CN108752400A - The preparation method of aurantiin dihydrochalcone - Google Patents
The preparation method of aurantiin dihydrochalcone Download PDFInfo
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- CN108752400A CN108752400A CN201810706176.7A CN201810706176A CN108752400A CN 108752400 A CN108752400 A CN 108752400A CN 201810706176 A CN201810706176 A CN 201810706176A CN 108752400 A CN108752400 A CN 108752400A
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
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- C—CHEMISTRY; METALLURGY
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C07H1/08—Separation; Purification from natural products
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Abstract
The invention discloses a kind of preparation methods of aurantiin dihydrochalcone, include the following steps：Orange peel and/or the dried immature fruit of citron orange are dried and ultramicro grinding；Subcritical Water Extraction is carried out to citrus peel meal；Aurantiin extracting solution is purified, is eluted；Aurantiin eluent is concentrated under reduced pressure, is freeze-dried；Hydrogenation is carried out to aurantiin；The pH value of hydrogenation solution is adjusted, is stood, is filtered, freeze-drying obtains aurantiin dihydrochalcone.Preparation method of the present invention has many advantages, such as that simple for process, easy to operate, of low cost, environmentally protective, high income, purity are high, the comprehensive utilization value of citrus and the dried immature fruit of citron orange can be improved, there are good application prospect and economic benefit, simultaneously organic solvent need not be used in preparation process, secondary pollution will not be brought to environment, it is a kind of environmentally friendly preparation method of great future, is suitable for preparing on a large scale, is convenient for industrialized utilization.
Description
Technical field
The invention belongs to bio-separation and chemosynthesis technical field, it is related to a kind of citrus active ingredient extraction and synthesis work
A kind of skill, and in particular to preparation method of aurantiin dihydrochalcone.
Background technology
Aurantiin dihydrochalcone (Naringin Dihydrochalcone) is a kind of sugariness agent by extensive concern,
Sugariness is 1000 times or so of sweetness of cane sugar, and clean taste, pleasant impression is lasting, and has effects that splendid shielding bitter taste.Aurantiin
Dihydrochalcone be particularly suitable for application as additive be added to dairy produce, fat and grease, frozen food, vegetable for processing, jelly,
In jam, soft drink, chewing gum, toothpaste and mouth containing tablet.Substitute of the aurantiin dihydrochalcone as sugar, can also subtract
Few human body to the intake of sugar, this to prevent it is fat and should not the patient of sugar be undoubtedly a Gospel.However, aurantiin dihydro is looked into
You can not directly obtain ketone from nature, need to be made using aurantiin of raw material.
Aurantiin is naturally occurring in orange peel (such as mandarin orange, tangerine, orange, shaddock pericarp), is a kind of containing neohesperidose base
Important citrus flavanones.However, aurantiin content in orange peel is relatively low.Therefore, how effectively from citrus peel
It is highly important for preparation of industrialization aurantiin dihydrochalcone that middle extraction, which obtains aurantiin,.
In the prior art, there are some reports to the extraction of the aurantiin in orange peel preparation, such as：Publication No. CN
A kind of patent document " extraction and separation process of aurantiin " of 107955051 A, the patent of 104817602 A of Publication No. CN
The patent document of document " a kind of extracting method and its application process of aurantiin ", 102617673 B of Publication No. CN is " a kind of
The method for isolating and purifying aurantiin and neohesperidin from the white cortex of Hu shaddock ".But a large amount of first is used in the above extraction process
The organic solvents such as alcohol, chloroform, petroleum ether, n-butanol, n-hexane and strong acid, strong base reagent, extraction cost is high, and is had using these
Solvent will produce a large amount of waste water, increases intractability and processing cost, causes serious pollution to the environment, and technological process is long, behaviour
Make the shortcomings of complicated, time-consuming, extraction cost is high, solvent residual amount is high, the presence of these problems so that these techniques cannot expire
Foot prepares the actual demand of aurantiin dihydrochalcone using aurantiin, limits the industrial metaplasia of aurantiin dihydrochalcone
Production.In addition, since orange peel and the dried immature fruit of citron orange contain pigment and lipoid substance, and existing extracting method can make these impurity components
It is dissolved with together with aurantiin, has prodigious influence to purifying aurantiin, be unfavorable for obtaining the aurantiin two with purity in high yield
Hydrogen chalcone.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide it is a kind of it is simple for process, easy to operate,
The preparation method of the high aurantiin dihydrochalcone of of low cost, environmentally protective, high income, purity.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of aurantiin dihydrochalcone, includes the following steps：
S1, orange peel and/or the dried immature fruit of citron orange are dried and ultramicro grinding, obtain citrus peel meal；
S2, using deoxidation distilled water as extractant, first time subcritical water is carried out to the citrus peel meal that is obtained in step S1
Extraction, press filtration discard filtrate, obtain filter residue；
S3, the filter residue obtained in step S2 is mixed with activated carbon, is carried out second by extractant of deoxidation distilled water
Subcritical Water Extraction, centrifugation, discards filter residue, obtains aurantiin extracting solution；
S4, the aurantiin extracting solution obtained in step S3 is purified using resin, to the shaddock ped being adsorbed on resin
Glycosides is eluted, and aurantiin eluent is obtained；
S5, the aurantiin eluent obtained in step S4 is concentrated under reduced pressure and is freeze-dried, obtain aurantiin；
S6, the aurantiin obtained in step S5 is dissolved in lye, catalyst is added, be passed through hydrogen and carry out hydrogenation,
Filtering, obtains hydrogenation solution；
The pH value of the hydrogenation solution obtained in S7, regulating step S6 is stood, and is filtered, and freeze-drying obtains aurantiin dihydro
Chalcone.
Above-mentioned preparation method, it is further improved, in the step S2, the weight of the deoxidation distilled water and citrus peel meal
Amount is than being 1: 4~1: 12.
Above-mentioned preparation method, further improved, in the step S2, the first time Subcritical Water Extraction is in nitrogen
It is carried out under atmosphere；The pressure of the first time Subcritical Water Extraction is 3MPa~12MPa；The first time Subcritical Water Extraction
Temperature is 80 DEG C~250 DEG C；The time of the first time Subcritical Water Extraction is 15min~70min.
Above-mentioned preparation method, further improved, in the step S3, the mass ratio of the activated carbon and filter residue is
0.5%~8%；The weight ratio of the deoxidation distilled water and filter residue is 1: 4~1: 12.
Above-mentioned preparation method, further improved, in the step S3, second of Subcritical Water Extraction is in nitrogen
It is carried out under atmosphere；The pressure of second of Subcritical Water Extraction is 2MPa~12MPa；Second of Subcritical Water Extraction
Temperature is 80 DEG C~225 DEG C；The time of second of Subcritical Water Extraction is 15min~70min；The centrifugation in rotating speed is
It is carried out under the conditions of 5000rpm~10000rpm；The time of the centrifugation is 10min~20min.
Above-mentioned preparation method, further improved, in the step S1, the orange peel is orange peel, orange peel, shaddock
At least one of skin, orange peel；The grain size of the citrus peel meal is 10 μm~50 μm.
Above-mentioned preparation method, it is further improved, in the step S4, the resin be D101 macroporous absorbent resins,
D4020 macroporous absorbent resins, AB-8 macroporous absorbent resins, D130 macroporous absorbent resins, HPD450 macroporous absorbent resins and D140
At least one of macroporous absorbent resin；The eluant, eluent used in the elution process is ethanol solution；The ethanol solution
Volumetric concentration is 65%~95%；The volume of the eluant, eluent is 5 times~15 times of resin volume.
Above-mentioned preparation method, further improved, in the step S5, described be concentrated under reduced pressure in temperature is 40 DEG C~80
It is carried out at DEG C.
Above-mentioned preparation method, it is further improved, in the step S6, the lye be sodium hydroxide solution and/or
Potassium hydroxide solution；The pH value of the lye is 9~14；The catalyst is palladium charcoal；By logical in the hydriding process
It is 0.5MPa~5MPa to enter hydrogen to maintain the pressure of reaction system；The time of the hydrogenation is 30min~240min.
Above-mentioned preparation method, it is further improved, in the step S7, hydrogenation solution is adjusted using concentrated acid；It is described dense
Acid is the concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid；The pH value of the hydrogenation solution is adjusted to 7~9；The time of the standing be 6h~
48h。
In the present invention, deoxidation distilled water is to be obtained by entering high pure nitrogen Gu in distilled water with removing remaining oxygen
?.
Compared with the prior art, the advantages of the present invention are as follows：
(1) the present invention provides a kind of preparation methods of aurantiin dihydrochalcone, are original with orange peel and/or the dried immature fruit of citron orange
Material is extracted to obtain aurantiin by Subcritical Water Extraction technology, then obtains shaddock ped by carrying out hydrogenation open loop to aurantiin
Glycosides dihydrochalcone.In the present invention, the suitable subcritical water of polarity is obtained using Subcritical Water Extraction technology, with this subcritical shape
Subcritical water under state is Extraction solvent, thus it is possible to vary the phase behavior of extraction system accelerates solvation effect, changes conventional solvent
Under the conditions of heterogeneous reaction be homogeneous reaction, increase diffusion coefficient, reduce mass transfer and heat transmission resistance, can not only be in shorter time
Inside reach extraction equilibrium, shorten processing time, while the distribution of extraction product can also be controlled, thus, it is possible to efficiently extract to obtain
Aurantiin, high income, the purity of gained aurantiin are high, so as to realize to aurantiin selective extraction, specially：To citrus
Skin powder carries out Subcritical Water Extraction, and lipid material and fat-soluble pigment extract from citrus peel meal and are dissolved in Asia and face at this time
In boundary's aqueous solution, centrifugation discards supernatant liquid, realizes the removal to lipoid substance and fat-soluble pigment, gained filter residue and activated carbon
Mixing, continues Subcritical Water Extraction, and aurantiin is in filter residue from extracting and be dissolved in subcritical water solution at this time, and
Water colo(u)r in filter residue is tightly held by activated carbon, and discards filter residue, and realization effectively removes lipid material and pigment.The present invention
It is only using subcritical water as Extraction solvent in extraction process, this is a kind of environmentally friendly solvent, does not introduce organic solvent,
It not will produce a large amount of organic wastewaters, and made during no solvent residue in product, non-secondary pollution, while Subcritical Water Extraction
High temperature and pressure can be such that microbiological pollution that may be present in raw material is addressed completely, securely and reliably.The present invention
In, aurantiin is extracted using the extraction process of high-purity nitrogen gas shielded aurantiin, and using deoxidation distilled water, high temperature is avoided and draws
The oxygenolysis of the active principle risen.Compared with organic solvent, the present invention is environmental-friendly using subcritical water as Extraction solvent, money
Source is abundant, has many advantages, such as that extraction efficiency higher, cost be lower, green cleaning, can overcome aurantiin extraction in existing method
Rate is low, raw material availability is low, using organic solvent the defects of.(it is such as extraction with organic solvent compared to existing general extraction methods
The extracting method of agent), the present invention extracts aurantiin using Subcritical Water Extraction technology, with simple and practicable, extraction time is short, extraction
The advantages that taking extractant green efficient, used to clean, is environmentally friendly, is a kind of green extraction.On this basis, of the invention
Using the high-purity aurantiin extracted using Subcritical Water Extraction technology as raw material, height is prepared by hydrogenation open loop
The aurantiin dihydrochalcone of yield, high-purity.In the present invention, by the synthesis of the extraction of aurantiin and aurantiin dihydrochalcone
Coupling is got up, and is improved the utilization rate of active principle in raw material, is improved production efficiency.Preparation method of the present invention has technique letter
The advantages that single, easy to operate, of low cost, environmentally protective, high income, high purity, can improve the comprehensive profit of citrus and the dried immature fruit of citron orange
With value, there are good application prospect and economic benefit, while organic solvent need not be used in preparation process, ring will not be given
Secondary pollution is brought in border, is a kind of environmentally friendly preparation method of great future, is suitable for preparing on a large scale, convenient for industrialization
It utilizes.
(2) in preparation method of the present invention, Subcritical Water Extraction condition has great influence to the yield and purity of aurantiin,
Present invention optimizes the conditions of Subcritical Water Extraction thus, specially：The pressure of first time Subcritical Water Extraction be 3MPa~
12MPa, temperature are 80 DEG C~250 DEG C；The pressure of second of Subcritical Water Extraction is 2MPa~12MPa, and temperature is 80 DEG C~225
℃.In the present invention, pass through polarity, the surface tension of pressure and temperature change water during optimization first time Subcritical Water Extraction
And viscosity, the subcritical water for being easier to dissolving fat-soluble pigment and lipoid substance is obtained, more fat-soluble pigments and fat are made
Class compound is dissolved into subcritical water, to further increase the removal rate to fat-soluble pigment and lipoid substance.Herein
On the basis of, polarity, surface that the present invention passes through pressure and temperature change water during optimizing second of Subcritical Water Extraction
Power and viscosity obtain the subcritical water for being easier to dissolving aurantiin, more aurantiins are made to be dissolved into subcritical water, and due to
Activated carbon is added simultaneously during Subcritical Water Extraction, the activated carbon being added at this time can adsorb water colo(u)r, to
The removal rate for further increasing pigment further increases the yield and purity of aurantiin.In addition, in the present invention, by extracting
Impurity substances are removed during aurantiin, can also simplify purification process, further decrease operation difficulty, improve extraction efficiency.
It can be seen that in preparation method of the present invention, the yield of aurantiin can be further increased by optimizing Subcritical Water Extraction condition
And purity, it thus can also further increase the yield and purity of aurantiin dihydrochalcone, obtain higher yield and more high-purity
The aurantiin dihydrochalcone of degree, and enable to the technique of preparation method simpler, operation is more convenient, and cost is lower,
Resource utilization higher, preparation efficiency higher.
Description of the drawings
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical solution in the embodiment of the present invention carries out clear, complete description.
Fig. 1 is the process flow chart that aurantiin dihydrochalcone is prepared in the embodiment of the present invention 1.
Specific implementation mode
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
In following embodiment, unless otherwise noted, material therefor and instrument are commercially available, and technique used is common process,
Device therefor is conventional equipment, and the data obtained is the average value of the above experiment three times.
Embodiment 1：
A kind of preparation method of aurantiin dihydrochalcone, process flow chart is as shown in Figure 1, include the following steps：
(1) by orange peel drying and ultramicro grinding, citrus peel meal is obtained, the wherein grain size of citrus peel meal is 20 μm.
(2) citrus peel meal obtained in step (1) is packed into subcritical abstraction kettle, is passed through high pure nitrogen, while according to de-
The weight ratio of oxygen distilled water and citrus peel meal is 1: 12, and deoxidation distilled water is added into subcritical abstraction kettle and (in the present embodiment, takes off
Oxygen distilled water is to be obtained by entering high pure nitrogen Gu in distilled water with removing remaining oxygen), it is 6MPa, temperature in pressure
It is progress first time Subcritical Water Extraction 60min at 250 DEG C, cooling, press filtration discards filtrate obtained by press filtration, obtains filter residue, the filter
Slag continues on for Subcritical Water Extraction.
(3) it is 5% according to the mass ratio of activated carbon and filter residue, the filter residue obtained in step (2) is mixed with activated carbon
Even, gained mixture is fitted into subcritical abstraction kettle, is 1: 8 according to the weight ratio of deoxidation distilled water and filter residue, toward subcritical extraction
Addition deoxidation distilled water in kettle is taken, while being passed through high pure nitrogen, is carried out in the case where pressure is 4.5MPa, temperature is 150 DEG C second
Subcritical Water Extraction 50min, cooling, gained mixes slag liquid and centrifuges 15min in the case where rotating speed is 8000rpm, discards centrifugation gained filter
Slag collects supernatant, obtains aurantiin extracting solution.
(4) the aurantiin extracting solution obtained in step (3) is purified using D130 macroporous absorbent resins, then with body
The ethanol solution of product concentration 90% elutes the D130 macroporous absorbent resins for being adsorbed with aurantiin as eluant, eluent, eluant, eluent
Volume be 7 times of D130 macroporous absorbent resin volumes, obtain aurantiin eluent.
(5) the aurantiin eluent obtained in step (4) is concentrated under reduced pressure at 50 DEG C, is freeze-dried, must purifies
Aurantiin, wherein the yield of the aurantiin be 8.3%, purity 82%.
(6) at normal temperatures, the aurantiin obtained in step (5) is dissolved in the potassium hydroxide solution that pH value is 11, is added
Palladium charcoal is passed through hydrogen as catalyst, and pressure is made to maintain 0.8MPa, carries out hydrogenation 160min under agitation,
It is filtered to remove palladium charcoal, gained filtrate is hydrogenation solution.
(7) it uses the pH value of filtering gained filtrate (hydrogenation solution) in concentrated sulfuric acid regulating step (6) to 7, stands for 24 hours, filtering,
Filtering gained sediment is freeze-dried, aurantiin dihydrochalcone is obtained.
1 Subcritical water extraction conditions of the embodiment of the present invention, the yield of aurantiin and purity, aurantiin dihydrochalcone
Yield and purity, as shown in serial number 1 in table 1.In addition, in the embodiment of the present invention, different subcritical abstraction conditions pair have also been investigated
The influence of aurantiin, aurantiin dihydrochalcone yield and purity, preparation method used is substantially the same manner as Example 1, difference
Place is as shown in table 1.
The different preparation conditions of table 1 are to extraction aurantiin and the influence for preparing aurantiin dihydrochalcone
As shown in Table 1, the method for the present invention can improve aurantiin and aurantiin dihydrochalcone yield and purity, wherein shaddock
Skin glycosides yield is up to 8.5%, and purity is up to 97%；Aurantiin dihydrochalcone yield is up to 94%, and purity reaches 95%, this says
Bright the method for the present invention is conducive to improve the yield and purity of aurantiin, aurantiin dihydrochalcone.
Embodiment 2
Investigate influence of the different macroreticular resins to aurantiin extraction effect：
Take D101 macroporous absorbent resins, D4020 macroporous absorbent resins, AB-8 macroporous absorbent resins, D130 macroporous absorption trees
Fat, HPD450 macroporous absorbent resins and D140 macroporous absorbent resins, each 2.0g are added separately in 1 step of 30mL embodiments (3)
It in obtained supernatant, stands after fully absorption reaches saturation and filters (for 24 hours) at room temperature, measure shaddock in the front and back sample liquid of absorption
After the content of skin glycosides and the ethanol solution elution for being 90% with volumetric concentration in eluent aurantiin content, as a result such as 2 institute of table
Show.Table 2 is the adsorption capacity and analytic ability comparing result of different macroreticular resins.
Adsorption rate and desorption efficiency of the macroreticular resin to limonin is calculated as follows.
Adsorption rate (%)=(C0-C1)/C0×100
Desorption efficiency (%)=C2/(C0-C1)×100
In formula：C0For target component solution concentration, mg/mL in initial sample；
C1For target component concentration in filtrate after resin adsorption saturation, mg/mL.
C2For target component concentration, mg/mL in stripping liquid.
The adsorption capacity and analytic ability comparing result of the different macroreticular resins of table 2
| Macroreticular resin | Adsorption capacity (mg/g) | Resolution factor (%) |
| D101 | 62.8 | 78.7 |
| D130 | 95.2 | 96.2 |
| D140 | 86.3 | 68.4 |
| HPD450 | 71.7 | 95.8 |
| D4020 | 89.6 | 43.5 |
| AB-8 | 93.4 | 86.0 |
As shown in Table 2, it is screened by 6 kinds of macroreticular resins of Static Adsorption and desorption experiment pair, the results showed that：D130 is big
Macroporous adsorbent resin shows best absorption property and desorption effect, and the adsorption capacity to aurantiin is 95.2%, resolution factor
It is 96.2%, is the resin for capableing of preferable enriching and purifying aurantiin.
Comparative example 1
A method of aurantiin dihydrochalcone is prepared, is included the following steps：
(1) by fresh shaddock ped at 50 DEG C freeze-day with constant temperature, be crushed to 2mm, obtain shaddock peel powder；According to the body of shaddock peel powder and water
Product is than being 1:5, shaddock peel powder is impregnated into 30min in water, stirring to colourless, filtering is dry, obtains shaddock ped granulated slag.
(2) at 25 DEG C, the shaddock ped granulated slag obtained in step (1) is immersed into isometric saturation Ca (OH)2In, it is in frequency
Ultrasound 30min under conditions of 25KHz, obtains shaddock ped granulated slag mixed liquor.
(3) it with the pH value of the shaddock ped granulated slag mixed liquor obtained in 5mol/L NaOH solutions regulating step (2) to 13, filters,
The hydrochloric acid that 1mol/L is added neutralizes, until pH value is 4.5, gained sediment filtering is dried in vacuo at 70 DEG C, obtains thick shaddock ped
Glycosides.
(4) by the thick aurantiin obtained in step (3) with containing NaOH and ethyl alcohol aqueous solution (in the aqueous solution, NaOH's
A concentration of 1g/mL, the volumetric concentration of ethyl alcohol are 50%) to dissolve, and 1mol/L salt acid for adjusting pH value is added to 5.0 in filtering, and gained is heavy
Starch is washed with the ethanol solution that volumetric concentration is 50%, is washed with water to close to neutrality, is dried in vacuo, is refined at 70 DEG C
Aurantiin, yield 5.82%, purity 62.2%.
(5) at normal temperatures, the refined aurantiin obtained in step (4) is dissolved in the potassium hydroxide solution that pH is 11, is added
Enter palladium charcoal as catalyst, be passed through hydrogen, pressure is made to maintain 0.8MPa, carries out hydrogenation 160min under agitation,
It is filtered to remove palladium charcoal, the pH value for adjusting filtrate with the concentrated sulfuric acid is stood for 24 hours, filtering to 7, and filtering gained sediment is taken to be freezed
It is dry, obtain aurantiin dihydrochalcone, yield 80%, purity 65%.
Comparative example 2
A method of aurantiin dihydrochalcone is prepared, is included the following steps：
(1) citrus peel meal obtained in 100g embodiments 1 is taken, uses 1200mL, 1000mL, 800mL ethanol solution (body successively
A concentration of 40%) refluxing extraction of product, reflux extracting time is respectively 2h, 1.5h, 1h.Merge extracting solution obtained by 3 refluxing extractions,
It is concentrated in the case where pressure is 0.04MPa, it is 1.15 to be concentrated into proportion, and 3.5 times of amount water are added in concentrate, stirs evenly, centrifuges, from
Supernatant D130 macroporous absorbent resins obtained by the heart adsorb, and are desorbed with the ethanol solution of volumetric concentration 60%.Add into stripping liquid
Enter 2.5% (i.e. the addition of activated carbon is refer to desorbed solution gross mass 2.5%) activated carbon, return stirring decoloration 2.5h, cooling
Filtering, it is 1.55 that filtrate decompression, which is concentrated into proportion, is cooled to 35 DEG C of crystallization 14h, obtains crystal crude product.Crystal crude product is centrifuged,
Centrifugation gained precipitation crude product is recrystallized 3 times with water.The material recrystallized is poured into centrifuge and is centrifuged, centrifugation gained precipitation is used
Water wash obtains aurantiin precipitation.It is dry, dry gained aurantiin essence at 75 DEG C that aurantiin precipitation, which is put into baking oven in temperature,
Product crush, and cross 80 mesh sieve, obtain aurantiin finished product, yield 2.82%, purity 82.7%.
(2) at normal temperatures, the aurantiin finished product obtained in step (2) is dissolved in the potassium hydroxide solution that pH is 11, is added
Enter palladium charcoal as catalyst, be passed through hydrogen, it is 0.8MPa to be passed through Hydrogen Vapor Pressure, carries out hydrogenation under agitation
160min is filtered to remove palladium charcoal, and the pH value for adjusting filtrate with the concentrated sulfuric acid is stood for 24 hours, filtering to 7, take filtering gained sediment into
Row freeze-drying, obtains aurantiin dihydrochalcone, yield 83%, purity 76.3%.
In summary, preparation method of the present invention can improve the yield and purity of aurantiin, the wherein high income of aurantiin
Up to 8.5%, purity is up to 97%, while can also improve the yield and purity of aurantiin dihydrochalcone, wherein aurantiin two
The yield of hydrogen chalcone is up to 94%, and purity is up to 95%.In addition, in preparation method of the present invention, flow is simplified, shortens week
Phase, have many advantages, such as it is simple for process, easy to operate, of low cost, simultaneously because not using methanol, petroleum ether, n-butanol etc.
Organic solvent, sewage quantity greatly reduce, economic and environment-friendly, are very suitable for mass producing, it is easy to accomplish industrialization.And comparative example 1
In used a large amount of strong acid, highly basic, environmental pollution is more serious, and to be not easy to removal clean for the harmful substance being added, can
Human body can be injured, be unfavorable for industrialized production；Extraction process flow is complicated in comparative example 2, and required time is longer, aurantiin
Extraction needs to use a large amount of ethyl alcohol, of high cost, as direct emission enters sewage after ethyl alcohol is discarded, environmental pollution can be caused, if place
It is discharged after reason, increases entreprise cost, be unfavorable for industrialized production.In addition, the aurantiin purity obtained by comparative example 1 and 2 is not
Enough ideals are easy to generate toxic side effect to human body after eating.Therefore, existing customary preparation methods (such as comparative example 1 and comparison are compared
Example 2), preparation method of the present invention is with simple for process, easy to operate, of low cost, environmentally protective, resource utilization is high, prepares
The advantages that efficient, high income, high purity, can improve the comprehensive utilization value of citrus, there is good application prospect and warp
Ji benefit, while organic solvent need not be used in preparation process, secondary pollution will not be brought to environment, be a kind of great future
Environmentally friendly preparation method, be suitable for preparing on a large scale, be convenient for industrialized utilization.
Above example is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that being led for this technology
For the those of ordinary skill in domain, improvements and modifications without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of aurantiin dihydrochalcone, which is characterized in that include the following steps：
S1, orange peel and/or the dried immature fruit of citron orange are dried and ultramicro grinding, obtain citrus peel meal；
S2, using deoxidation distilled water as extractant, first time Subcritical Water Extraction is carried out to the citrus peel meal that is obtained in step S1,
Press filtration discards filtrate, obtains filter residue；
S3, the filter residue obtained in step S2 is mixed with activated carbon, carrying out second of Asia as extractant using deoxidation distilled water faces
Boundary's water extraction, centrifugation discard filter residue, obtain aurantiin extracting solution；
S4, the aurantiin extracting solution obtained in step S3 is purified using resin, to the aurantiin that is adsorbed on resin into
Row elution, obtains aurantiin eluent；
S5, the aurantiin eluent obtained in step S4 is concentrated under reduced pressure and is freeze-dried, obtain aurantiin；
S6, the aurantiin obtained in step S5 is dissolved in lye, catalyst is added, be passed through hydrogen and carry out hydrogenation, filter,
Obtain hydrogenation solution；
The pH value of the hydrogenation solution obtained in S7, regulating step S6 is stood, and is filtered, and freeze-drying obtains aurantiin dihydro Cha Er
Ketone.
2. preparation method according to claim 1, which is characterized in that in the step S2, the deoxidation distilled water and mandarin orange
The weight ratio of orange peel powder is 1: 4~1: 12.
3. preparation method according to claim 2, which is characterized in that in the step S2, the first time subcritical water
Extraction carries out in a nitrogen atmosphere；The pressure of the first time Subcritical Water Extraction is 3MPa~12MPa；The first time Asia is faced
The temperature of boundary's water extraction is 80 DEG C~250 DEG C；The time of the first time Subcritical Water Extraction is 15min~70min.
4. preparation method according to claim 1, which is characterized in that in the step S3, the activated carbon and filter residue
Mass ratio is 0.5%~8%；The weight ratio of the deoxidation distilled water and filter residue is 1: 4~1: 12.
5. preparation method according to claim 4, which is characterized in that in the step S3, second of subcritical water
Extraction carries out in a nitrogen atmosphere；The pressure of second of Subcritical Water Extraction is 2MPa~12MPa；Second of Asia is faced
The temperature of boundary's water extraction is 80 DEG C~225 DEG C；The time of second of Subcritical Water Extraction is 15min~70min；It is described from
The heart carries out under the conditions of rotating speed is 5000rpm~10000rpm；The time of the centrifugation is 10min~20min.
6. preparation method according to any one of claims 1 to 5, which is characterized in that in the step S1, the citrus
Pericarp is at least one of orange peel, orange peel, shaddock ped, orange peel；The grain size of the citrus peel meal is 10 μm~50 μm.
7. preparation method according to any one of claims 1 to 5, which is characterized in that in the step S4, the resin
For D101 macroporous absorbent resins, D4020 macroporous absorbent resins, AB-8 macroporous absorbent resins, D130 macroporous absorbent resins, HPD450
At least one of macroporous absorbent resin and D140 macroporous absorbent resins；The eluant, eluent used in the elution process is molten for ethyl alcohol
Liquid；The volumetric concentration of the ethanol solution is 65%~95%；The volume of the eluant, eluent is 5 times~15 times of resin volume.
8. preparation method according to any one of claims 1 to 5, which is characterized in that in the step S5, the decompression
It is to be carried out at 40 DEG C~80 DEG C to be concentrated in temperature.
9. preparation method according to any one of claims 1 to 5, which is characterized in that in the step S6, the lye
For sodium hydroxide solution and/or potassium hydroxide solution；The pH value of the lye is 9~14；The catalyst is palladium charcoal；The hydrogen
Change in reaction process maintains the pressure of reaction system for 0.5MPa~5MPa by being passed through hydrogen；The time of the hydrogenation is
30min~240min.
10. preparation method according to any one of claims 1 to 5, which is characterized in that in the step S7, use is dense
Acid adjusts hydrogenation solution；The concentrated acid is the concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid；The pH value of the hydrogenation solution is adjusted to 7~9；
The time of the standing is 6h~48h.
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| CN113666976A (en) * | 2021-08-23 | 2021-11-19 | 西南大学 | Method for preparing naringin dihydrochalcone by circulating spray hydrogenation |
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| CN113666976A (en) * | 2021-08-23 | 2021-11-19 | 西南大学 | Method for preparing naringin dihydrochalcone by circulating spray hydrogenation |
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