CN102617387B - Method for separating capsaicinoids monomers from capsaicinoids compounds - Google Patents
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Abstract
The invention discloses a method for separating capsaicinoids monomers from capsaicinoids compounds. According to the method, polar organic solvents are used as solvents, binary mixed solvents formed by weak polar organic solvents and middle-grade polar organic solvents are used as extracting agents; or polar organic solvent water solution is used as solvents, weak polar organic solvents are used as extracting agents, a fractionation extraction method is adopted for efficiently separating the capsaicinoids monomers from the capsaicinoids compounds containing capsaicinoids, dihydro capsaicinoids and the like. The method has the advantages that the separation efficiency is high, the solvent consumption is small, safety and environment protection are realized, the industrial production is easy, and the like.
Description
Technical field
The present invention relates to the separation method of capsaicin monomer, belong to technical field of chemical engineering, be specifically related to a kind of from capsaicin compound the method for separating pepper alkali monomer.
Background technology
The natural capsicum alkaloid compound is to separate the extremely pungent vanilla amide alkaloid of a class that obtains from the solanaceae plant pepper fruit, studies show that, that capsaicin compound has is antibacterial, analgesia, hypertension, reducing blood-fat, promotion appetite isoreactivity, in addition, also be widely used in the aspects such as foodstuffs industry, military ammunition, PCO.
The main component of capsaicin compound is capsicine and Dihydrocapsaicin, and total mass mark both can reach more than 90%, also has in addition Nordihydrocapsaicin, Homodihydrocapsaicin I and homocpsaicin etc. more than ten to plant material.Capsicine is the main active ingredient of capsaicin compound, it is clear and definite in the neural mechanism of action, act on the Arg-Pro-Lys-Pro-Gln-Gln-Phe-Phe-Gly-Leu-Met-NH2 on C type Sensory neurone, by to affect the release of Arg-Pro-Lys-Pro-Gln-Gln-Phe-Phe-Gly-Leu-Met-NH2 synthetic and store with receptors bind, local Arg-Pro-Lys-Pro-Gln-Gln-Phe-Phe-Gly-Leu-Met-NH2 is reduced, stop peripheroneural Sensory conduction, thereby reach the effect of pain relieving.Capsicine mainly is used as external-use analgesic, giving up drug habits and easing pain agent, pruritus, stomach strengthening and digestion promoting agent, preventing heart disease medicine, diet pill, sterilant and is used for military use etc. at present.The effect of some phenolic material mass-energy antagonism capsicines to neuropeptide in capsaicine crude product, synthesizing of the Arg-Pro-Lys-Pro-Gln-Gln-Phe-Phe-Gly-Leu-Met-NH2 of increase C type Sensory neurone aggravates the pain and inflammation.Therefore capsicine must just have pharmaceutical use through purifying.
Due to capsicine and other capsaicin compound textural differences very little, monomer separation comparatively the difficulty.Existing capsaicin monomer separation method comprises column chromatography, preparative chromatography, counter-current extraction, simulation moving-bed partition method and complex reaction partition method etc.Existing capsaicin monomer separation purification method is mainly to obtain the capsaicin compound of complicated component through methods such as alcohol extractings as raw material take red chilly powder or capsicum oil, then therefrom separates obtaining capsaicin monomer.
(1) Chinese patent application CN 200910148379.X has reported a kind of take capsicum oil or red chilly powder as raw material, alcoholic extract obtains capsaicin compound, pass through again the processing step such as separation and purification, monomer crude product recrystallization of macroporous adsorbent resin, produce purity greater than 98% capsicine, Dihydrocapsaicin, Nordihydrocapsaicin monomer, three's yield is all greater than 85%;
(2) Chinese patent ZL200610068854.9 discloses a kind of method for preparing purified of capsicine of monomer, employing is loaded to the capsaicine crude product on the affinity chromatographic column of anticipating, use the organic solvent wash-out, fraction collection, the elutriant concentrating under reduced pressure that obtains boils off solvent, obtains capsaicin monomer.This invention is easy and simple to handle, separation efficiency is high, but the silica gel that this affinity chromatographic column uses silver salt to process is prepared from, and the expensive and silica gel of silver salt can not be reused, and cost is higher;
(3) Chinese patent ZL 200710114310.6 discloses a kind of preparation method of high-purity capsaicin monomer.Separating solvent systems is comprised of halogenated alkane, alcohol, water etc.Solvent system is placed in standing demix after the separating funnel shake well, gets and be mutually stationary phase, lower is moving phase mutually.Take in the mixing solutions that a certain amount of sample is dissolved in upper and lower phase.At first stationary phase is filled chromatography column with pump with certain flow rate, then head end and the six-way injection valve with post joins.The opening speed controller, when making turn up 800r/min, beginning enters moving phase with the 2.0ml/min flow pump, when moving phase flows out chromatographic column, loading is collected each peak that separates, and obtains highly purified Dihydrocapsaicin, capsicine, three kinds of monomers of Nordihydrocapsaicin.
(4) Chinese patent ZL 200810060471.6 disclose a kind of from capsaicin compound the method for separating high-purity capsaicin monomer, make moving phase with one or both solvents in methyl alcohol, ethanol, acetonitrile and the mixed solution of water, as stationary phase, adopt the simulated moving bed system of open loop form to isolate high-purity capsaicin monomer once from the capsaicin compound that contains capsicine, Dihydrocapsaicin and Nordihydrocapsaicin with carbon 18 silica gel.Simulated Moving-Bed Parex Process is successive processes, and the method technique is simple, and capsaicin monomer purity and yield are all higher; But higher to equipment requirements, and be the chromatographic run process, treatment capacity is little, and solvent consumption is large;
(5) Chinese patent application CN 02134583.X discloses a kind of method of making high-purity capsaicin take capsaicine as raw material, take commercially available capsaicine as raw material, capsaicine is dissolved in hydrophilic organic solvent, and carry out complex reaction with the aqueous solution of silver ion, use again hydrophobic nature organic solvent Processing Ag ionic complex, after removing silver ions, then process concentrated solution with alkali, acid etc., reclaim at last high-purity capsaicin.
Above patent or patent application provide the separation purification method of capsaicin monomer from different perspectives, yet the restriction due to the factor of production, adopt the mode separation and purification of chromatographic column wash-out or macroporous resin comparatively consuming time, and subsequent step (comprising recrystallization etc.) solvent and filler consumption are large, are unsuitable for scale operation; Add the method complex operation complexity such as silver ion complexation agent, utilize in a large number organic solvent also to be unfavorable for environmental friendliness.Therefore, set up a kind of fast, simple, the capsaicin monomer separation purification method is imperative efficiently.
Summary of the invention
Extraction is a kind of isolation technique simple, easy to operate, that be easy to suitability for industrialized production of installing, and its key is to extract the structure of two-phase system.Extraction agent not only will form with solvent the two-phase system of low mutual solubility, and will have than highly selective target compound.Capsaicin compound has phenolic hydroxyl group and amide group, boiling point is lower, have very high-dissolvability under normal temperature in the organic solvents such as short chain alcohol, acetonitrile, acetone, dimethyl sulfoxide (DMSO), ethyl acetate, and solubleness is very little in water and weak/non-polar solvent (as alkane, alkene).In binary extraction system (as ethyl acetate-water, n-butanol-water, methyl alcohol-normal hexane, acetonitrile-normal hexane etc.) commonly used, wherein one is the organic solvent very high to capsicine solubleness mutually, and other one water or the weakly polar organic solvent very low to capsicine solubleness often mutually, the capsicine partition ratio is very low, separation selectivity is poor thereby cause.
For improving the distribution behavior of capsicine, can add the third solvent in binary extraction system, the third solvent can add entry or low-pole phase, increase capsicine in the solubleness of this phase, also can be added to the organic solvent phase very high to capsicine solubleness, reduce capsicine in the solubleness of this phase, thereby reach the purpose of regulating the capsicine partition ratio.Two-phase to traditional binary extraction system adds respectively another kind of solvent simultaneously, form quaternary extraction two-phase system, also can reach the purpose of regulating capsicine distribution behavior although namely regulate simultaneously capsicine in the method for two phase solubilities, but quaternary extraction system forms complicated, the recycling difficulty of extraction agent and washing composition is larger, does not therefore consider.
From improving capsicine to optionally angle consideration of Dihydrocapsaicin, capsicine and Dihydrocapsaicin textural difference only are that capsicine has carbon-carbon double bond and Dihydrocapsaicin does not have, thereby cause polarity both and to carry out the ability of π-π effect variant with other materials.Therefore, can extract the organic solvent that the polarity of two-phase system or selection contain two keys by adjusting is that extraction agent improves capsicine to the selectivity of Dihydrocapsaicin.
For the mixture of capsicine and Dihydrocapsaicin, take methyl alcohol as solvent, take normal hexane as extraction agent, carry out single-stage extraction under 30 ℃, the partition ratio of capsicine and Dihydrocapsaicin is all less than 0.01; Methanol aqueous solution take the methyl alcohol molar fraction as 25% is as solvent, and normal hexane is extraction agent, and under same experimental conditions, the partition ratio of capsicine and Dihydrocapsaicin is respectively 0.07 and 0.15, and Dihydrocapsaicin reaches 2.1 to the capsicine selectivity; Methanol aqueous solution take the methyl alcohol molar fraction as 30% is as solvent, and the 1-hexene is extraction agent, and the partition ratio of capsicine and Dihydrocapsaicin is respectively 0.31 and 0.63, and Dihydrocapsaicin reaches 2.0 to the capsicine selectivity.Hence one can see that, adopts suitable ternary two-phase extraction system to be used for can obtaining to be more conducive to separating of capsicine and Dihydrocapsaicin the partition ratio of suitability for industrialized production and selectivity coefficient preferably.
Based on above result of study, the present invention proposes a kind ofly take the ternary two-phase system as extraction system, through multistage fractionation extraction, separate the method that obtains the higher capsicine of purity from capsaicin compound.
A kind of from capsaicin compound the method for separating pepper alkali monomer, comprise the following steps:
(1) take capsaicin compound as raw material, be made into stock liquid take polar organic solvent as solvent, the binary mixed solvent that forms take weakly polar organic solvent and middle polarity organic solvent is as extraction agent, take with the stock liquid solvent phase with solvent as washing composition, carry out fractionation extraction; Perhaps, take capsaicin compound as raw material, the binary mixed solvent that forms take polar organic solvent and water is made into stock liquid as solvent, take weakly polar organic solvent as extraction agent, take with the stock liquid solvent phase with solvent as washing composition, carry out fractionation extraction;
Described fractionation extraction is divided into extraction section and washing section, extraction agent enters the fractionation extraction system from the extraction section first step, stock liquid enters the fractionation extraction system from the last step of extraction section, washing composition enters the fractionation extraction system from the first step of washing section, last step merging stock liquid in extraction section enters extraction section together, extraction phase carries out multi-stage counter current extraction mutually with washing, flow out from the first step of washing section the extraction liquid that is rich in Dihydrocapsaicin, flow out the raffinate of enrichment capsicine from the first step of extraction section, collect raffinate;
(2) with the raffinate in step (1) through vacuum concentration, washing and drying, obtain capsicine.
The capsaicin compound raw material that the present invention adopts can directly be bought from market, also can separate obtaining from capsicum.Capsaicin compound mainly is comprised of capsicine and Dihydrocapsaicin, contains in addition Nordihydrocapsaicin, Homodihydrocapsaicin I etc.In described capsaicin compound, the gross weight percentage composition of capsicine and Dihydrocapsaicin is preferably more than 40%.
According to the difference of different extraction system treatment capacities, in stock liquid, the total concn of capsaicin compound is preferably 1 grams per liter～150 grams per liters.If the excessive concentration of capsaicin compound in stock liquid, the viscosity of stock liquid is too large, is unfavorable for extracting mass transfer process; If in stock liquid, the concentration of capsaicin compound is too low, have that feed throughput is little, solvent loss is large, the shortcoming such as less economical of technique, does not have good industrial application value.
Described ternary two-phase extraction system is polar organic solvent-weakly polar organic solvent/middle polarity organic solvent or polar organic solvent/water-weakly polar organic solvent.Compare with binary two-phase extraction system, adopt partition ratio that ternary two-phase extraction system can make capsaicin compound in suitable scope, and capsicine and Dihydrocapsaicin are had better selectivity.
Described polar organic solvent is selected a kind of in methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol, acetonitrile, furfural, acetone, dimethyl sulfoxide (DMSO), tetramethylene sulfone, dimethyl formamide, N-Methyl pyrrolidone, propylene carbonate.
It is that 6～14 straight-chain paraffin, carbonatoms are a kind of in 6～10 1-alkene, benzene, toluene, o-Xylol, m-xylene, p-Xylol that described weakly polar organic solvent is selected carbonatoms.
Described middle polarity organic solvent is selected a kind of in methyl acetate, ethyl acetate, butylacetate, methyl tertiary butyl ether.
The molar fraction of the binary mixed solvent Semi-polarity organic solvent that described polar organic solvent and water form is preferably 20%～95%.
The binary mixed solvent that polar organic solvent of the present invention or polar organic solvent and water form has higher solubility to capsaicin compound.If the molar fraction of the polar organic solvent in binary mixed solvent is too high, the partition ratio of capsaicin compound is too high, is unfavorable for industrial applications; If the molar fraction of polar organic solvent is too low, the solubleness to capsicine is too little, and the extraction process treatment capacity is low.
In the binary mixed solvent that described weakly polar organic solvent and middle polarity organic solvent form, the molar fraction of middle polarity organic solvent is preferably in 10%.
Binary extractant and stock liquid solvent that weakly polar organic solvent of the present invention or weakly polar organic solvent and middle polarity organic solvent form can form two-phase system.If in binary extractant, the molar fraction of middle polarity organic solvent is too high, can cause the mutual solubility of extraction two-phase system larger, separation selectivity reduces.
Described washing composition and raw material solvent are selected homogeneous solvent, when capsaicin compound is had better dissolving power, can form the less liquid of mutual solubility-liquid two-phase system with extraction agent.
The service temperature of described fractionation extraction is preferably 20 ℃～70 ℃, if temperature is too low, the two-phase rate of mass transfer reduces, and reaches the extraction equilibrium required time longer, is unfavorable for production operation; If excess Temperature, solvent evaporates is serious, can reduce partition ratio and the selectivity of fractionation extraction.
When carrying out fractionation extraction, consider the factors such as quality product, production cost, the stream ratio between stock liquid, extraction agent, washing composition three is 0.2～8: 6.7～60: 1.
existing fractionation extraction equipment (as shown in Figure 1) is adopted in fractionation extraction of the present invention, fractionation extraction is divided into extraction section and washing section, extraction agent enters the fractionation extraction system from the extraction section first step, stock liquid enters the fractionation extraction system from the last step of extraction section, washing composition enters the fractionation extraction system from the first step of washing section, merge stock liquid at the extraction section last step and enter together extraction section, extraction phase carries out multi-stage counter current extraction mutually with washing, flow out from the first step of washing section the extraction liquid that is rich in Dihydrocapsaicin, flow out the raffinate of enrichment capsicine from the first step of extraction section, collect raffinate.
The present invention adopts high performance liquid chromatography (HPLC) method to carry out quantitative analysis to the concentration of capsicine, and HPLC concrete analysis condition is: Waters X-Bridge C
18Post (3.9 * 150mm, particle diameter 5 μ m), 30 ℃ of column temperatures, moving phase is methyl alcohol: water=70: 30 (v/v), flow velocity 1ml/min, detector are UV-detector, wavelength is 218nm.
In the present invention, the method for calculation of yield and purity are as follows:
The weight of capsicine * 100% in the weight/raw material of capsicine in yield=product;
The total mass of the quality/product of capsicine * 100% in absolute purity=product;
Capsicine: the quality of capsicine in Dihydrocapsaicin relative content=product: the quality of Dihydrocapsaicin in product.
Compared with prior art, the present invention has following advantage:
1. the present invention adopts ternary two-phase extraction system separating pepper alkali from capsaicin compound, this extraction system has higher selection separating power to the close capsaicin compound of structure, the purity of the capsicine that obtains through separation method of the present invention is: absolute purity＞90%, capsicine: Dihydrocapsaicin relative content＞95: 5 (w: w, mass ratio), have broad application prospects;
2. the present invention adopts the fractionation extraction technology, and is easy and simple to handle, and the consumption of industrial chemicals less, production capacity is high, cost is low;
3. the inventive method adopts the condition of optimizing, and the purity of capsicine and the rate of recovery all can reach more than 95%.
Description of drawings
Fig. 1 is the structural representation of existing multistage fractionation extraction equipment.
Embodiment
To help to understand the present invention by following embodiment, but also limit never in any form content of the present invention.
with commercial capsaicin compound (capsicine wherein, the overall weight percent of Dihydrocapsaicin is 92%) be made into the tetramethylene sulfone aqueous solution (the tetramethylene sulfone molar fraction is 20%) stock liquid that capsaicin compound concentration is 3 grams per liters, take dodecane as extraction agent, take the tetramethylene sulfone aqueous solution (the tetramethylene sulfone molar fraction is 20%) as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 0.3: 20: 1, under 30 ℃ in fractionation extraction device shown in Figure 1 (totally 15 grades of extraction sections, totally 6 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 98.9%, capsicine: the Dihydrocapsaicin relative content is 99.1: 0.9, and yield is 98.7%.
with commercial capsaicin compound (capsicine wherein, the overall weight percent of Dihydrocapsaicin is 92%) be made into methanol aqueous solution (the methyl alcohol molar fraction is 95%) stock liquid that capsaicin compound concentration is 50 grams per liters, take the 1-octene as extraction agent, take methanol aqueous solution (the methyl alcohol molar fraction is 95%) as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 6: 50: 1, under 55 ℃ in fractionation extraction device shown in Figure 1 (totally 17 grades of extraction sections, totally 3 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 98.3%, capsicine: the Dihydrocapsaicin relative content is 98.8: 1.2, and yield is 99.0%.
Embodiment 3
capsicum skin powder is repeatedly leached with ethanol, filtrate is concentrated, add again the alcohol of volume fraction 70% to stir under thermal condition, the Diluted Alcohol that is dissolved with capsaicin compound obtains capsicine and Dihydrocapsaicin after concentrated distillation overall weight percent is 78% solid capsaicin compound, the solid and the acetonitrile that obtain are made into the stock liquid that capsaicin compound concentration is 85 grams per liters, take n-hexane/ethyl acetate binary mixed solvent (wherein the molar fraction of ethyl acetate is 5%) as extraction agent, take acetonitrile as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 2.6: 27: 1, under 45 ℃ in fractionation extraction device shown in Figure 1 (totally 16 grades of extraction sections, totally 8 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 95.9%, capsicine: the Dihydrocapsaicin relative content is 97.2: 2.8, and yield is 96.5%.
Embodiment 4
capsicum skin powder is repeatedly leached with ethanol, filtrate is concentrated, add again the alcohol of volume fraction 60% to stir under thermal condition, the Diluted Alcohol that is dissolved with capsaicin compound obtains capsicine and Dihydrocapsaicin after concentrated distillation overall weight percent is 42% solid capsaicin compound, the solid and the aqueous acetone solution (molar fraction of acetone is 60%) that obtain are made into the stock liquid that capsaicin compound concentration is 90 grams per liters, take benzene as extraction agent, take aqueous acetone solution (molar fraction of acetone is 60%) as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 0.3: 6.7: 1, under 50 ℃ in fractionation extraction device shown in Figure 1 (totally 16 grades of extraction sections, totally 15 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 95.1%, capsicine: the Dihydrocapsaicin relative content is 96.8: 3.2, and yield is 96.3%.
Embodiment 5
capsicum skin powder is repeatedly leached with ethanol, filtrate is concentrated, add again the alcohol of volume fraction 65% to stir under thermal condition, the Diluted Alcohol that is dissolved with capsaicin compound obtains capsicine and Dihydrocapsaicin after concentrated distillation overall weight percent is 59% solid capsaicin compound, the solid and the N-Methyl pyrrolidone that obtain are made into the stock liquid that capsaicin compound concentration is 150 grams per liters, take normal heptane/ethyl acetate binary mixed solvent (wherein the molar fraction of ethyl acetate is 1%) as extraction agent, take N-Methyl pyrrolidone as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 8: 60: 1, under 45 ℃ in fractionation extraction device shown in Figure 1 (totally 8 grades of extraction sections, totally 7 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 96.7%, capsicine: the Dihydrocapsaicin relative content is 97.8: 2.2, and yield is 97.1%.
Embodiment 6
with commercial capsaicin compound (capsicine wherein, the overall weight percent of Dihydrocapsaicin is 92%) be made into dimethyl sulphoxide aqueous solution (the dimethyl sulfoxide (DMSO) molar fraction is 55%) stock liquid that capsaicin compound concentration is 20 grams per liters, take n-decane as extraction agent, with dimethyl sulphoxide aqueous solution (the dimethyl sulfoxide (DMSO) molar fraction is 55%) washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 5.3: 21: 1, under 70 ℃ in fractionation extraction device shown in Figure 1 (totally 12 grades of extraction sections, totally 8 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 98.7%, capsicine: the Dihydrocapsaicin relative content is 99.3: 0.7, and yield is 98.2%.
Embodiment 7
capsicum skin powder is repeatedly leached with ethanol, filtrate is concentrated, add again the alcohol of volume fraction 70% to stir under thermal condition, the Diluted Alcohol that is dissolved with capsaicin compound obtains capsicine and Dihydrocapsaicin after concentrated distillation overall weight percent is 78% solid capsaicin compound, the solid and the dimethyl formamide that obtain are made into the stock liquid that capsaicin compound concentration is 120 grams per liters, take dodecane/methyl tertiary butyl ether binary mixed solvent (wherein the molar fraction of methyl tertiary butyl ether is 10%) as extraction agent, take dimethyl formamide as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 0.9: 10: 1, under 40 ℃ in fractionation extraction device shown in Figure 1 (totally 10 grades of extraction sections, totally 7 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 95.2%, capsicine: the Dihydrocapsaicin relative content is 96.7: 3.3, and yield is 96.1%.
Embodiment 8
capsicum skin powder is repeatedly leached with ethanol, filtrate is concentrated, add again the alcohol of volume fraction 65% to stir under thermal condition, the Diluted Alcohol that is dissolved with capsaicin compound obtains capsicine and Dihydrocapsaicin after concentrated distillation overall weight percent is 59% solid capsaicin compound, the solid and the furfural aqueous solution (wherein the molar fraction of furfural is 80%) that obtain are made into the stock liquid that capsaicin compound concentration is 10 grams per liters, take the 1-octene as extraction agent, take furfural aqueous solution (wherein the molar fraction of furfural is as 80%) as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 2.6: 42: 1, under 20 ℃ in fractionation extraction device shown in Figure 1 (totally 8 grades of extraction sections, totally 8 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 96.2%, capsicine: the Dihydrocapsaicin relative content is 98.1: 1.9, and yield is 97.3%.
Embodiment 9
capsicum skin powder is repeatedly leached with ethanol, filtrate is concentrated, add again the alcohol of volume fraction 65% to stir under thermal condition, the Diluted Alcohol that is dissolved with capsaicin compound obtains capsicine and Dihydrocapsaicin after concentrated distillation overall weight percent is 62% solid capsaicin compound, the solid and the propyl carbinol that obtain are made into the stock liquid that capsaicin compound concentration is 140 grams per liters, take the tetradecane/butylacetate binary mixed solvent (wherein the molar fraction of butylacetate is 2%) as extraction agent, take dimethyl formamide as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 7.3: 16: 1, under 40 ℃ in fractionation extraction device shown in Figure 1 (totally 18 grades of extraction sections, totally 10 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 97.6%, capsicine: the Dihydrocapsaicin relative content is 98.3: 1.7, and yield is 99.2%.
Embodiment 10
with commercial capsaicin compound (capsicine wherein, the overall weight percent of Dihydrocapsaicin is 92%) be made into the propylene carbonate aqueous solution (the propylene carbonate molar fraction is 30%) stock liquid that capsaicin compound concentration is 10 grams per liters, take o-Xylol as extraction agent, take the propylene carbonate aqueous solution (the propylene carbonate molar fraction is 30%) as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 3.2: 10: 1, under 55 ℃ in fractionation extraction device shown in Figure 1 (totally 9 grades of extraction sections, totally 10 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 99.3%, capsicine: the Dihydrocapsaicin relative content is 99.8: 0.2, and yield is 99.3%.
Embodiment 11
with commercial capsaicin compound (capsicine wherein, the overall weight percent of Dihydrocapsaicin is 92%) be made into ethylene glycol the stock liquid that capsaicin compound concentration is 60 grams per liters, take 1-nonene/butylacetate binary mixed solvent (wherein the molar fraction of butylacetate is 0.5%) as extraction agent, take ethylene glycol as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 0.5: 6.7: 1, under 20 ℃ in fractionation extraction device shown in Figure 1 (totally 16 grades of extraction sections, totally 7 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 93.2%, capsicine: the Dihydrocapsaicin relative content is 94.3: 5.7, and yield is 92.4%.
Embodiment 12
capsicum skin powder is repeatedly leached with ethanol, filtrate is concentrated, add again the alcohol of volume fraction 70% to stir under thermal condition, the Diluted Alcohol that is dissolved with capsaicin compound obtains capsicine and Dihydrocapsaicin after concentrated distillation overall weight percent is 78% solid capsaicin compound, the solid and the Virahol that obtain are made into the stock liquid that capsaicin compound concentration is 90 grams per liters, take 1-nonene/methyl acetate binary mixed solvent (wherein the molar fraction of methyl acetate is 6%) as extraction agent, take Virahol as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 6.2: 19: 1, under 35 ℃ in fractionation extraction device shown in Figure 1 (totally 19 grades of extraction sections, totally 7 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 94.3%, capsicine: the Dihydrocapsaicin relative content is 95.7: 4.3, and yield is 92.1%.
Embodiment 13
with commercial capsaicin compound (capsicine wherein, the overall weight percent of Dihydrocapsaicin is 92%) be made into aqueous ethanolic solution (wherein the molar fraction of ethanol is 20%) stock liquid that capsaicin compound concentration is 15 grams per liters, take m-xylene as extraction agent, take aqueous ethanolic solution (wherein the molar fraction of ethanol is 20%) as washing composition, stock liquid, extraction agent, stream ratio between the washing composition three is 3.9: 18: 1, under 55 ℃ in fractionation extraction device shown in Figure 1 (totally 15 grades of extraction sections, totally 6 grades of washing sections) carry out fractionation extraction in, collect raffinate, remove through vacuum concentration and anhydrate and organic solvent, after washing, drying obtains final product.Analyze through HPLC, in final product, the absolute purity of capsicine is 94.1%, capsicine: the Dihydrocapsaicin relative content is 95.9: 4.1, and yield is 93.5%.
Claims (1)
1. the method for a separating pepper alkali monomer from capsaicin compound, is characterized in that, comprises the following steps:
(1) take capsaicin compound as raw material, be made into stock liquid take polar organic solvent as solvent, the binary mixed solvent that forms take weakly polar organic solvent and middle polarity organic solvent is as extraction agent, take with the stock liquid solvent phase with solvent as washing composition, carry out fractionation extraction; Perhaps, take capsaicin compound as raw material, the binary mixed solvent that forms take polar organic solvent and water is made into stock liquid as solvent, take weakly polar organic solvent as extraction agent, take with the stock liquid solvent phase with solvent as washing composition, carry out fractionation extraction;
The gross weight percentage composition of capsicine and Dihydrocapsaicin 〉=40% in described capsaicin compound;
In described stock liquid, the total concn of capsaicin compound is 1 grams per liter～150 grams per liters;
Described polar organic solvent is a kind of in methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol, acetonitrile, furfural, acetone, dimethyl sulfoxide (DMSO), tetramethylene sulfone, dimethyl formamide, N-Methyl pyrrolidone, propylene carbonate;
Described weakly polar organic solvent is that carbonatoms is that 6～14 straight-chain paraffin, carbonatoms are a kind of in 6～10 1-alkene, benzene, toluene, o-Xylol, m-xylene, p-Xylol;
Described middle polarity organic solvent is a kind of in methyl acetate, ethyl acetate, butylacetate, methyl tertiary butyl ether;
In the binary mixed solvent that described weakly polar organic solvent and middle polarity organic solvent form, the molar fraction of middle polarity organic solvent is in 10%;
The molar fraction of the binary mixed solvent Semi-polarity organic solvent that described polar organic solvent and water form is 20%～95%;
The service temperature of described fractionation extraction is 20 ℃～70 ℃;
Stream ratio between described stock liquid, extraction agent, washing composition three is 0.2～8:6.7～60:1; Described fractionation extraction is divided into extraction section and washing section, extraction agent enters the fractionation extraction system from the extraction section first step, stock liquid enters the fractionation extraction system from the last step of extraction section, washing composition enters the fractionation extraction system from the first step of washing section, last step merging stock liquid in extraction section enters extraction section together, extraction phase carries out multi-stage counter current extraction mutually with washing, flow out from the first step of washing section the extraction liquid that is rich in Dihydrocapsaicin, flow out the raffinate of enrichment capsicine from the first step of extraction section, collect raffinate;
(2) with the raffinate in step (1) through vacuum concentration, washing and drying, obtain capsicine.
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