CN109879917A - A kind of method that Exocarpium Citri Grandis extract adds hydrogen to prepare aurantiin dihydrochalcone sweetener - Google Patents
A kind of method that Exocarpium Citri Grandis extract adds hydrogen to prepare aurantiin dihydrochalcone sweetener Download PDFInfo
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Abstract
The present invention relates to sweetener fields, provide a kind of method that Exocarpium Citri Grandis extract adds hydrogen to prepare aurantiin dihydrochalcone sweetener, and Exocarpium Citri Grandis crushed material is first carried out alcohol extracting-water precipitating processing, obtains Exocarpium Citri Grandis aurantiin monomer；Ring-opening reaction is carried out after again mixing Exocarpium Citri Grandis aurantiin monomer, alkali hydroxide soln, obtains reaction solution；Reaction solution is crossed after cation exchange resin and palladium rhenium catalyst mixes with mixed alcoholic solvent and carries out hydrogenation reaction, obtains aurantiin dihydrochalcone sweetener.For preparation method provided by the invention using the high Exocarpium Citri Grandis of cheap and easy to get, naringin content as initial feed, method is simple, at low cost；The present invention utilizes palladium rhenium catalyst catalytic hydrogenation reaction; method of hydrotreating is efficiently quick, easy to operate; and the present invention being capable of effective protection catalyst; it prevents palladium rhenium catalyst from contacting with water and hydro-thermal reaction inactivation occurs; extend the service life of catalyst; it is also able to satisfy the demand of Exocarpium Citri Grandis products diversification, there is stronger exploitation prospect.
Description
Technical field
The present invention relates to sweetener technical field, in particular to a kind of Exocarpium Citri Grandis extract adds hydrogen to prepare aurantiin dihydro to look into
The method of your ketone sweetener.
Background technique
Dihydrochalcone is a kind of efficient sweetener, is mainly characterized by that sweet taste is salubrious, happy, and without rear bitter taste, sweet taste comes
It obtains slowly, rear taste is longer, with the increase of concentration, declines to the relative sweetness of sucrose, and can reduce people to bitter in beverage and medicament
The sensitivity of taste.
Aurantiin dihydrochalcone is a kind of novel dihydrochalcone-type sweetening agent, and sugariness is the 500~700 of sucrose
Times, have the characteristics that high sugariness, low heat value.The patent of Publication No. CN103772455A provides a kind of aurantiin dihydro and looks into ear
The preparation process of ketone, this method are successively walked through synthetic reaction, decoloration, filtering, acidification, crystallization, centrifugation etc. using aurantiin as raw material
Suddenly crude product aurantiin dihydrochalcone being obtained, crude product aurantiin dihydrochalcone is dissolved again, filter, crystallize, being centrifuged and etc.
The aurantiin dihydrochalcone refined.The method does not announce the extraction source of aurantiin using aurantiin as raw material, and should
Method and step is more, complex process.
Exocarpium Citri Grandis be rutaceae Citrus grandis or shaddock prematurity or maturescent dry outer epidermal layer, be clinically used for controlling
Treatment cough due to wind-cold evil, the abundant expectoration circulation of vital energy in the wrong direction, dyspepsia heating and the bored equal diseases of evil of vomitting ruffian, are Guangdong famous and expensive special local product medicinal materials.Flavones is Exocarpium Citri Grandis
One of principle active component has the effects that anti-oxidant, anti-aging, adjusts metabolism, removes fatigue and improve immunity.
Aurantiin and a small amount of Rhoifolin, Poncirus glycosides and neohesperidin are mainly contained in Exocarpium Citri Grandis flavone component.At present to Exocarpium Citri Grandis
Exploitation extracts shaddock ped currently without Exocarpium Citri Grandis mainly in medicine materical crude slice, beverage, health liquor, health protection tea, oral solution, tablet and capsule etc.
Glycosides prepares the correlative study that dihydro looks into youngster's ketone sweetener.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of Exocarpium Citri Grandis extracts, and hydrogen to be added to prepare aurantiin dihydrochalcone sweet tea
The method of taste agent.Method provided by the invention prepares aurantiin dihydrochalcone sweetener, preparation method by raw material of Exocarpium Citri Grandis
Simply, at low cost, new direction is provided for Exocarpium Citri Grandis resource application.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of method that Exocarpium Citri Grandis extract adds hydrogen to prepare aurantiin dihydrochalcone sweetener, comprising the following steps:
(1) Exocarpium Citri Grandis crushed material is subjected to alcohol extracting-water precipitating processing, obtains Exocarpium Citri Grandis aurantiin monomer；
(2) ring-opening reaction is carried out after mixing the Exocarpium Citri Grandis aurantiin monomer and alkali hydroxide soln, is obtained
Ring-opening reaction liquid；It is dried after ring-opening reaction liquid is crossed cation exchange resin, obtains open-loop products；
(3) open-loop products, palladium rhenium catalyst and mixed alcoholic solvent are mixed, then pass to hydrogen and carries out hydrogenation reaction,
Obtain aurantiin dihydrochalcone sweetener.
Preferably, in the step (1) Exocarpium Citri Grandis crushed material the preparation method comprises the following steps: successively being cut after Exocarpium Citri Grandis is softened
Piece and crushing obtain Exocarpium Citri Grandis crushed material；The granularity of the Exocarpium Citri Grandis crushed material is 80~100 mesh.
Preferably, the softening specifically: Exocarpium Citri Grandis is placed in water vapour and is steamed；The temperature of the steaming is 40~80
DEG C, the time is 0.5~1.5h, and the amount ratio of the Exocarpium Citri Grandis and water is 1g:10~30mL.
Preferably, alcohol extracting-water precipitating is handled in the step (1) specifically: is mixed Exocarpium Citri Grandis crushed material and ethyl alcohol and is mentioned
It takes, obtains ethanol extract；The ethanol extract is concentrated, medicinal extract is obtained；Into the medicinal extract plus water carries out crystallization, obtains
Exocarpium Citri Grandis aurantiin monomer.
Preferably, the temperature of the extraction is 40~80 DEG C, and the time is 4~6h, and solid-liquid ratio is 1g:10~30mL；It is described
The volumetric concentration of ethyl alcohol is 40~50%；The volume ratio of the medicinal extract and water is 1:2~5.
Preferably, the mass concentration of alkali hydroxide soln is 2~10% in the step (2)；The Exocarpium Citri Grandis
The mass ratio of aurantiin monomer and alkali metal hydroxide is 6g:1~5g.
Preferably, the temperature of the ring-opening reaction be 30~50 DEG C, the time be 30~100min, speed of agitator be 300~
500r/min。
Preferably, alcoholic solvent is methanol/ethanol-isobutanol mixed solvent in step (3)；The open-loop products, palladium rhenium are urged
The amount ratio of agent and mixed alcoholic solvent is 6g:0.01~0.05g:30~80mL；
The temperature of the hydrogenation reaction is 60~100 DEG C, and the time is 4~12h, and Hydrogen Vapor Pressure is 0.5~2.5MPa.
Preferably, the palladium rhenium catalyst includes carrier and the palladium and rhenium that are supported on carrier；The carrier is active carbon；
The mass percentage of palladium is 2~5% in the catalyst, and the mass percentage of rhenium is 1.5~2.5%.
Preferably, after the completion of the hydrogenation reaction further include: filter hydrogenation reaction product system, obtain recycling catalyst
And filtrate；Concentrate after the filtrate to be separated to mixed alcoholic solvent adds water to carry out crystallisation by cooling, and aurantiin dihydro is obtained after filtering
Chalcone sweetener.
The present invention provides a kind of methods that Exocarpium Citri Grandis extract adds hydrogen to prepare aurantiin dihydrochalcone sweetener, wherein
Exocarpium Citri Grandis crushed material is first subjected to alcohol extracting-water precipitating processing, obtains Exocarpium Citri Grandis aurantiin monomer；Again by Exocarpium Citri Grandis aurantiin monomer, alkali
Ring-opening reaction is carried out after metal hydroxide solutions mixing, obtains ring-opening reaction liquid；Ring-opening reaction liquid is crossed into cation exchange tree
Rouge is simultaneously dried, and obtained open-loop products and palladium rhenium catalyst and mixed alcoholic solvent are mixed, and is passed through hydrogen and is carried out hydrogenation reaction, obtains
Aurantiin dihydrochalcone sweetener.Preparation method provided by the invention is mentioned using Exocarpium Citri Grandis as initial feed using alcohol precipitation water
Method extracts the Flavonoid substances aurantiin in Exocarpium Citri Grandis, then by alkaline hydrolysis open loop and adds hydrogen that shaddock ped is prepared aurantiin
Glycosides dihydrochalcone sweetener；And the present invention utilize palladium rhenium catalyst catalytic hydrogenation reaction, the catalyst hydrogenation activity and
The more typical Pd/C catalyst of selectivity is higher, and the thermoactive ability of water resistant is more preferable, and the long service life of catalyst repeats
It uses, further reduced the preparation cost of sweetener；Ring-opening reaction liquid is crossed resin cation by the present invention, can be removed wherein
Alkali metal cation, catalyst can be effectively protected.Embodiment the result shows that, the shaddock ped that method provided by the invention obtains
Glycosides dihydrochalcone sweetener purity can achieve 95.5%~99.9%, and the conversion ratio of reactant can achieve in hydrogenation reaction
95% or so, and after the reuse of palladium rhenium catalyst 10 times, catalytic activity is basically unchanged.
Detailed description of the invention
Fig. 1 is the flow diagram of the embodiment of the present invention 1；
Fig. 2 is the infrared spectrogram of 1 gained hydrogenation products of the embodiment of the present invention；
Fig. 3 is the first mass spectrometric figure of 1 gained hydrogenation products of the embodiment of the present invention；
Fig. 4 is the second order ms figure of 1 gained hydrogenation products of the embodiment of the present invention；
Fig. 5 is the first mass spectrometric figure of aurantiin dihydrochalcone standard items；
Fig. 6 is the second order ms figure of aurantiin dihydrochalcone standard items；
Fig. 7 is the scanning electron microscope (SEM) photograph of 1 gained hydrogenation products of the embodiment of the present invention；
Fig. 8 is the active testing result figure of palladium rhenium catalyst in the embodiment of the present invention 1.
Specific embodiment
The present invention provides a kind of methods that Exocarpium Citri Grandis extract adds hydrogen to prepare aurantiin dihydrochalcone sweetener, including
Following steps:
(1) Exocarpium Citri Grandis crushed material is subjected to alcohol extracting-water precipitating processing, obtains Exocarpium Citri Grandis aurantiin monomer；
(2) ring-opening reaction is carried out after mixing the Exocarpium Citri Grandis aurantiin monomer, alkali hydroxide soln, is opened
Ring reaction solution；It is dried after ring-opening reaction liquid is crossed cation exchange resin, obtains open-loop products；
(3) open-loop products, palladium rhenium catalyst and alcoholic solvent are mixed, then passes to hydrogen and carry out hydrogenation reaction, obtains
To aurantiin dihydrochalcone sweetener.
Exocarpium Citri Grandis crushed material is carried out alcohol extracting-water precipitating processing by the present invention, obtains Exocarpium Citri Grandis aurantiin monomer.In the present invention,
The preparation method of the Exocarpium Citri Grandis crushed material is preferred are as follows: is successively sliced and is crushed after softening Exocarpium Citri Grandis, obtains Exocarpium Citri Grandis
Crushed material；In the present invention, the softening is particularly preferred as: Exocarpium Citri Grandis being placed in water vapour and is steamed；The temperature of the steaming
Preferably 40~80 DEG C, more preferably 50~70 DEG C, the time of the steaming is preferably 0.5~1.5h, more preferably 1h, describedization
The amount ratio of Exocarpium Citri Rubrum and water is preferably 1g:10~30mL, more preferably 1g:15~25mL.In the present invention, the thickness of the slice
Degree is preferably 3~5mm, more preferably 4mm.In the present invention, the granularity of Exocarpium Citri Grandis crushed material obtained by the crushing is preferably 80
~100 mesh, more preferably 90 mesh；The present invention does not have particular/special requirement to the kind of the Exocarpium Citri Grandis, uses those skilled in the art
The Exocarpium Citri Grandis of known kind, such as positive texturing Exocarpium Citri Rubrum.
In the present invention, the alcohol extracting-water precipitating processing specifically: Exocarpium Citri Grandis crushed material and ethyl alcohol are mixed and extracted, is obtained
To ethanol extract；The ethanol extract is concentrated, medicinal extract is obtained；Into the medicinal extract plus water carries out crystallization, obtaining tangerine
Red aurantiin monomer.
In the present invention, the temperature of the extraction is preferably 40~80 DEG C, more preferably 50~70 DEG C, the extraction when
Between preferably 4~6h, more preferably 5h, the solid-liquid ratio of the extraction is preferably 1g:10~30mL, more preferably 1g:15~
25mL；The volumetric concentration of the ethyl alcohol is preferably 40~50%, and more preferably 45%；The present invention does not have the degree of the concentration
Particular/special requirement can obtain sticky medicinal extract；In a specific embodiment of the present invention, it is preferable to use revolving method progress is dense
Contracting, and the ethyl alcohol steamed recycling is reused.In the present invention, the volume ratio of the medicinal extract and water be preferably 1:2~
5, more preferably 1:3~4；In the present invention, the temperature of the crystallization is preferably 10 DEG C, and the present invention is preferably quiet under refrigerated conditions
It sets until crystal is precipitated completely；After the completion of crystallization, the crystallization mixture filtration drying that the present invention will preferably obtain obtains Exocarpium Citri Grandis
Aurantiin monomer；The present invention does not have particular/special requirement to the temperature of the drying, can be complete by the moisture drying in crystal.
In the present invention, the Exocarpium Citri Grandis aurantiin monomer has structure shown in Formulas I.
The present invention is dissolved in organic solvent characteristic not soluble in water using the Flavonoid substances in Exocarpium Citri Grandis, is mentioned using alcohol precipitation water
Method extracts, and the present invention uses ethyl alcohol as the effective extracting flavone of solvent energy, the precipitating using water as flavones
Agent can further reduce the cost；In addition, having a large amount of water-soluble substances dissolutions when ethyl alcohol volumetric concentration is lower than 40%, leading
It causes to filter difficulty, so the present invention is using 40~50% ethyl alcohol as extractant；And ethyl alcohol has the characteristics that volatile, convenience
Recycling ethyl alcohol is reused, and is extracted remaining filter residue and be can be used as fertilizer.
After obtaining Exocarpium Citri Grandis aurantiin monomer, the present invention is molten by the Exocarpium Citri Grandis aurantiin monomer and alkali metal hydroxide
Ring-opening reaction is carried out after liquid mixing, obtains ring-opening reaction liquid.In the present invention, the alkali metal hydroxide is preferably hydroxide
Potassium and/or sodium hydroxide；The mass concentration of the alkali hydroxide soln is preferably 2~10%, and more preferably 5~8%；
The mass ratio of the Exocarpium Citri Grandis aurantiin monomer and alkali metal hydroxide is preferably 6g:1~5g, more preferably 6g:2~4g.
In the present invention, the temperature of the ring-opening reaction is preferably 30~50 DEG C, and more preferably 40 DEG C, the ring-opening reaction
Time be preferably 30~100min, more preferably 60~90min, the speed of agitator of the ring-opening reaction is preferably 300~
500r/min, more preferably 400r/min.During ring-opening reaction, the pyranone ring in Exocarpium Citri Grandis aurantiin cracks,
Gained open-loop products (aurantiin chalcone) have structure shown in Formula II.
After the completion of ring-opening reaction, the present invention is dried after obtained ring-opening reaction liquid is crossed cation exchange resin, is opened
Ring product.Ring-opening reaction liquid by being crossed the alkali metal cation (Na in cation exchange resin removing reaction solution by the present invention+Or
K+), prevent the presence of alkali metal cation from leading to the inactivation of catalyst in subsequent step；The present invention can have in this way
Imitate guard catalyst.The present invention does not have particular/special requirement to the type of the cation exchange resin, uses those skilled in the art
Well known cation exchange resin；The conditions such as flow velocity of the present invention to the reaction solution in cation exchange resin do not have
There is particular/special requirement, uses condition well known to those skilled in the art.The present invention passes through in drying removal ring-opening reaction liquid
Obtained open-loop products are carried out subsequent hydrogenation reaction by moisture, so that it is anti-to prevent palladium rhenium catalyst from contacting generation hydro-thermal with water
It should inactivate, further extend the service life of catalyst.The present invention does not have particular/special requirement, energy to the temperature and time of the drying
It is enough to completely remove the moisture in ring-opening reaction liquid.
After obtaining open-loop products, the present invention mixes the open-loop products, palladium rhenium catalyst and mixed alcoholic solvent, then passes to
Hydrogen carries out hydrogenation reaction, obtains aurantiin dihydrochalcone sweetener.In the present invention, the mixed alcoholic solvent is preferably first
Alcohol-ethyl alcohol-isobutanol mixed solvent；The volume of the methanol/ethanol-isobutanol in the mixed solvent methanol, ethyl alcohol and isobutanol
Than being preferably 1:1~3:1, more preferably 1:1:1.
In the present invention, palladium and rhenium that the palladium rhenium catalyst preferably includes carrier and is supported on carrier；The carrier
Preferably active carbon；The mass percentage of palladium is preferably 2~5% in the palladium rhenium catalyst, and more preferably 3~4%；It is described
The mass percentage of rhenium is preferably 1.5~2.5%, more preferably 2% in palladium rhenium catalyst.The present invention utilizes palladium rhenium catalyst
Catalytic hydrogenation reaction, the more typical Pd/C catalyst of the hydrogenation activity of the catalyst, selectivity is higher, and the thermoactive energy of water resistant
Power is more preferable, so that the service life is longer for catalyst.
In the present invention, the palladium rhenium catalyst is preferably prepared by equi-volume impregnating, specifically includes following step
It is rapid: palladium salt solution, rhenium salting liquid and active carbon are mixed and impregnated, then the activated carbon after dipping is successively dried and
Hydrogen reducing to get arrive palladium rhenium catalyst of the invention.In the present invention, the time of the dipping is preferably 12h；The hydrogen
The temperature of reduction is preferably 250~500 DEG C, and more preferably 300~400 DEG C；The present invention does not have the type of the palladium salt and rhenium salt
There is particular/special requirement, uses the palladium salt and rhenium salt of type known to those skilled in the art；The present invention to the palladium salt solution and
The concentration of rhenium salting liquid does not have particular/special requirement, and the palladium loaded on active carbon and rhenium can be made to meet quality percentage described in above scheme
Content.
In the present invention, the amount ratio of the open-loop products, palladium rhenium catalyst and mixed alcoholic solvent be preferably 6g:0.01~
0.05g:30~80mL, more preferably 6g:0.02~0.04g:50~70mL.
In the present invention, the temperature of the hydrogenation reaction is preferably 60~100 DEG C, more preferably 70~90 DEG C, described to add
The time of hydrogen reaction is preferably 4~12h, more preferably 6~10h, and the Hydrogen Vapor Pressure of the hydrogenation reaction is preferably 0.5~
2.5MPa, more preferably 1~2MPa.Method hydroconversion condition provided by the invention is mild and low in cost, high-efficiency and economic, has
Stronger exploitation prospect.
In the present invention, the hydrogenation reaction products therefrom is aurantiin dihydrochalcone sweetener, has formula III institute
Show structure.
After hydrogenation reaction, the present invention preferably filters hydrogenation reaction product system, obtains recycling catalyst and filtrate；
Concentrate after the filtrate to be separated to mixed alcoholic solvent adds water to carry out crystallisation by cooling, and aurantiin dihydrochalcone sweet tea is obtained after filtering
Taste agent.In the present invention, filtering gained recycling catalyst can be reused directly, activity declines without carrying out any processing
Slow down slow；In the present invention, the concentration is preferably spin concentration, and the present invention is recycled mixed alcoholic solvent by being concentrated；This
Invention does not have particular/special requirement to the volume ratio of concentrate obtained by the concentration and water, can crystallize aurantiin dihydrochalcone and analyse
Out；The temperature of the cooling is preferably 4~25 DEG C, and more preferably 10 DEG C；The present invention preferably passes through standing and carries out cooling knot
Crystalline substance, the present invention do not have particular/special requirement to the time of the standing, and crystallization can be precipitated completely as far as possible；This hair after filtering
It is bright further preferably to dry filtration product, obtain dry aurantiin dihydrochalcone sweetener.
In the present invention, gained aurantiin dihydrochalcone sweetener is white or light yellow crystal, and has higher sweet tea
Degree, salubrious mouthfeel have effects that splendid shielding bitter taste.
Scheme provided by the invention is described in detail below with reference to embodiment, but they cannot be interpreted as pair
The restriction of the scope of the present invention.
Embodiment 1
(1) Exocarpium Citri Grandis softens 8min, and slice to 3mm smashes to 80 mesh, prepares Exocarpium Citri Grandis aurantiin with water extraction and alcohol precipitation method,
Extraction conditions are as follows: extraction time 5h, 40 DEG C of Extracting temperature, solid-liquid ratio 1g:30mL, the volumetric concentration of ethyl alcohol is 45%, is obtained
Exocarpium Citri Grandis ethanol extract recycles ethyl alcohol, is concentrated to get medicinal extract, adds 2 times of volume of water refrigerations are static to be precipitated to crystal, crosses and be filtered dry
It is dry, obtain Exocarpium Citri Grandis aurantiin powder, purity 95.1%.
(2) it takes Exocarpium Citri Grandis aurantiin 6.0g, 10% sodium hydroxide solution 30g (i.e. wherein solute sodium hydroxide is added
Gross mass is 3g), 30min is reacted, is filtered using cation exchange resin, to remove sodium ion, obtains open-loop products after drying；
(3) mixed alcohol 30ml (wherein the volume ratio of methanol, ethyl alcohol and isobutanol is 1:1:1) is added in open-loop products, adds
Entering 0.01g palladium rhenium catalyst, (carrier is carbon, and the mass percentage of palladium is 2% in catalyst, and the mass percentage of rhenium is
0.5%) it, is passed through the hydrogen of 0.5MP air pressure, micro- to be heated to 60 DEG C and be stirred to react 6h, obtained product filters recycling catalyst,
Filtrate spin concentration recycles mixed alcohol, and concentrate adds refrigeration after water to stand precipitation to be crystallized, dries after filtering, obtain hydrogenation products,
As aurantiin dihydrochalcone sweetener；Sweetener is taken out, is saved with the dry plastic bag sealing of cleaning.Preparation process signal
Figure is shown in Fig. 1.
Hydrogenation products characterization: gained aurantiin dihydrochalcone sweetener is white crystal, infrared spectrogram such as Fig. 2 institute
Show, according to fig. 2 as can be seen that catalytic hydrogenation product is in infrared light 3390.27cm-1(-OH)、1629.44cm-1(conjugation-C=
O)、2923.84cm-1(methyl-CH3)、1513.18cm-1、1438.52cm-1There is absorption at (phenyl ring), it can according to infrared spectrogram
Tentatively to infer product as aurantiin dihydrochalcone.
Gained hydrogenation products are analyzed using liquid chromatography/mass spectrometry combined instrument, the first mass spectrometric of gained hydrogenation products
Figure is as shown in figure 3, second order ms figure is as shown in Figure 4；The first mass spectrometric figures of aurantiin dihydrochalcone standard items as shown in figure 5,
Second order ms figure is as shown in Figure 6；By Fig. 3~6 it is found that the mass spectrogram of hydrogenation modification product and aurantiin dihydrochalcone standard items
Unanimously, m/z582.9 is plus cation peak occurs in hydrogen, introduces after sodium shift reagen and quasi-molecular ions occurs in m/z604.9；In m/
The quasi-molecular ions that z275.5 occurs, the aglycon quasi-molecular ions after glucosyl group is sloughed for the compound；In the fragment that m/z421.6 occurs
Peak, to slough the fragment peak that rhamnopyranosyl generates, it follows that the hydrogenation products that the present embodiment obtains are aurantiin dihydro Cha Er
Ketone.
In addition, the liquid phase purity of liquid chromatography results display gained aurantiin dihydrochalcone sweetener is 95.5%.
The scanning electron microscope (SEM) photograph of gained hydrogenation products is as shown in fig. 7, can be seen that manufactured in the present embodiment plus hydrogen according to Fig. 7
Product is uniform granular solids.
Sugariness test: referring to the sense organ comparison method of sugariness, formulating sugariness measuring method: weighing sucrose 10g, add water 100mL,
10% sucrose solution is made.Separately take sweetener W (10/n) g, add water 100mL dissolve, be made into respectively concentration be 0.125%,
0.1%, 0.067%, 0.05%, 0.04%, 0.0313%, 0.025%, 0.0125% sample.Looking for 20 people, (men and women each one
Half) two kinds of solution are tasted in comparison, and statistics thinks sugariness and the comparable number of 10% sweetness, and the most persons of number is taken to carry out
It calculates.When sweetener soln is suitable with 10% sweetness, n value is the multiple that sweetener is equivalent to sweetness of cane sugar,
N=10/W at this time.
It is as shown in table 1 according to the sugariness measurement result of the above method:
The measurement result of 1 sugariness of table
As can be seen from Table 1, the sugariness result that sense organ comparison method measures are as follows: Naringin DC (aurantiin dihydro Cha Er
Ketone) standard items sugariness be 400；The sugariness of Naringin DC (aurantiin dihydrochalcone manufactured in the present embodiment) is 400；
The sugariness of NHDC (neohesperidin dihydrochalcone) is 800；Sucralose is 400；The sugariness of saccharin sodium is 500；Aspartame
Sugariness with acesulfame potassium is 100.
Catalyst activity test: step (3) are repeated using the palladium rhenium catalyst of recycling, number of repetition is 10 times, and test is urged
Agent uses activity, and test result is shown in Fig. 8, and wherein conversion ratio is that open-loop products are converted into aurantiin dihydrochalcone sweetener
Molar percentage.
According to Fig. 8 as can be seen that reuse 10 times after, the catalytic activity of palladium rhenium catalyst substantially there is no variation,
The conversion ratio of reactant can achieve 90% or more, illustrate the catalyst have very high catalytic activity, and service life compared with
It is long.
Embodiment 2
(1) Exocarpium Citri Grandis softens 10min, and slice to 5mm smashes to 100 mesh, prepares Exocarpium Citri Grandis shaddock ped with water extraction and alcohol precipitation method
Glycosides, extraction conditions are as follows: extraction time 5h, 80 DEG C of Extracting temperature, solid-liquid ratio 1g:10mL, the volumetric concentration of ethyl alcohol is 50%, is obtained
To Exocarpium Citri Grandis ethanol extract, ethyl alcohol is recycled, medicinal extract is concentrated to get, added 3 times of volume of water refrigerations are static to be precipitated to crystal, cross and be filtered dry
It is dry, obtain Exocarpium Citri Grandis aurantiin powder.
(2) it takes Exocarpium Citri Grandis aurantiin 6.0g, 10% potassium hydroxide solution 50g (i.e. wherein solute potassium hydroxide is added
Gross mass is 5g), 50min is reacted, is filtered using cation exchange resin, to remove potassium ion, obtains open-loop products after drying；
(3) mixed alcohol 80ml (wherein the volume ratio of methanol, ethyl alcohol and isobutanol is 1:1:1) is added in open-loop products, adds
Entering 0.03g palladium rhenium catalyst, (carrier is carbon, and the mass percentage of palladium is 5% in catalyst, and the mass percentage of rhenium is
1.5%) it, is passed through the hydrogen of 0.1MP air pressure, micro- to be heated to 80 DEG C and be stirred to react 5h, obtained product filters recycling catalyst,
Filtrate spin concentration recycles mixed alcohol, and concentrate adds refrigeration after water to stand precipitation to be crystallized, dries after filtering, obtain aurantiin dihydro
Chalcone sweetener；Sweetener is taken out, is saved with the dry plastic bag sealing of cleaning.
Gained aurantiin dihydrochalcone sweetener is white crystal, and liquid phase purity is 95.8%, the characterization of hydrogenation products
As a result similar with sugariness test result and embodiment 1.
Embodiment 3
(1) Exocarpium Citri Grandis softens 10min, and slice to 4mm smashes to 90 mesh, prepares Exocarpium Citri Grandis aurantiin with water extraction and alcohol precipitation method,
Extraction conditions are as follows: extraction time 5h, 50 DEG C of Extracting temperature, solid-liquid ratio 1g:20mL, the volumetric concentration of ethyl alcohol is 40%, is obtained
Exocarpium Citri Grandis ethanol extract recycles ethyl alcohol, is concentrated to get medicinal extract, adds 2 times of volume of water refrigerations are static to be precipitated to crystal, crosses and be filtered dry
It is dry, obtain Exocarpium Citri Grandis aurantiin powder.
(2) it takes Exocarpium Citri Grandis aurantiin 6.0g, 10% sodium hydroxide solution 20g (i.e. wherein solute sodium hydroxide is added
Gross mass is 2g), be added the deionized water of 100ml, react 80min, filtered using cation exchange resin, with remove potassium from
Son obtains open-loop products after drying；
(3) mixed alcohol 40ml (wherein the volume ratio of methanol, ethyl alcohol and isobutanol is 1:1:1) is added in open-loop products, adds
Entering 0.05g palladium rhenium catalyst, (carrier is carbon, and the mass percentage of palladium is 5% in catalyst, and the mass percentage of rhenium is
1.5%) it, is passed through the hydrogen of 0.25MP air pressure, micro- to be heated to 90 DEG C and be stirred to react 4h, obtained product filters recycling catalysis
Agent, filtrate spin concentration recycle mixed alcohol, and concentrate adds refrigeration after water to stand precipitation to be crystallized, dries after filtering, obtain aurantiin
Dihydrochalcone sweetener；Sweetener is taken out, is saved with the dry plastic bag sealing of cleaning.
Gained aurantiin dihydrochalcone sweetener is white crystal, and liquid phase purity is 99.9%；The characterization of hydrogenation products
As a result similar with sugariness test result and embodiment 1.
According to above embodiments it is found that method provided by the invention can with effective protection catalyst, and hydroconversion condition it is mild,
It is efficiently quick, easy to operate, at the same using Exocarpium Citri Grandis as raw material, it is cheap and easy to get, and it is able to satisfy the need of Exocarpium Citri Grandis products diversification again
It asks, there is stronger exploitation prospect.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method that Exocarpium Citri Grandis extract adds hydrogen to prepare aurantiin dihydrochalcone sweetener, which is characterized in that including with
Lower step:
(1) Exocarpium Citri Grandis crushed material is subjected to alcohol extracting-water precipitating processing, obtains Exocarpium Citri Grandis aurantiin monomer；
(2) ring-opening reaction is carried out after mixing the Exocarpium Citri Grandis aurantiin monomer and alkali hydroxide soln, obtains open loop
Reaction solution；It is dried after ring-opening reaction liquid is crossed cation exchange resin, obtains open-loop products；
(3) open-loop products, palladium rhenium catalyst and mixed alcoholic solvent are mixed, then passes to hydrogen and carry out hydrogenation reaction, obtains
Aurantiin dihydrochalcone sweetener.
2. the method according to claim 1, wherein in the step (1) Exocarpium Citri Grandis crushed material preparation method
Are as follows: it is successively sliced and is crushed after softening Exocarpium Citri Grandis, obtain Exocarpium Citri Grandis crushed material；The granularity of the Exocarpium Citri Grandis crushed material is
80~100 mesh.
3. according to the method described in claim 2, it is characterized in that, the softening specifically: Exocarpium Citri Grandis to be placed in water vapour
It is steamed；The temperature of the steaming is 40~80 DEG C, and the time is 0.5~1.5h, the amount ratio of the Exocarpium Citri Grandis and water be 1g:10~
30mL。
4. the method according to claim 1, wherein alcohol extracting-water precipitating is handled in the step (1) specifically: will change
Exocarpium Citri Rubrum crushed material and ethyl alcohol mixing extract, and obtain ethanol extract；The ethanol extract is concentrated, medicinal extract is obtained；To
In the medicinal extract plus water carries out crystallization, obtains Exocarpium Citri Grandis aurantiin monomer.
5. according to the method described in claim 4, it is characterized in that, the temperature of the extraction be 40~80 DEG C, the time be 4~
6h, solid-liquid ratio are 1g:10~30mL；The volumetric concentration of the ethyl alcohol is 40~50%；The volume ratio of the medicinal extract and water is 1:2
~5.
6. the method according to claim 1, wherein in the step (2) alkali hydroxide soln matter
Measuring concentration is 2~10%；The mass ratio of the Exocarpium Citri Grandis aurantiin monomer and alkali metal hydroxide is 6g:1~5g.
7. the time is the method according to claim 1, wherein the temperature of the ring-opening reaction is 30~50 DEG C
30~100min, speed of agitator are 300~500r/min.
8. the method according to claim 1, wherein mixing alcoholic solvent in step (3) is methanol/ethanol-isobutanol
Mixed solvent；The amount ratio of the open-loop products, palladium rhenium catalyst and alcoholic solvent is 6g:0.01~0.05g:30~80mL；
The temperature of the hydrogenation reaction is 60~100 DEG C, and the time is 4~12h, and Hydrogen Vapor Pressure is 0.5~2.5MPa.
9. method according to claim 1 or 8, which is characterized in that the palladium rhenium catalyst includes carrier and is supported on load
Palladium and rhenium on body；The carrier is active carbon；The mass percentage of palladium is 2~5% in the catalyst, the quality hundred of rhenium
Dividing content is 1.5~2.5%.
10. the method according to claim 1, wherein after the completion of the hydrogenation reaction further include: by hydrogenation reaction
Product system filtering, obtains recycling catalyst and filtrate；It is cold that concentrate after the filtrate to be separated to mixed alcoholic solvent adds water to carry out
But it crystallizes, aurantiin dihydrochalcone sweetener is obtained after filtering.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735919A (en) * | 2021-09-28 | 2021-12-03 | 深圳市真味生物科技有限公司 | Method for preparing naringin dihydrochalcone sweetener by adding hydrogen into pummelo peel extract and prepared naringin dihydrochalcone sweetener |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113735919A (en) * | 2021-09-28 | 2021-12-03 | 深圳市真味生物科技有限公司 | Method for preparing naringin dihydrochalcone sweetener by adding hydrogen into pummelo peel extract and prepared naringin dihydrochalcone sweetener |
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