydration. The traditional production process has long flow, low yield, high consumption of water, electricity, steam and the like and high production cost.
The invention patent of the applicant's prior application with publication number CN106589010A discloses a method for simultaneously producing L-arabinose and D-galactose, which comprises the steps of hydrolyzing, neutralizing, decoloring, filtering, desalting, separating the concentrated mixed sugar solution by a simulated moving bed chromatographic separation device to obtain a solution rich in L-arabinose and a solution rich in D-galactose, and then respectively concentrating and crystallizing to obtain an L-arabinose crystal product and a D-galactose crystal product. In the invention, rhamnose and glucuronic acid in the hydrolysate are not extracted and are discharged as impurities. The invention aims to simultaneously produce four products of arabinose, galactose, rhamnose and glucuronic acid.
Disclosure of Invention
Aiming at the defects in the existing Arabic gum extraction process, the invention provides a new process for acidolysis and extraction of Arabic gum.
The invention aims to provide an improved method for extracting arabinose, galactose, rhamnose and glucuronic acid from Arabic gum, and four products of L-arabinose, D-galactose, L-rhamnose and D-glucuronic acid can be obtained simultaneously.
Hydrolyzing Arabic gum under acidic condition to obtain mixed solution of arabinose, galactose, rhamnose, glucuronic acid and a small amount of heterosugar, neutralizing, filtering and concentrating to obtain concentrated solution, and then decoloring, deionizing and separating with a device for decoloring, deionizing and separating the mixture at the same time to obtain: (1) Concentrating and crystallizing the arabinose-rich solution to obtain crystallized arabinose;
(2) Concentrating and crystallizing the galactose-rich solution to obtain crystalline galactose;
(3) Mixing the mixed sugar solution rich in galactose and rhamnose with a crystallization mother liquor of galactose, performing chromatographic separation to obtain a rhamnose-rich solution, and then concentrating and crystallizing to obtain crystallized rhamnose;
(4) The solution rich in glucuronic acid is deionized, concentrated and crystallized to obtain the crystal glucuronic acid.
The invention relates to a method for preparing arabinose, galactose, rhamnose and glucuronic acid by taking Arabic gum as a raw material, which adopts the main technical scheme that the steps are as follows:
step 1: dissolving Arabic gum, and blending to obtain a mixture with the mass percentage concentration of 10-35%, and optimally 20-25%; adding dilute sulfuric acid or dilute hydrochloric acid to adjust the pH value of the solution to 0.1-3.0, and optimally to 0.1-0.6; hydrolyzing at 90-138 ℃ for 4-15 hours to obtain hydrolysate; standing the hydrolysate for 1~2 hours, filtering to obtain supernatant, neutralizing with alkali until the pH value is 3.0-5.5, filtering, and concentrating to obtain concentrated solution.
Step 2: and (2) decoloring, deionizing and separating the concentrated solution obtained in the step (1) by using a device for decoloring, deionizing and separating the mixture at the same time to obtain: the arabinose liquid A is rich; rich in galactose liquid B; rich in mixed sugar liquid C; rich in glucuronic acid solution D; pigment and ionic liquid S.
And step 3: and (3) concentrating, crystallizing and drying the arabinose-rich liquid A obtained in the step (2) to obtain the crystalline L-arabinose.
And 4, step 4: and (3) concentrating, crystallizing and drying the galactose-rich liquid B obtained in the step (2) to obtain the crystal D-galactose.
And 5: and (3) mixing the mixed sugar solution C rich in the galactose and the rhamnose obtained in the step (2) with the crystallization mother liquor G obtained in the step (4), and then separating by using a chromatographic separation device to obtain a rhamnose solution E rich in the rhamnose and a galactose solution F rich in the galactose.
And 6: concentrating, crystallizing and drying the rhamnose-rich liquid E obtained in the step 5 to obtain crystallized rhamnose; and (3) mixing the galactose-rich liquid F obtained in the step (5) with the galactose liquid B obtained in the step (2).
And 7: and (3) removing ions from the glucuronic acid-rich liquid D obtained in the step (2), and then concentrating, crystallizing and drying to obtain the crystallized glucuronic acid.
Further, the chromatographic separation device in step 5 is a program simulated moving bed chromatographic separation device, and the total number of the chromatographic separation device is 6, the chromatographic column is filled with an adsorption medium, and the adsorption medium is calcium type cation adsorption resin or calcium type molecular sieve; the eluent used was pure water. Separating by a chromatographic device to obtain a rhamnose-rich liquid E and a galactose-rich liquid F; concentrating, crystallizing and drying the rhamnose-rich liquid E to obtain crystallized rhamnose; and (3) mixing the galactose-rich liquid F with the galactose liquid B obtained in the step (2), concentrating, crystallizing and drying to obtain the crystal D-galactose.
In order to achieve the object of the present invention, the present invention provides an apparatus for treating decolorization and deionization of a concentrated solution after hydrolysis of gum arabic while separating the mixture.
The device is provided with 4 chromatographic columns which are connected in series, and the chromatographic columns consist of a chromatographic column, a booster pump, a conductivity meter, a connecting pipe, an isolating valve, an eluent pipe, a material pipe, a circulating flow meter, a raffinate Yu Yeguan, a raffinate flow meter, a raffinate flow regulating valve, a pigment and ionic liquid branch, a glucuronate branch, an extract pipe, an extract flow meter, an extract flow regulating valve, an arabinose liquid branch, a galactose liquid branch and a mixed sugar liquid branch; also comprises an arabinose liquid tank, a galactose liquid tank, a mixed sugar liquid tank, a glucuronic acid liquid tank, a pigment and ion liquid tank; an eluent valve is connected to the inlet of each chromatographic column; the inlet of the 1 st chromatographic column is connected with a material valve; the eluent valve and the material valve are respectively connected with the eluent pipe and the material pipe; the outlet of each chromatographic column is connected with a raffinate valve; the extraction Yu Yefa is connected with a raffinate pipe; the raffinate pipe is provided with a raffinate liquid flowmeter and a raffinate liquid flow regulating valve which are used for detecting and regulating the flow; the raffinate pipe is divided into two branches after passing through a raffinate flow regulating valve: the first branch is a pigment and ionic liquid branch and is connected to the pigment and the ionic liquid tank; the second branch is a glucuronic acid liquid branch and is connected to a glucuronic acid liquid tank; the last chromatographic column is connected with an extraction liquid valve; the extraction liquid valve is connected with an extraction liquid pipe; the extracting solution pipe is provided with an extracting solution flowmeter and an extracting solution flow regulating valve for detecting and regulating the flow; the liquid extracting pipe is divided into three branches after passing through an extracting liquid flow regulating valve: the first branch is an arabinose liquid branch and is connected to an arabinose liquid groove; the second branch is a galactose solution branch and is connected to a galactose solution tank; the third branch is a mixed sugar solution branch and is connected to the mixed sugar solution tank.
Furthermore, the device for decoloring, deionizing and separating the mixture simultaneously has 4 chromatographic columns which are connected in series; a material distributor for uniformly distributing materials is arranged above and below each chromatographic column; the chromatographic column is filled with an adsorption medium; the adsorption medium is sodium type cation adsorption resin; the eluent used was pure water.
In order to achieve the purpose of the invention, the invention also provides an operation method of the device for decoloring, deionizing and separating the mixture.
The device operation comprises three processes: feeding, eluting and internally circulating.
The device for decolorizing, deionizing and separating the mixture used in the invention comprises 4 chromatographic columns which are connected in series, wherein the numbers of the columns are Z1, Z2, Z3 and Z4. The device periodically operates, each period is divided into 10 processes, starting from the process 1 to the process 10, and then returning to the process 1 to continuously and circularly operate; the 10 processes are as follows:
process 1: feeding on Z1; and (4) discharging the rich mixed sugar liquid from the Z4, feeding the rich mixed sugar liquid into an extraction liquid pipe, passing through an extraction liquid flow meter and an extraction liquid flow regulating valve, feeding the rich mixed sugar liquid into a mixed sugar liquid groove, and feeding the rich mixed sugar liquid into a VC valve.
And (2) a process: feeding on Z1; the part Z1 is rich in glucuronic acid liquid, enters a raffinate Yu Yeguan extraction, passes through a raffinate flow meter and a raffinate flow regulating valve, enters a glucuronic acid liquid branch and enters a glucuronic acid liquid tank; an eluent is added on Z2; and (4) discharging the galactose-rich liquid from the Z4, feeding the galactose-rich liquid into an extraction liquid pipe, passing through a flow meter and a flow control valve, feeding the galactose-rich liquid into a galactose liquid tank.
And 3, process: an eluent is added on Z4; and (4) discharging arabinose-rich liquid from the Z4 lower part, entering an extraction liquid pipe, passing through an extraction liquid flow meter and an extraction liquid flow regulating valve, entering an arabinose liquid branch, and entering an arabinose liquid groove.
And 4, process: the material does not enter and exit the system, and the system performs internal circulation.
And (5) a process: an eluent is added on Z3; and (3) discharging the pigment and the ionic liquid from the Z2, feeding the pigment and the ionic liquid into a lifting Yu Yeguan, and feeding the pigment and the ionic liquid into a pigment and ionic liquid tank after passing through a flowmeter, a flow regulating valve and a pigment ion branch.
And 6, a process: the material does not enter and exit the system, and the system performs internal circulation.
And (7) a process: an eluent is added on Z4; and (3) discharging the pigment and the ionic liquid from the Z3, feeding the pigment and the ionic liquid into a lifting Yu Yeguan, and feeding the pigment and the ionic liquid into a pigment and ionic liquid tank through a flowmeter, a flow regulating valve and a pigment ion branch.
And (8) a process: the material does not enter and exit the system, and the system performs internal circulation.
And a process 9: an eluent is added on Z1; and (3) discharging the pigment and the ionic liquid from the Z4, feeding the pigment and the ionic liquid into a lifting Yu Yeguan, and feeding the pigment and the ionic liquid into a pigment and ionic liquid tank through a flowmeter, a flow regulating valve and a pigment ion branch.
The process 10: the material does not enter and exit the system, and the system performs internal circulation.
In the process 1,2,3,5,7,9, the volume of feed liquid entering the chromatographic system is equal to the volume of feed liquid flowing out of the chromatographic system at the same time, and the volume is accumulated by a flow meter, and the accumulated amount is used for controlling the beginning and the end of feeding and discharging; in process 4,6,8, 10, the volumetric amount of material that is recirculated is metered and accumulated by a recirculation flow meter on the connecting tube, and the accumulated amount is used to control the amount of internal recirculation.
After the treatment of the device, the following are obtained: the pigment and the ionic liquid S are rich, and the part is discharged as waste liquid; the arabinose liquid A is rich; rich in galactose liquid B; rich in mixed sugar liquid C; is rich in glucuronic acid solution D.
Further, in step 7 of the technical scheme, when removing ions from the glucuronic acid solution D rich in glucose, a conventional ion exchange or automatic ion exchange method can be adopted to remove the ions.
As a further improvement of the present invention, in step 7 of the technical solution, when removing ions from the glucuronic acid solution D rich in glucuronic acid, a second set of the device for decoloring, deionizing and separating the mixture of the present invention can be used to remove ions from the glucuronic acid solution D rich in glucuronic acid.
As a further improvement of the invention, the number of the tandem chromatographic columns forming the chromatographic system can be n, n =3 to 12, and each period is divided into 2n +2 processes during the operation.
The method of the invention can simultaneously produce four products of L-arabinose, D-galactose, L-rhamnose and D-glucuronic acid by hydrolyzing Arabic gum at one time, decoloring, filtering, concentrating and other conventional processes, then performing the refining treatment procedures of deionization, separation and the like, concentrating and crystallizing. The method of the invention utilizes a device for decoloring, deionizing and separating the mixture, not only has high efficiency of deionizing, but also can separate the saccharides in the mixed sugar solution. The method has the advantages of high utilization rate of raw materials, short production flow, and repeated return of crystallization mother liquor of each product for separation and extraction.
Drawings
FIG. 1 is a process diagram of the process of the present invention.
FIG. 2 is the HPLC chromatogram of the mixture after hydrolysis of Arabic gum.
FIG. 3 is a schematic diagram of an apparatus for decolorizing, deionizing and separating mixtures for use in the present invention.
The components in the drawings are as follows: the device comprises a chromatographic column 1, a booster pump 2, a conductivity meter 3, a connecting pipe 4, an isolating valve 5, an eluent pipe 6, a material pipe 7, a circulating flow meter 10, a material valve VF and eluent valves VW 1-VW 4; the device comprises raffinate valves VS 1-VS 4, a raffinate pipe 8, a raffinate flowmeter 81, a raffinate flow regulating valve 82, a VE valve, an impurity branch 83 and a pigment ion liquid tank; a VD valve, a glucuronic acid liquid branch 84 and a glucuronic acid liquid tank; an extraction liquid valve VX, an extraction liquid pipe 9, an extraction liquid flowmeter 91, an extraction liquid flow regulating valve 92, a VA valve, an arabinose liquid branch 93 and an arabinose liquid groove; a VB valve, a galactose liquid branch 94 and a galactose liquid tank; a VC valve, a mixed sugar liquid branch 95 and a mixed sugar liquid groove.
FIG. 4 is a schematic view of 10 processes for one cycle of operation of an apparatus for decolorizing, deionizing and separating mixtures used in the present invention.
In the figure, the column is in bold to indicate that material is flowing through.
Detailed description of the preferred embodiment
The process and effect of the present invention will be described below with reference to the accompanying drawings and specific examples, but the present invention is not limited by the following examples.
Example 1, acacia gum is crushed and dissolved at 30 to 40 ℃ to be prepared into 25 mass percent concentration, dilute sulphuric acid is added to adjust the pH value of the solution to 0.3, and hydrolysis is carried out for 12 hours at 105 ℃ to obtain hydrolysate; standing the hydrolysate for 1~2 hours, filtering to obtain supernatant, neutralizing with alkali to pH 4.0-5.0, filtering, and concentrating to obtain concentrated solution.
Example 2, the apparatus for decoloring deionizing and simultaneously separating a mixture used in the present invention, as shown in fig. 3, comprises a chromatography column 1, a booster pump 2, a conductivity meter 3, a connection pipe 4, an isolation valve 5, an eluent pipe 6, a material pipe 7, and a circulation flow meter 10; yu Yeguan 8, a raffinate flow meter 81, a raffinate flow regulating valve 82, a pigment and ionic liquid branch 83 and a glucuronic acid liquid branch 84; an extraction liquid pipe 9, an extraction liquid flow meter 91, an extraction liquid flow regulating valve 92, an arabinose liquid branch 93, a galactose liquid branch 94 and a mixed sugar liquid branch 95; an arabinose liquid tank, a galactose liquid tank, a mixed sugar liquid tank, a glucuronic acid liquid tank, a pigment and an ion liquid tank; an eluent valve VW 1-VW 4 is connected to an inlet of each chromatographic column; the inlet of the 1 st chromatographic column is connected with a material valve VF; the eluent valves VW 1-VW 4 and the material valve VF are respectively connected with the eluent pipe 6 and the material pipe 7; the outlet of each chromatographic column is connected with a raffinate valve VS 1-VS 4; the residual liquid extracting valves VS 1-VS 4 are connected with a residual liquid extracting pipe 8; the raffinate pipe 8 is provided with a raffinate liquid flowmeter 81 and a raffinate liquid flow regulating valve 82 for detecting and regulating flow; the raffinate pipe 8 is divided into two branches after passing through the raffinate flow regulating valve 82: the first branch is a pigment and ionic liquid branch 83 which enters a pigment and ionic liquid tank after passing through a VE valve; the second branch is a glucuronic acid liquid branch 84, and enters a glucuronic acid liquid tank after passing through a VD valve; the last chromatographic column is connected with an extraction liquid valve VX; the extraction liquid valve VX is connected with an extraction liquid pipe 9; the extracting liquid pipe 9 is provided with an extracting liquid flowmeter 91 and an extracting liquid flow regulating valve 92 for detecting and regulating the flow; the liquid extracting pipe is divided into three branches after passing through an extracting liquid flow regulating valve 92: the first branch is an arabinose liquid branch 93 which enters an arabinose liquid groove after passing through a VA valve; the second branch is a galactose liquid branch 94 which enters a galactose liquid tank after passing through a VB valve; the third branch is a mixed sugar solution branch 95 which enters the mixed sugar solution tank through a VC valve.
In this example, the device for decoloring, deionizing and separating the mixture simultaneously has 4 chromatographic columns connected in series, the numbers of the columns are Z1, Z2, Z3 and Z4; the upper part and the lower part of the chromatographic column are provided with distributing devices for uniformly distributing materials; the chromatographic column is filled with an adsorption medium which is sodium type cation adsorption resin; the eluent used was pure water.
As a further improvement of the invention, the number of the tandem chromatographic columns constituting the chromatographic system can be n, wherein n =3 to 12.
Example 3, the operation process of the apparatus for decoloring deionizing and simultaneously separating a mixture described in example 2 comprises three processes: feeding, eluting and internally circulating.
The device operates periodically, for a chromatographic system formed by connecting 4 chromatographic columns in series, the column numbers are Z1, Z2, Z3 and Z4, each period is divided into 10 processes, starting from the process 1 to the process 10, and then returning to the process 1 for continuous circulation; the 10 processes are as follows:
process 1: feeding materials on the Z1, discharging the mixed sugar liquid C rich in Z4, feeding the mixed sugar liquid C into an extracting liquid pipe 9, passing through an extracting liquid flow meter 91 and an extracting liquid flow regulating valve 92, feeding the mixed sugar liquid C into a mixed sugar liquid groove 95, and feeding the mixed sugar liquid C into a VC valve.
And (2) a process: feeding materials on the Z1, discharging a solution D rich in glucuronic acid from the Z1, entering a raffinate pipe 8, passing through a raffinate flow meter 81, a raffinate flow regulating valve 82 and a glucuronic acid solution branch 84, and entering a glucuronic acid solution tank after passing through a VD valve. And eluent is added on Z2, and the rich galactose liquid B is discharged from Z4, enters an extraction liquid pipe 9, passes through an extraction liquid flow meter 91 and an extraction liquid flow regulating valve 92, enters a galactose liquid branch 94, passes through a VB valve, and enters a galactose liquid tank.
And 3, process: and (3) eluting the Z4 with an eluent, discharging the arabinose-rich liquid A from the Z4, feeding the arabinose-rich liquid A into an extraction liquid pipe 9, passing through an extraction liquid flow meter 91 and an extraction liquid flow regulating valve 92, feeding the arabinose-rich liquid A into an arabinose liquid branch 93, and feeding the arabinose liquid A into an arabinose liquid tank after passing through a VA valve.
And 4, process: the material does not enter and exit the system, and the system performs internal circulation.
And (5) a process: and (3) feeding an eluent on the Z3, discharging the pigment and the ionic liquid from the Z2, feeding the pigment and the ionic liquid into a raffinate liquid pipe 8, passing through a raffinate liquid flow meter 81, a raffinate liquid flow regulating valve 82 and a pigment ion branch 83, and feeding the pigment and the ionic liquid into a pigment and ionic liquid tank.
And 6, a process: the material does not enter and exit the system, and the system performs internal circulation.
And (7) a process: and (4) eluting the solution on the Z4, discharging the pigment and the ionic liquid from the Z3, and feeding the pigment and the ionic liquid into a raffinate liquid tube 8, a raffinate liquid flow meter 81, a raffinate flow regulating valve 82 and a pigment ion branch 83 to a pigment and ionic liquid tank.
And (8) a process: the material does not enter and exit the system, and the system performs internal circulation.
And a process 9: and (3) feeding eluent on the Z1, discharging the pigment and the ionic liquid under the Z4, and feeding the pigment and the ionic liquid into a raffinate liquid pipe 8, a raffinate liquid flow meter 81, a raffinate liquid flow regulating valve 82 and a pigment ion branch 83 to a pigment and ionic liquid tank.
The process 10: the material does not enter and exit the system, and the system performs internal circulation.
In the process 1,2,3,5,7,9, the volume of the feed liquid entering the chromatographic system is equal to the volume of the feed liquid flowing out of the chromatographic system at the same time, and the volume is measured and accumulated through the raffinate flow meter 81 or the extract flow meter 91, and the accumulated volume is used for controlling the start and the end of feeding and discharging; in process 4,6,8, 10, the volumetric amount of material undergoing internal circulation is metered and accumulated by the circulation flow meter 10, and the accumulated amount is used to control the amount of internal circulation.
The concentrated solution obtained in example 1 is decolorized, deionized and separated by the device for decolorizing and deionizing and separating mixtures described in example 2, and the following components are obtained:
(1) Pigment and ionic liquid, wherein the pigment and the ionic liquid belong to waste liquid and are discharged to a sewage treatment system.
(2) The arabinose liquid A is rich, wherein the arabinose content is 90.0 to 95.0 percent.
(3) The galactose-rich liquid B contains 85.0 to 90.0 percent of galactose.
(4) The sugar is rich in a mixed sugar solution C, wherein the content of galactose is 50.0-55.0%, the content of rhamnose is 20.0-25.0%, and the content of other sugars is 20.0-30.0%.
(5) The glucuronic acid liquid D is rich in glucuronic acid, wherein the content of glucuronic acid is 70.0-80.0%.
Example 4, the glucuronic acid solution D rich in glucuronate obtained in example 3 mainly comprises a glucuronic acid solution and pigment ion mixed solution. The glucuronic acid solution D obtained in example 2 is deionized and depigmented by a conventional ion exchange or automatic ion exchange apparatus to obtain a glucuronic acid solution with the ions and pigments removed.
As a further improvement of the invention, the glucuronate-rich liquid D obtained in example 2 is deionized and depigmented by a second set of apparatus for simultaneous separation of the mixture and decolorization and deionization according to the invention, to obtain a deionized and depigmented glucuronate-rich liquid.
Example 5 the arabinose-rich liquid a and galactose-rich liquid B obtained in example 2 and the glucose-rich acid liquid obtained in example 4 after ion removal were concentrated, crystallized in an aqueous solution, and dried by a conventional method to obtain a crystalline arabinose product, a crystalline galactose product, and a crystalline glucuronic acid product.
The arabinose crystallization mother liquor and the glucuronic acid crystallization mother liquor are mixed with new materials and then crystallized before returning to respective concentration working procedures; or, after returning to and mixing with the concentrated acidolysis solution of example 1, the mixture was decolorized, deionized, and separated by an apparatus for simultaneously separating the mixture and decolorizing and deionizing the mixture.
Example 6, after extracting a galactose product from the galactose-rich liquid B crystal in example 5, the mother solution of the crystallization was mixed with the mixed sugar solution C in example 3 in a manner similar to the composition thereof, concentrated to a concentration of 50 to 60% by mass, and then separated by a chromatographic separation apparatus.
The chromatographic separation device is a program simulated moving bed chromatographic separation device, and has 6 chromatographic columns, wherein calcium type cation adsorption resin is filled in the chromatographic columns as an adsorption medium, the used eluent is pure water, and the separation temperature is 60 to 65 ℃.
After separation by a chromatographic separation device, two components are obtained: rich in rhamnose solution E and rich in galactose solution F. The rhamnose-rich component E has the rhamnose content of 70.0-75.0%; the galactose content in the galactose-rich liquid F component is 85.0 to 88.0 percent.
And concentrating the rhamnose-rich liquid E by a conventional method, crystallizing by an aqueous solution method, and drying to obtain a crystallized rhamnose finished product.
The galactose-rich liquid F was mixed with the galactose-rich liquid B obtained in example 3, and the mixture was subjected to concentration, crystallization, and drying of galactose.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. The method for preparing arabinose, galactose, rhamnose and glucuronic acid is characterized in that Arabic gum is hydrolyzed under an acidic condition to obtain a mixed solution of arabinose, galactose, rhamnose and glucuronic acid, the mixed solution is neutralized, filtered and concentrated to obtain a concentrated solution, and then a device for decoloring, deionizing and separating the mixture at the same time is used for decoloring, deionizing and separating to obtain:
(1) Concentrating and crystallizing the arabinose-rich solution to obtain crystalline L-arabinose;
(2) Concentrating and crystallizing the galactose-rich solution to obtain crystalline D-galactose;
(3) Mixing the mixed sugar solution rich in galactose and rhamnose with a crystallization mother solution of galactose, performing chromatographic separation to obtain a solution rich in L-rhamnose, and then concentrating and crystallizing to obtain crystallized L-rhamnose;
(4) Removing ions from the solution rich in glucuronic acid, concentrating, and crystallizing to obtain crystalline D-glucuronic acid.
2. The method according to claim 1, characterized by the following specific steps:
step 1: dissolving Arabic gum, blending into 10-35% mass percent concentration, adding dilute sulfuric acid or dilute hydrochloric acid to adjust the pH value of the solution to 0.1-3.0, and hydrolyzing at 90-138 ℃ for 4-15 hours to obtain hydrolysate; standing the hydrolysate for 1~2 hours, filtering to obtain supernatant, neutralizing with alkali until the pH value is 3.0-5.5, filtering, and concentrating to obtain a concentrated solution;
step 2: and (3) decoloring, deionizing and separating the concentrated solution obtained in the step (1) by using a device for decoloring, deionizing and separating a mixture at the same time to obtain: the arabinose liquid A is rich; rich in galactose liquid B; rich in mixed sugar liquid C; rich in glucuronic acid solution D; pigment and ionic liquid S;
and 3, step 3: concentrating, crystallizing and drying the arabinose-rich liquid A obtained in the step 2 to obtain crystallized L-arabinose;
and 4, step 4: concentrating, crystallizing and drying the galactose-rich liquid B obtained in the step 2 to obtain crystalline D-galactose;
and 5: mixing the mixed sugar solution C rich in galactose and rhamnose obtained in the step 2 with the crystallization mother solution G obtained in the step 4, and then separating by using a chromatographic separation device to obtain a rhamnose solution E rich in galactose and a galactose solution F rich in galactose;
step 6: concentrating, crystallizing and drying the rhamnose-rich liquid E obtained in the step 5 to obtain crystallized L-rhamnose; mixing the galactose-rich liquid F obtained in the step 5 with the galactose liquid B obtained in the step 2;
and 7: and (3) removing ions from the glucuronic acid solution D obtained in the step (2), and then concentrating, crystallizing and drying to obtain the crystalline D-glucuronic acid.
3. The method of claim 2, wherein: the chromatographic separation device in the step 5 is a program simulated moving bed chromatographic separation device, and the total number of chromatographic columns is 6; the chromatographic column is filled with an adsorption medium which is calcium type cation adsorption resin or a calcium type molecular sieve; the eluent used was pure water.
4. A device for processing decoloration deionization of acacia gum hydrolysis concentrate and separating mixture simultaneously, characterized by: the system comprises a chromatographic system consisting of 4 chromatographic columns which are connected in series, wherein the chromatographic system consists of a chromatographic column (1), a booster pump (2), a conductivity meter (3), a connecting pipe (4), an isolating valve (5), an eluent pipe (6), a material pipe (7), a circulating flow meter (10), a raffinate pipe (8), a raffinate flow meter (81), a raffinate flow regulating valve (82), a VE valve, a pigment and an ionic liquid branch (83); a VD valve and a glucuronic acid liquid branch (84); an extracting liquid pipe (9), an extracting liquid flow meter (91) and an extracting liquid flow regulating valve (92); a VA valve, an arabinose liquid branch (93), a VB valve and a galactose liquid branch (94); a VC valve and a mixed sugar liquid branch (95); an eluent valve VW 1-VW 4 is connected to an inlet of each chromatographic column; the eluent valves VW 1-VW 4 are connected with an eluent pipe (6); the inlet of the 1 st chromatographic column Z1 is connected with a material valve VF; the material valve VF is connected with a material pipe (7); the outlet of each chromatographic column is connected with raffinate liquid valves VS 1-VS 4; the raffinate valve VS 1-VS 4 is connected with a raffinate pipe (8); the raffinate pipe (8) is provided with a raffinate flow meter (81) and a raffinate flow regulating valve (82), and then is divided into two branches: the first branch is a pigment and ionic liquid branch (83) which enters a pigment and ionic liquid tank after passing through a VE valve; the second branch is a glucuronic acid liquid branch (84) which enters a glucuronic acid liquid tank after passing through a VD valve; the last chromatographic column is connected with an extraction liquid valve VX; the extraction liquid valve VX is connected with an extraction liquid pipe (9); extract flowmeter (91), extract flow control valve (92) are equipped with on extract pipe (9), then divide into three branch road: the first branch is an arabinose liquid branch (93) which enters an arabinose liquid groove after passing through a VA valve; the second branch is a galactose liquid branch (94) which enters a galactose liquid tank after passing through a VB valve; the third branch is a mixed sugar liquid branch (95) which enters a mixed sugar liquid tank after passing through a VC valve.
5. The apparatus of claim 4, wherein a distributor for uniform distribution of material is located above and below the column; the chromatographic column is filled with an adsorption medium; the adsorption medium is sodium type cation adsorption resin; the eluent used was pure water.
6. Method of operating a device according to claim 4 or 5, characterized in that:
(1) The device operation comprises at least three processes: feeding, eluting and internally circulating;
(2) The device runs periodically, each period is divided into 10 processes, starting from the process 1 to the process 10, and then returning to the process 1 for continuous circulation;
(3) In the feeding and elution steps, the volume amount of feed liquid or eluent entering the chromatographic system is equal to the volume amount of feed liquid flowing out of the chromatographic system at the same time, and the volume amount is metered and accumulated through a raffinate flow meter (81) or an extract flow meter (91), and the accumulated amount is used for controlling the amount of feeding, eluent entering or discharging; in the step of internal circulation, the volume of the material undergoing internal circulation is metered and accumulated by a circulation flow meter (10), and the accumulated amount is used for controlling the amount of internal circulation.
(4) The device can separate out pigment and ionic liquid, and extract arabinose liquid, galactose liquid, mixed sugar liquid and glucuronic acid liquid.
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| CN110150635A (en) * | 2019-05-09 | 2019-08-23 | 苏州禾研生物技术有限公司 | A kind of method that Arabic gum prepares composite syrup |
| CN110226694A (en) * | 2019-06-03 | 2019-09-13 | 苏州凯祥生物科技有限公司 | A kind of preparation method and applications of high-content sandlwood syrup |
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