CN109384820A - The method for preparing arabinose, galactolipin, rhamnose and glucuronic acid - Google Patents
The method for preparing arabinose, galactolipin, rhamnose and glucuronic acid Download PDFInfo
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Abstract
Arabic gum hydrolyzes in acid condition, obtain arabinose, galactolipin, rhamnose and glucuronic acid mixed liquor, it neutralizes, filtering, concentration, obtain concentrate, then decoloration, deionization, separation, it obtains: (1) being rich in the solution of arabinose, concentration, crystallization obtain crystallized arabinose；(2) it is rich in the solution of galactolipin, concentration, crystallization obtain crystallization galactolipin；(3) it is rich in the mixed sugar liquid of galactolipin and rhamnose, after mixing with the crystalline mother solution of galactolipin, then carries out chromatographic isolation, obtains the solution rich in rhamnose, is then concentrated, crystallizes, obtain crystallization rhamnose；(4) it is rich in the solution of glucuronic acid, ion is removed to it, is then concentrated, crystallizes, obtain crystal glucose aldehydic acid.
Description
Technical field
The present invention relates to the production technologies of a kind of L-arabinose, D- galactolipin, L- rhamnose and D-Glucose aldehydic acid.Tool
Body is related to one kind using Arabic gum as raw material, while preparing the production skill of arabinose, galactolipin, rhamnose and glucuronic acid
Art field.
Background technique
Arabic gum is thickener that is a kind of from a wealth of sources, safe and harmless and being degraded by human body parts.Arabic gum has
Two kinds of components, polysaccharide and small part and polysaccharide are with the protein of Covalent bonding together.Polysaccharide in Arabic gum is after acidolysis
Available L-arabinose, D- galactolipin, L- rhamnose, D-Glucose aldehydic acid, oligosaccharides and other miscellaneous sugars mixture.
L-arabinose (L-Arabinose) is also known as L- pectinose, is a kind of sweetener that heat is extremely low, can be effective
Inhibit and block human body to the metabolic conversion of sucrose, so as to inhibiting fat, preventing and treating disease relevant to hyperglycemia；
L-arabinose is also used as medicine intermediate, is used to prepare antiviral anticancer drug, while being also used in biochemistry thin
The preparation of bacterium culture medium and perfume synthesis etc..L-arabinose is seldom present in nature in the form of free state, usually
In conjunction with other monosaccharide, be present in the form of heteroglycan or L- araban or L- araban-D- galactolipin colloid,
In hemicellulose, bacterial polysaccharides and certain glucosides.Currently, L-arabinose majority is by from some natural or half-natural raw material
Middle extraction preparation, including some plant fibers or hemicellulose class (such as corn, bagasse, stalk), beet pulp and Arabic gum
Deng.
D- galactolipin is a kind of important pharmaceutical intermediate.In Arabic gum acid hydrolysis solution in addition to containing L-arabinose, D-
Galactose content is also higher, and to improve raw material availability and economic benefit, the L-arabinose and D- galactolipin in acid hydrolysis solution are equal
Separation and Extraction is needed to come out.Domestic existing patent is concentrated mainly on the separation and Extraction of L-arabinose, seldom mentions to D- galactolipin
And.
Rhamnose is distributed widely in plant as a kind of micro sugar, but content is not high.Rhamnose can be used to measure
The permeability of enteron aisle can be used as sweetener for producing flavors and fragrances, also act as pharmaceutical raw material etc..CN103755776B is disclosed
A kind of yellow ginger extracts turmeric saponin, the method that is then converted into rhamnose by turmeric saponin again；CN103937854A is disclosed
The method for preparing rhamnose using rutin.
Glucuronic acid (Glucuronic acid), abbreviation Artogicurol are that the primary hydroxyl group of glucose is oxidized to carboxyl
The compound of formation, is distributed widely in animals and plants.There are Arabic gum, bassora gums etc. in the form of a uronic acid in plant
It is the important component for constituting pectin, mucus and higher polysaccharides in natural gum.In animal body, glucuronic acid and glycoside acid
Form complex storage in the tissue.Glucuronic acid molecular formula is C6H10O7, relative molecular weight 194.14, powder or white
Acicular crystal.Glucuronic acid aqueous solution is unstable, easily forms 3,6- glucurone and is in tautomeric equilibrium state, D-
Glucuronic acid in the presence of heating and having strong acid is also easy to that decarboxylation occurs and generates CO2, furans and other cracking products.Portugal
Grape uronic acid can be combined into nontoxic glucuronide conjugate with internal poisonous substance and be discharged, and have liver detoxification effect, be used for liver
Inflammation, cirrhosis, food and drug poisoning.Glucuronic acid still constitutes the important component of connective tissue, can be used for treating joint
Scorching and collagenosis.
Current conventionally produced L-arabinose and D- galactolipin are mostly used using Arabic gum as raw material, pass through me
Primary glue hydrolyzes in acid condition, controls different hydrolysising conditions and obtains the mixed liquor of L-arabinose and D- galactolipin, will mix
After closing the decontaminations such as liquid decoloration, desalination, with organic solvent extraction and precipitation purification L-arabinose, then it is concentrated, and for the first time
Crystallization, centrifugal dehydration obtain corresponding L-arabinose and D- galactolipin crude product.Traditional processing technology long flow path, yield is not
Height, the consumption such as water, electricity, steam is high, high production cost.
The patent of invention of the Publication No. CN106589010A applied before applicant disclose it is a kind of and meanwhile produce L- Ah
The method for drawing uncle's sugar and D- galactolipin uses the mixed sugar liquid after Arabic gum hydrolysis, neutralization, decoloration, filtering, desalination, concentration
Moving bed imitation chromatogram separation facility separation, obtains solution, the solution rich in D- galactolipin rich in L-arabinose, then respectively
From concentration, crystallization, L-arabinose crystalline product and D- galactolipin crystalline product are obtained.There is no extract hydrolyzate in the invention
In rhamnose and glucuronic acid, and exhausted as impurity.And the purpose of the invention patent is to produce me simultaneously
Uncle sugar, four kinds of galactolipin, rhamnose and glucuronic acid products.
Summary of the invention
For the deficiency in existing Arabic gum extraction process, the present invention provides a kind of Arabic gum acidolysis, extract
New process.
The object of the present invention is to provide a kind of improved from Arabic gum extraction arabinose, galactolipin, rhamnose and Portugal
The method of grape uronic acid can simultaneously obtain four L-arabinose, D- galactolipin, L- rhamnose, D-Glucose aldehydic acid products.
Arabic gum hydrolyzes in acid condition, obtains arabinose, galactolipin, rhamnose, glucuronic acid and a small amount of miscellaneous
The mixed liquor of sugar, neutralized, filtering, concentration, obtains concentrate, is then carried out with the device of decoloration deionization while separating mixture
Decoloration, deionization, separation, obtain: (1) being rich in the solution of arabinose, concentration, crystallization obtain crystallized arabinose；
(2) it is rich in the solution of galactolipin, concentration, crystallization obtain crystallization galactolipin；
(3) it is rich in the mixed sugar liquid of galactolipin and rhamnose, after mixing with the crystalline mother solution of galactolipin, then carries out chromatography point
From obtaining the solution rich in rhamnose, be then concentrated, crystallize, obtain crystallization rhamnose；
(4) it is rich in the solution of glucuronic acid, deionization, concentration, crystallization are carried out to it, obtain crystal glucose aldehydic acid.
It is of the invention using Arabic gum as raw material, prepare the side of arabinose, galactolipin, rhamnose and glucuronic acid
Method, main technical schemes step are as follows:
Step 1: mass percent concentration 10 ~ 35% is deployed into after Arabic gum is dissolved, optimal is 20 ~ 25%；Dilute sulfuric acid is added
Or dilute hydrochloric acid is adjusted to solution pH value 0.1 ~ 3.0, optimal is 0.1 ~ 0.6；90 ~ 138 DEG C at a temperature of hydrolyze 4 ~ 15 hours, obtain water
Solve liquid；Hydrolyzate stands 1 ~ 2 hour, leaching supernatant liquor alkali neutralization to pH value 3.0 ~ 5.5, then filters, is concentrated, must be concentrated
Liquid.
Step 2: by step 1 gained concentrate with decoloration deionization simultaneously separating mixture device decolourized, go from
Son, separation, obtain: rich in Arabic liquid glucose A；Rich in gala liquid glucose B；Rich in mixed sugar liquid C；Rich in glucuronic acid liquid D；Color
Element and ionic liquid S.
Step 3: step 2 is resulting rich in Arab liquid glucose A concentration, crystallization, drying, obtain crystallization L-arabinose.
Step 4: gala liquid glucose B concentration, crystallization, drying will be rich in obtained by step 2, D- galactolipin must be crystallized.
Step 5: the mixed sugar liquid C of galactolipin and rhamnose will be rich in obtained by step 2, crystallize gained with step 4 galactolipin
Crystalline mother solution G mixing, then separated, obtained rich in sandlwood liquid glucose E and rich in gala liquid glucose F with chromatographic separation device.
Step 6: sandlwood liquid glucose E concentration, crystallization, drying will be rich in obtained by step 5, obtain crystallization rhamnose；By step (5) institute
It obtains and is mixed rich in gala liquid glucose F with the resulting gala liquid glucose B of step 2.
Step 7: the resulting glucuronic acid liquid D that is rich in of step 2 being removed into deionization, is then concentrated, crystallizes, is dry, must tie
Brilliant glucuronic acid.
Further, chromatographic separation device described in step 5 is program mode moving bed imitation chromatogram separation facility, is shared
6 chromatographic columns, adsorbing medium is filled in chromatographic column, and adsorbing medium is that calcium cation adsorbs resin or calcium type molecular sieve；It is used
Eluant, eluent is pure water.After chromatogram arrangement separates, obtain rich in sandlwood liquid glucose E and rich in gala liquid glucose F；Rich in sandlwood liquid glucose E
Concentration, crystallization, drying, obtain crystallization rhamnose；After being mixed rich in gala liquid glucose F with the resulting gala liquid glucose B of step 2, concentration, knot
It is brilliant, dry, D- galactolipin must be crystallized.
In order to achieve the object of the present invention, the present invention provides a kind of for handling the concentrate after Arabic gum hydrolyzes
The device of decoloration deionization while separating mixture.
Device has 4 mutual concatenated chromatographic columns, by chromatographic column, boost pump, conductivity meter, connecting tube, isolating valve,
Eluant, eluent pipe, expects pipe, recycle stream meter, raffinate liquid pipe, raffinate stream meter, raffinate stream adjustable valve, pigment and ionic liquid
Branch, glucuronic acid liquid branch, extract liquid pipe, extract flow meters, extracting solution flow control valve, Arabic liquid glucose branch,
Gala liquid glucose branch, mixed sugar liquid branch composition；There are also arabinose liquid bath, galactolipin liquid bath, mixed sugar liquid bath, grape alditols
Acid storage and pigment and ion liquid bath；Each chromatographic column import is connected with eluant, eluent valve；1st chromatographic column import is connected with material
Valve；The eluant, eluent valve and material valve are connect with eluant, eluent pipe and expects pipe respectively；Each column outlet is connected with raffinate valve；It mentions
Extraction raffinate valve is connect with raffinate liquid pipe；Raffinate stream meter, raffinate stream adjustable valve are installed in raffinate liquid pipe, for detecting,
Adjust flow；Raffinate liquid pipe is after raffinate stream adjustable valve, and be divided into two branches: first branch is pigment and ionic liquid
Branch is connected to pigment and ion liquid bath；Second branch is glucuronic acid liquid branch, is connected to glucuronic acid liquid bath；
The last one chromatographic column is connected with extracting solution valve；The extracting solution valve is connect with liquid pipe is extracted；It extracts and extracting solution is housed in liquid pipe
Flowmeter, extracting solution flow control valve, for detecting, adjusting flow；It is divided into three after extracting the extracted liquid stream adjustable valve of liquid pipe
A branch: first branch is Arabic liquid glucose branch, is connected to arabinose liquid bath；Second branch is gala liquid glucose branch
Road is connected to galactolipin liquid bath；Third branch is mixed sugar liquid branch, is connected to mixed sugar liquid bath.
Further, the device of decoloration deionization while separating mixture has 4 mutual concatenated chromatographic columns；Each chromatography
Column has the distributing device for evenly distributing material up and down；Adsorbing medium is filled in chromatographic column；Adsorbing medium is sodium form Cation adsorption
Resin；Eluant, eluent used is pure water.
In order to achieve the object of the present invention, the present invention also provides above-mentioned decoloration deionization while the devices of separating mixture
Operation method.
Device operation includes three processes: charging, elution, interior circulation.
The device of decoloration deionization and separating mixture, has 4 chromatographic columns to be mutually connected in series, column number is used in the present invention
Z1,Z2,Z3,Z4.Device cycling service, each period is divided into 10 processes, since process 1, until process 10, then returns
Process 1, continuous circulation carry out；10 processes are as follows:
Process 1:Z1 upper feeding；Go out under Z4 and be rich in mixed sugar liquid, and enter extracting solution pipe, extracted flow meters extract liquid stream
After adjustable valve, into mixed sugar liquid branch, mixed sugar liquid slot is entered after VC valve.
Process 2:Z1 upper feeding；Under Z1 go out be rich in glucuronic acid liquid, and enter raffinate pipe, through raffinate stream meter,
Raffinate stream adjustable valve, into glucuronic acid liquid branch, into glucuronic acid liquid bath；The enterprising eluant, eluent of Z2；Go out under Z4
Rich in gala liquid glucose, and enter extracting solution pipe, through flowmeter, flow control valve, into gala liquid glucose branch, into gala liquid glucose
Slot.
The enterprising eluant, eluent of process 3:Z4；Go out under Z4 rich in Arabic liquid glucose, and enters extracting solution pipe, extracted flow quantity
After meter, extracting solution flow control valve, into Arabic liquid glucose branch, into arabinose liquid bath.
Process 4: material does not pass in and out system, and system carries out interior circulation.
The enterprising eluant, eluent of process 5:Z3；Go out pigment and ionic liquid under Z2, and enters raffinate pipe, through flowmeter, flow tune
After saving valve, pigment ion branch, into pigment and ion liquid bath.
Process 6: material does not pass in and out system, and system carries out interior circulation.
The enterprising eluant, eluent of process 7:Z4；Go out pigment and ionic liquid under Z3, and enters raffinate pipe, through flowmeter, flow tune
Valve, pigment ion branch are saved, into pigment and ion liquid bath.
Process 8: material does not pass in and out system, and system carries out interior circulation.
The enterprising eluant, eluent of process 9:Z1；Go out pigment and ionic liquid under Z4, and enters raffinate pipe, through flowmeter, flow tune
Valve, pigment ion branch are saved, into pigment and ion liquid bath.
Process 10: material does not pass in and out system, and system carries out interior circulation.
In process 1,2,3,5,7,9, flowed out into the material liquid volume amount of chromatographic system and same time from chromatographic system
Feed liquid volume be it is equal, measured and accumulated by flowmeter, cumulant is used to control the beginning and end of input and output material；
In process 4,6,8,10, material carries out the interior volume recycled and measures accumulation, cumulant by the recycle stream meter in connecting tube
For controlling the amount of interior circulation.
Obtain after above-mentioned apparatus is handled: rich in pigment and ionic liquid S, this part is exhausted as waste liquid；Rich in Arab
Liquid glucose A；Rich in gala liquid glucose B；Rich in mixed sugar liquid C；Rich in glucuronic acid liquid D.
Further, in the step 7 of technical solution, when to removing deionization rich in glucuronic acid liquid D, can be used it is conventional from
The method that son exchange or automatic ion exchange remove deionization.
As a further improvement of the present invention, in the step 7 of technical solution, deionization is removed to rich in glucuronic acid liquid D
When, the device of second set of decoloration deionization of the invention separating mixture simultaneously can also be used, to rich in glucuronic acid liquid D into
Row removes deionization.
As a further improvement of the present invention, the chromatography in series column number for forming chromatographic system can be n, n=3 ~ 12, operation
When each period be divided into 2n+2 process.
Method of the invention, Arabic gum once hydrolyze, through conventional process such as decoloration, filtering, concentrations, then through deionization,
The refinement treatments processes such as separation, concentration, crystallization, can produce L-arabinose, D- galactolipin, L- rhamnose and D-Glucose simultaneously
Four products of aldehydic acid.Method of the invention is utilized the device of decoloration deionization while separating mixture, not only removes deionization
It is high-efficient, moreover it is possible to while separating the carbohydrate in mixed sugar liquid.Method of the invention, raw material availability is high, and production procedure is brief, respectively
The crystalline mother solution of product is repeatable to return to separation and Extraction.
Detailed description of the invention
Fig. 1 is the technical process schematic diagram of the method for the present invention.
Fig. 2 is the mixed liquor HPLC spectrogram after Arabic gum hydrolysis.
Fig. 3 is the apparatus structure schematic diagram of decoloration deionization and separating mixture used in the present invention.
Each component is as follows in attached drawing: chromatographic column 1, boost pump 2, conductivity meter 3, connecting tube 4, isolating valve, 5, eluant, eluent pipe 6,
Expects pipe 7, recycle stream meter 10 expect valve VF, eluant, eluent valve VW1 ~ VW4；Raffinate valve VS1 ~ VS4, raffinate liquid pipe 8, raffinate stream
Meter 81, raffinate stream adjustable valve 82, VE valve, impurity branch 83, pigment ion liquid bath；VD valve, glucuronic acid liquid branch
84, glucuronic acid liquid bath；Extracting solution valve VX extracts liquid pipe 9, extracts flow meters 91, extracting solution flow control valve 92, VA
Valve, Arabic liquid glucose branch 93, arabinose liquid bath；VB valve, gala liquid glucose branch 94, galactolipin liquid bath；VC valve, mixed sugar liquid
Branch 95, mixed sugar liquid bath.
Fig. 4 is 10 process letters of the device operation a cycle of decoloration deionization used in the present invention and separating mixture
Figure.
Show there is material to flow through when chromatographic column is black matrix in attached drawing.
Example is embodied
Technical process and effect of the invention are illustrated below in conjunction with attached drawing and specific implementation example, but the present invention is not by following reality
Apply the limitation of example.
Embodiment 1, Arabic gum is crushed, and is dissolved at 30 ~ 40 DEG C, and mass percent concentration 25% is deployed into, and is added dilute
Sulfuric acid is adjusted to solution pH value 0.3,105 DEG C at a temperature of hydrolyze 12 hours, obtain hydrolyzate；Hydrolyzate stands 1 ~ 2 hour, leaching
Then supernatant liquor alkali neutralization filters, is concentrated, obtain concentrate to pH value 4.0 ~ 5.0.
Embodiment 2, the present invention used in decoloration deionization simultaneously separating mixture device, as shown in Fig. 3, by chromatography
Column 1, boost pump 2, conductivity meter 3, connecting tube 4, isolating valve, 5, eluant, eluent pipe 6, expects pipe 7, recycle stream meter 10；Raffinate liquid pipe
8, raffinate stream meter 81, raffinate stream adjustable valve 82, pigment and ionic liquid branch 83, glucuronic acid liquid branch 84；It mentions
Liquid flowing tube 9 extracts flow meters 91, extracting solution flow control valve 92, Arabic liquid glucose branch 93, gala liquid glucose branch 94, mixes
Liquid glucose branch 95 is closed to form；There are also arabinose liquid bath, galactolipin liquid bath, mixed sugar liquid bath, glucuronic acid liquid bath and pigments
With ion liquid bath；Each chromatographic column import is connected with eluant, eluent valve VW1 ~ VW4；1st chromatographic column import is connected with material valve VF；Institute
It states eluant, eluent valve VW1 ~ VW4 and material valve VF is connect with the eluant, eluent pipe 6 and the expects pipe 7 respectively；Each column outlet connects
It is connected to raffinate valve VS1 ~ VS4；The raffinate valve VS1 ~ VS4 is connect with raffinate liquid pipe 8；It is equipped in the raffinate liquid pipe 8
Raffinate stream meter 81, raffinate stream adjustable valve 82, for detecting, adjusting flow；The raffinate liquid pipe 8 passes through raffinate
After flow control valve 82, be divided into two branches: first branch is pigment and ionic liquid branch 83, enter after VE valve pigment and
Ion liquid bath；Second branch is glucuronic acid liquid branch 84, and glucuronic acid liquid bath is entered after VD valve；The last one color
Spectrum column is connected with extracting solution valve VX；The extracting solution valve VX is connect with liquid pipe 9 is extracted；Extracting solution is housed in the extraction liquid pipe 9
Flowmeter 91, extracting solution flow control valve 92, for detecting, adjusting flow；The extracted liquid stream adjustable valve of extraction liquid pipe
Be divided into three branches after 92: first branch is Arabic liquid glucose branch 93, and arabinose liquid bath is entered after VA valve；Second
Branch is gala liquid glucose branch 94, and galactolipin liquid bath is entered after VB valve；Third branch is mixed sugar liquid branch 95, through VC valve
Enter mixed sugar liquid slot afterwards.
In the present embodiment, the device of decoloration deionization while separating mixture has 4 mutual concatenated chromatographic columns, and column number is
Z1,Z2,Z3,Z4；The chromatographic column has the distributing device for evenly distributing material up and down；Adsorbing medium is filled in the chromatographic column,
The adsorbing medium is sodium form Cation adsorption resin；Eluant, eluent used is pure water.
As a further improvement of the present invention, the chromatography in series column number for forming chromatographic system can be n, n=3 ~ 12.
The device operational process of embodiment 3, the separating mixture simultaneously of decoloration deionization described in embodiment 2 includes three mistakes
Journey: charging, elution, interior circulation.
Device cycling service, for 4 Coupled columns composition chromatographic system, column number be Z1, Z2, Z3, Z4, each
Period is divided into 10 processes, and since process 1, until process 10, then return course 1, continuous circulation are carried out；10 processes are such as
Under:
Process 1:Z1 upper feeding goes out under Z4 and is rich in mixed sugar liquid C, and enters extracting solution pipe 9, and extracted flow meters 91 extract
After liquid stream adjustable valve 92, into mixed sugar liquid branch 95, mixed sugar liquid slot is entered after VC valve.
Process 2:Z1 upper feeding goes out under Z1 and is rich in glucuronic acid liquid D, and enters raffinate pipe 8, through raffinate stream meter
81, raffinate stream adjustable valve 82, glucuronic acid liquid branch 84 enter glucuronic acid liquid bath after VD valve.Z2 is enterprising to be washed
Agent is taken off, goes out under Z4 and is rich in gala liquid glucose B, and enter extracting solution pipe 9, extracted flow meters 91, extracting solution flow control valve 92
Afterwards, into gala liquid glucose branch 94, galactolipin liquid bath is entered after VB valve.
Process 3:Z4 enterprising eluant, eluent goes out under Z4 rich in Arabic liquid glucose A, and enters extracting solution pipe 9, extracted flow quantity
After meter 91, extracting solution flow control valve 92, into Arabic liquid glucose branch 93, arabinose liquid bath is entered after VA valve.
Process 4: material does not pass in and out system, and system carries out interior circulation.
Process 5:Z3 enterprising eluant, eluent goes out pigment and ionic liquid under Z2, and enters raffinate pipe 8, through raffinate stream meter
81, after raffinate stream adjustable valve 82, pigment ion branch 83, into pigment and ion liquid bath.
Process 6: material does not pass in and out system, and system carries out interior circulation.
Process 7:Z4 enterprising eluant, eluent goes out pigment and ionic liquid under Z3, and enters raffinate pipe 8, through raffinate stream meter
81, raffinate stream adjustable valve 82, pigment ion branch 83, into pigment and ion liquid bath.
Process 8: material does not pass in and out system, and system carries out interior circulation.
Process 9:Z1 enterprising eluant, eluent goes out pigment and ionic liquid under Z4, and enters raffinate pipe 8, through raffinate stream meter
81, raffinate stream adjustable valve 82, pigment ion branch 83, into pigment and ion liquid bath.
Process 10: material does not pass in and out system, and system carries out interior circulation.
In process 1,2,3,5,7,9, flowed out into the material liquid volume amount of chromatographic system and same time from chromatographic system
Feed liquid volume be it is equal, by raffinate stream meter 81 or extract flow meters 91 metering accumulation, cumulant use
In the beginning and end of control input and output material；In process 4,6,8,10, material carries out the interior volume recycled by recycle stream meter
10 metering accumulations, cumulant are used to control the amount of interior circulation.
1 gained concentrate of embodiment is carried out with the device of decoloration deionization as described in example 2 while separating mixture
Decoloration, deionization, separation obtain following component:
(1) pigment and ionic liquid, the pigment and ionic liquid of this part belong to waste liquid, drain into sewage disposal system.
(2) it is rich in Arabic liquid glucose A, wherein arabinose content 90.0 ~ 95.0%.
(3) it is rich in gala liquid glucose B, wherein galactose content 85.0 ~ 90.0%.
(4) it is rich in mixed sugar liquid C, wherein galactose content 50.0 ~ 55.0%, sandlwood sugared content 20.0 ~ 25.0%, other sugar
Content 20.0 ~ 30.0%.
(5) it is rich in glucuronic acid liquid D, wherein glucuronic acid content 70.0 ~ 80.0%.
Embodiment 4 is rich in glucuronic acid liquid D obtained in embodiment 3, and component is mainly glucuronic acid liquid and color
Plain Ar ion mixing liquid.With conventional ion exchange or automatic ion exchanging device, to obtained in embodiment 2 be rich in glucuronic acid
Liquid D carries out deionization, depigmentaton, after obtaining deionization and pigment rich in glucuronic acid liquid.
As a further improvement of the present invention, with the dress of second set of decoloration deionization while separating mixture of the invention
It sets, deionization, depigmentaton is carried out to glucuronic acid liquid D is rich in obtained in embodiment 2, after obtaining deionization and pigment
Rich in glucuronic acid liquid.
Embodiment 5, by embodiment 2 it is resulting rich in Arabic liquid glucose A, it is resulting rich in gala liquid glucose B and embodiment 4
It is rich in glucuronic acid liquid after removing deionization, is concentrated according to a conventional method, aqua-solution method crystallization, drying, obtains crystallization Ah
Draw the sugared finished product of uncle, crystallization galactolipin finished product and crystal glucose aldehydic acid finished product.
Before arabinose crystalline mother solution, glucuronic acid crystalline mother solution return to respective enrichment process, with new material one
It is crystallized after playing mixing；Or after return is mixed with the acidolysis concentrate of embodiment 1, mixing is separated simultaneously with decoloration deionization together
The device of object decolourized, deionization, separation.
Embodiment 6, after extracting gala sugar product rich in gala liquid glucose B crystallization in embodiment 5, the composition and reality of crystalline mother solution
The composition rich in mixed sugar liquid C applied in example 3 is similar, and the two is mixed, mass percent concentration 50 ~ 60% is concentrated into, then uses
Chromatographic separation device is separated.
The chromatographic separation device is program mode moving bed imitation chromatogram separation facility, shares 6 chromatographic columns, chromatographic column
Calcium cation absorption resin is inside filled as adsorbing medium, eluant, eluent used is pure water, and separation temperature is 60 ~ 65 DEG C.
After chromatographic separation device separates, two components are obtained: rich in sandlwood liquid glucose E and rich in gala liquid glucose F.Rich in mouse
In Lee's liquid glucose component E, sandlwood sugared content 70.0 ~ 75.0%；Rich in gala liquid glucose F component, galactose content 85.0 ~ 88.0%.
It is concentrated according to a conventional method rich in sandlwood liquid glucose E, aqua-solution method crystallization, drying, obtains crystallization rhamnose finished product.
Composition rich in gala liquid glucose F is resulting similar rich in gala liquid glucose B composition to embodiment 3, after the two is mixed
Into the concentration, crystallization, drying process of galactolipin.
Although the present invention is disclosed as above with preferred embodiments, they be not for limiting the present invention, it is any to be familiar with this
Those skilled in the art can make various changes or retouch from working as, therefore protection model of the invention without departing from the spirit and scope of the invention
Enclosing should be subject to what claims hereof protection scope was defined.
Claims (6)
1. the method for preparing arabinose, galactolipin, rhamnose and glucuronic acid, which is characterized in that Arabic gum is in acidity
Under the conditions of hydrolyze, obtain arabinose, galactolipin, rhamnose and glucuronic acid mixed liquor, neutralize, filtering, concentration, must be concentrated
Then liquid is decolourized, deionization, separation with the device of decoloration deionization while separating mixture, is obtained:
(1) it is rich in the solution of arabinose, concentration, crystallization obtain crystallization L-arabinose；
(2) it is rich in the solution of galactolipin, concentration, crystallization must crystallize D- galactolipin；
(3) it is rich in the mixed sugar liquid of galactolipin and rhamnose, after mixing with the crystalline mother solution of galactolipin, then carries out chromatography point
From obtaining the solution rich in L- rhamnose, be then concentrated, crystallize, L- rhamnose must be crystallized；
(4) it is rich in the solution of glucuronic acid, ion is removed to it, is then concentrated, crystallizes, D-Glucose aldehyde must be crystallized
Acid.
2. method according to claim 1, which is characterized in that specific step is as follows:
Step 1: mass percent concentration 10 ~ 35% is deployed into after Arabic gum is dissolved, addition dilute sulfuric acid or dilute hydrochloric acid are adjusted to molten
Liquid pH value 0.1 ~ 3.0,90 ~ 138 DEG C at a temperature of hydrolyze 4 ~ 15 hours, obtain hydrolyzate；Hydrolyzate stands 1 ~ 2 hour, leaching
Then supernatant liquor alkali neutralization filters, is concentrated, obtain concentrate to pH value 3.0 ~ 5.5；
Step 2: step 1 gained concentrate being decolourized with the device of decoloration deionization while separating mixture, deionization, is divided
From obtaining: rich in Arabic liquid glucose A；Rich in gala liquid glucose B；Rich in mixed sugar liquid C；Rich in glucuronic acid liquid D；Pigment and
Ionic liquid S；
Step 3: step 2 is resulting rich in Arab liquid glucose A concentration, crystallization, drying, obtain crystallization L-arabinose；
Step 4: gala liquid glucose B concentration, crystallization, drying will be rich in obtained by step 2, D- galactolipin must be crystallized；
Step 5: the mixed sugar liquid C of galactolipin and rhamnose will be rich in obtained by step 2, crystallized with step (4) galactolipin resulting
Crystalline mother solution G mixing, is then separated with chromatographic separation device, is obtained rich in sandlwood liquid glucose E and rich in gala liquid glucose F；
Step 6: sandlwood liquid glucose E concentration, crystallization, drying will be rich in obtained by step 5, L- rhamnose must be crystallized；It will be obtained by step (5)
It is mixed rich in gala liquid glucose F with the resulting gala liquid glucose B of step 2；
Step 7: the resulting glucuronic acid liquid D that is rich in of step 2 being removed into deionization, is then concentrated, crystallizes, is dry, D- must be crystallized
Glucuronic acid.
3. method according to claim 2, it is characterised in that: chromatographic separation device described in step 5 is program mode mould
Quasi- mobile bed chromatic separator, shares 6 chromatographic columns；Adsorbing medium is filled in the chromatographic column, the adsorbing medium is calcium
Type Cation adsorption resin or calcium type molecular sieve；Eluant, eluent used is pure water.
4. the device of decoloration deionization while separating mixture for handling Arabic gum hydrolysis concentrate, it is characterised in that: 4
A concatenated chromatographic column mutually forms chromatographic system, by chromatographic column (1), boost pump (2), conductivity meter (3), connecting tube (4),
Isolating valve, (5), expects pipe (7), recycle stream meter (10), raffinate liquid pipe (8), raffinate stream meter (81), mentions eluant, eluent pipe (6)
Extraction raffinate flow control valve (82), VE valve, pigment and ionic liquid branch (83)；VD valve, glucuronic acid liquid branch (84)；Extracting solution
It manages (9), extract flow meters (91), extracting solution flow control valve (92)；VA valve, Arabic liquid glucose branch (93), VB valve, gala
Liquid glucose branch (94)；VC valve, mixed sugar liquid branch (95) composition；Each chromatographic column import is connected with eluant, eluent valve VW1 ~ VW4；Institute
Eluant, eluent valve VW1 ~ VW4 is stated to connect with eluant, eluent pipe (6)；1st chromatographic column Z1 import is connected with material valve VF；The material valve VF
It is connect with expects pipe (7)；Each column outlet is connected with raffinate valve VS1 ~ VS4；The raffinate valve VS1 ~ VS4 and raffinate
Manage (8) connection；Raffinate stream meter (81), raffinate stream adjustable valve (82) are installed on the raffinate liquid pipe (8), then divided
At two branches: first branch is pigment and ionic liquid branch (83), and pigment and ion liquid bath are entered after VE valve；Second
Branch is glucuronic acid liquid branch (84), and glucuronic acid liquid bath is entered after VD valve；The last one chromatographic column, which is connected with, to be mentioned
Liquid taking valve VX；The extracting solution valve VX is connect with liquid pipe (9) are extracted；Equipped with extraction flow meters on the extraction liquid pipe (9)
(91), extracting solution flow control valve (92), be then divided into three branches: first branch is Arabic liquid glucose branch (93), warp
Enter arabinose liquid bath after VA valve；Second branch is gala liquid glucose branch (94), and galactolipin liquid bath is entered after VB valve；The
Three branches are mixed sugar liquid branch (95), and mixed sugar liquid slot is entered after VC valve.
5. device according to claim 4, which is characterized in that the chromatographic column has the cloth for evenly distributing material up and down
Device；Adsorbing medium is filled in the chromatographic column；The adsorbing medium is sodium form Cation adsorption resin；Eluant, eluent used is pure
Water.
6. the operation method of device described in claim 4 or 5, it is characterised in that:
(1) device operation includes at least three processes: charging, elution, interior circulation；
(2) device cycling service, each period is divided into 10 processes, since process 1, until process 10, and then return course
1, it is continuous to recycle；
(3) in charging, charging and the elution, elution the step of, into the feed liquid or the volume of eluant, eluent of chromatographic system and same
The volume for the feed liquid that one time flowed out from chromatographic system be it is equal, by impurity flowmeter (81) or extract flow meters
(91) metering accumulation, cumulant for controlling charging, into the amount of eluant, eluent or discharging；In the step of recycling inside, material is carried out
The volume of interior circulation is measured by recycle stream meter (10) to be accumulated, and cumulant is used to control the amount of interior circulation；
(4) device isolates pigment and ionic liquid, while isolating extract Arab liquid glucose, gala liquid glucose, mixed sugar liquid, Portugal
Grape alditol acid solution.
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Cited By (7)
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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 |
| CN110229195A (en) * | 2019-06-14 | 2019-09-13 | 广西福仪生物技术有限公司 | A method of extracting rhamnose from bagasse |
| 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 |
| 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 |
| CN114349802A (en) * | 2021-12-08 | 2022-04-15 | 安徽禾庚生物技术有限公司 | Production method of plant source D-tagatose |
| CN116199725A (en) * | 2023-03-15 | 2023-06-02 | 深通工程技术(深圳)有限公司 | Separation and purification method of glucuronic acid |
| CN116333012A (en) * | 2023-03-15 | 2023-06-27 | 深通工程技术(深圳)有限公司 | Preparation method of crystalline glucuronic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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| 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 |
| CN114349802A (en) * | 2021-12-08 | 2022-04-15 | 安徽禾庚生物技术有限公司 | Production method of plant source D-tagatose |
| CN116199725A (en) * | 2023-03-15 | 2023-06-02 | 深通工程技术(深圳)有限公司 | Separation and purification method of glucuronic acid |
| CN116333012A (en) * | 2023-03-15 | 2023-06-27 | 深通工程技术(深圳)有限公司 | Preparation method of crystalline glucuronic acid |
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