CN102433367B - Preparation method of microporous starch having high specific surface area - Google Patents
Preparation method of microporous starch having high specific surface area Download PDFInfo
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Abstract
The invention discloses a preparation method of microporous starch having a high specific surface area. The preparation method adopts native starch as a raw material and comprises the following steps of removing proteins, lipid and impurities of native starch, carrying out primary starch acid hydrolysis to a limited degree by low-frequency pulsed ultrasound induction, and carrying out enzymatic hydrolysis by amylase under the conditions of low-frequency pulsed ultrasound induction to obtain the microporous starch having a high specific surface area, wherein apertures having appropriate aperture sizes and appropriate depth are formed on the whole surface of the microporous starch having a high specific surface area. The specific surface area of the microporous starch obtained by the preparation method is larger than that of microporous starch obtained by a single enzymatic hydrolysis method by above 60%. A water and oil adsorption capability of the microporous starch obtained by the preparation method is higher than that of the microporous starch obtained by the single enzymatic hydrolysis method by above 30%.
Description
Technical field
The present invention relates to a kind of preparation method of microporous starch having high specific surface area, the micropore starch that the method is prepared, its specific surface area is than using separately the resulting specific surface area of enzyme solution Duo more than 60%, to the adsorptive power raising of water and grease more than 30%.
Background technology
Starch belongs to a kind of of polysaccharide, is the nutrient of storing in plant materials, and it and protein, fiber, grease, sugar, mineral substance etc. are present in the seed, root, piece root of farm crop jointly.Starch is the white powder of no color or smell, has grain pattern and water absorbability, density 1.499～1.513.Starch granules is water insoluble, and industrial is to utilize this character, adopts levigation method technique, and non-starch impurities is removed, and obtains the higher starch product of purity.Table 1 has provided the chemical constitution of starch in the frequently seen plants.
Table 1: the chemical constitution of starch
| Starch | Moisture (%) | Lipid (butt, %) | Protein (%) | Ash content (%) | Phosphorus (%) |
| Corn | 13 | 0.60 | 0.35 | 0.10 | 0.015 |
| Wheat | 14 | 0.80 | 0.40 | 0.15 | 0.060 |
| Glutinous corn | 13 | 0.20 | 0.25 | 0.07 | 0.007 |
| Potato | 19 | 0.05 | 0.06 | 0.40 | 0.080 |
| Cassava | 13 | 0.10 | 0.10 | 0.20 | 0.010 |
The starch granules water content is generally in the 10-20% left and right.Moisture in starch granules is equilibrium state with moisture in ambient air and exists, the dry air moisture that can shed, and there was dampness in the air can absorb moisture, the absorption of moisture and to scatter and disappear be reversible.And lipoid substance and starch molecule are combined into chelation structure and exist, and gelatinization, expansion and the dissolving of starch granules had stronger restraining effect.
Observe under opticmicroscope, polarizing microscope and scanning electronic microscope, corn starch granules is less, is many trilaterals, and potato starch particle is larger, and ovalize is spill on the tapioca (flour) particle.Table 2 has provided the size of common starch granules.
Table 2: different granule sizes
| Starch | Magnitude range (μ m) | Average range (μ m) |
| Corn | 5-25 | 15 |
| Potato | 15-100 | 33 |
| Cassava | 5-35 | 20 |
| Sweet potato | 15-55 | 30 |
| Wheat | 2-35 | -- |
| Chinese sorghum | 5-25 | 15 |
| Rice | 3-8 | 5 |
Starch granules has crystalline structure, intermolecular regular arrangement of the part of particle, and another one is amorphous structure, intermolecular arrangement does not have regularity in a jumble.Although starch molecule has numerous hydroxyls, wetting ability is very strong, and the starch granules ball is water insoluble, and this is because the cause by hydrogen bonded between hydroxyl, and wherein the moisture in particle has also participated in the combination of hydrogen chain; Simultaneously, starch granules also has perviousness, and water and the aqueous solution can freely infiltrate granule interior.Starch contacts with liquor iodi mitis very soon and to become blue, shows that iodine has infiltrated very soon granule interior and starch and reacted and present blueness; And blue starch granules is when meeting with hypo solution, and blue can the disappearance very soon shows that hypo solution has infiltrated granule interior very soon.This colour-change fast shows, starch granules has very high perviousness.The amorphous domain of starch granules inside has higher perviousness, and chemical reaction mainly just occurs in this zone.
Starch is comprised of amylose starch (amylocellulose) and amylopectin (starch cortex) two portions, and their shared ratios in starch are different with the kind of plant.Amylose starch is the chain compound that is combined into α-Isosorbide-5-Nitrae-glycosidic link by glucose, and the content in starch is about 10～30%.Amylose starch can be dissolved in hot water and not become pasty state, can is maltose by amylorrhexis, meets the aobvious blueness of iodine; And outside being connected divided by α-Isosorbide-5-Nitrae-glycosidic link between glucose molecule in amylopectin, also have with α-1, the 6-glycosidic link is connected, so with branch, approximately 20 glucose units just have a branch.Amylopectin is insoluble in cold water, and expanding with the hot water effect forms pasty state, and only having peripheral side chain can be maltose by amylorrhexis, meets iodine and is purple or red-violet colour.Table 3 has provided the content of straight chain and amylopectin in different varieties starch.
Table 3: the content of straight chain and amylopectin in different varieties starch
| Starch | Amylose content (%) | Amylopection content (%) |
| Corn | 27 | 73 |
| Glutinous corn | 0 | 100 |
| Chinese sorghum | 27 | 73 |
| Glutinous indian millet | 0 | 100 |
| Rice | 19 | 81 |
| Glutinous rice | 0 | 100 |
| Wheat | 27 | 73 |
| Potato | 20 | 80 |
| Cassava | 17 | 83 |
| Sweet potato | 18 | 82 |
| High straight-chain maize | 70 | 30 |
The chemical structural formula of starch can be write as (C
6H
10O
5)
n, C wherein
6H
10O
5Be AGU, n is the polymerization degree.Starch molecule is to slough water molecules by the polymer that is formed by connecting by glycosidic linkage by glucose, and the AGU quantity that forms starch molecule is called the polymerization degree.C
6H
10O
5The molecular weight of AGU is 162, multiply by the molecular weight that polymerization degree n can get starch.The potato amylose polymerization degree between 1000-6000, average approximately 3000; The corn amylose starch polymerization degree on average is about 800 between 200-1200.The polymerization degree of amylopectin is on average more than 1,000,000, and molecular weight is more than 200,000,000, for maximum in natural high moleculer eompound.
Porous-starch refers to adopt physics, machinery or biochemical method to make starch granules be formed a kind of New Modified Starch of hole to inside by the surface.At present, have following three kinds of methods can make porous-starch:
(1) physical method: as methods such as ultrasonication, sprayings;
(2) mechanical means: as mechanical impact etc.;
(3) biochemical method: as pure sex change, acid hydrolysis, enzymic hydrolysis etc.
In above-mentioned several method, when a certain method of independent use was carried out the preparation of micropore starch, not only each method itself existed certain limitation, and is as higher in the production cost of ultrasonication and mechanical impact method, is difficult for realizing industrialization; The porous-starch that spray method and pure degeneration methods form is a kind of solid popcorn polymer spheroid, and adsorption only occurs in the gully of surface irregularity, and adsorptive capacity is limited; Acid-hydrolysis method speed of reaction under gelatinization point is slower, and degraded differs, and randomness is strong, is difficult for forming poroid; Although and the enzyme hydrolysis method effect is better, enzyme itself is expensive, and production cost is larger etc., and the specific surface area of resulting micropore starch is all less, and is all limited to the adsorptive power of water and grease.
Summary of the invention
The object of the invention is to, a kind of preparation method of microporous starch having high specific surface area is provided, the micropore starch that the method is prepared, its specific surface area be than using separately the resulting specific surface area of enzyme solution Duo more than 60%, to the adsorptive power raising of water and grease more than 30%.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of preparation method of microporous starch having high specific surface area, it is characterized in that, the method is take ative starch as raw material, after protein in removing ative starch, lipid and impurity, induce the lower preliminary acid hydrolysis of starch being carried out limited extent in the low-frequency pulse ultrasonic wave, then carry out enzymolysis with amylase again under the low-frequency pulse ultrasonic wave is induced, namely obtain the microporous starch having high specific surface area that the surface is covered with suitable aperture and the degree of depth.
Concrete preparation is carried out as follows:
1) ative starch pre-treatment
The ative starch pre-treatment comprises the pre-gelatinization of protein in ative starch, lipid and Impurity removal and starch;
In ative starch, the process of protein, lipid and Impurity removal is:
The sig water of ative starch with concentration 0.2% soaked 0.5 hour～2.5 hours, carry out colloidal mill after immersion, cross 100-300 order mesh screen after colloidal mill, centrifugal, washing, 40 ℃ of dryings;
The process of the pre-gelatinization of starch is:
It is 15%～55% starch emulsion that dried starch is mixed with content, stirs 5min～25min under 55 ℃～85 ℃ conditions, centrifugal, and precipitation then 25 ℃～50 ℃ dryings, is pulverized;
2) the low-frequency pulse ultrasonic wave is induced the preliminary acid hydrolysis of starch of limited extent
Take starch after the pre-gelatinization of a certain amount of starch in beaker, be that 20%～70% even starch milk is placed in water-bath with sulfuric acid or hydrochloric acid furnishing starch content, carried out limited acid hydrolytic reaction 2 hours～30 hours with the ultrasonic wave of 20kHz～50kHz under room temperature-50 ℃, mixing speed 50r/min～250r/min condition, ultrasonic power is controlled at 100W～600W, ultrasonic pulse is every ultrasonic 10 seconds, interval 15 seconds, use saturated sodium carbonate solution neutralisation of sulphuric acid or hydrochloric acid, filtering and washing after hydrolysis reaction.
3) the low-frequency pulse ultrasonic wave amylorrhexis of inducing
Take the starch after appropriate preliminary acid hydrolysis, be that to be mixed with starch content be 30%～75% starch milk for 3.5～7.0 damping fluid with pH, be 100W～600W at ultrasonic power, ultrasonic pulse is every ultrasonic 10 seconds, interval 15 seconds, under the ultrasonic wave successive induction of frequency 20kHz～50kHz, preheating 5min～40min in the thermostat water bath of 40 ℃～65 ℃, stir 12h～60h with stirrer simultaneously, mixing speed is 50r/min～250r/min; Then the required enzyme amount of starch by theory hydrolysis 20%～80% adds amylase in the starch milk, stop enzyme reaction after water bath with thermostatic control vibration 24h, it is 1%～10% NaOH solution termination reaction with massfraction, suction filtration is washed to get the wet starch sample repeatedly at last, put in baking oven and dry to constant weight under 20 ℃～60 ℃ conditions, pulverize with pulverizer, namely obtain being microporous starch having high specific surface area.
Above-mentioned amylase is wherein one or more of α-amylase, saccharifying enzyme, glucoamylase.
Adopt the prepared micropore starch of operational path of the present invention, its specific surface area is than using separately the resulting specific surface area of enzyme solution to enlarge markedly, and the adsorptive power of water and grease is significantly improved.
Embodiment
According to technical scheme of the present invention, the preparation method of microporous starch having high specific surface area of the present invention, take ative starch as raw material, after protein in removing ative starch, lipid and impurity, induce the lower preliminary acid hydrolysis of starch being carried out limited extent in the low-frequency pulse ultrasonic wave, then carry out enzymolysis with amylase again under the low-frequency pulse ultrasonic wave is induced, namely obtain the microporous starch having high specific surface area that the surface is covered with suitable aperture and the degree of depth.
The applicant finds by the combination of different methods and the many experiments of different starch, through pretreated starch, under low-frequency pulse ultrasonic wave continuous action, at first after the preliminary hydrolysis of peracid, pass through again the enzymolysis of certain hour, the specific surface area of resulting micropore starch during than independent use acidolysis and enzyme solution resulting specific surface area enlarge markedly, the adsorptive power of water and grease all is significantly increased.
In experimentation, find that the principal element that affects the formation of porous-starch specific surface has:
(1) selection of ative starch and pre-treatment are comprising kind, source and the granularity etc. of ative starch;
(2) selection of ultrasonic power;
(3) selection of acid and acidolysis condition comprises the kind of acid, concentration, temperature and the reaction times etc. of acid;
(4) selection of enzyme and enzymatic hydrolysis condition comprises and giving birth to diastatic kind and source, living diastatic concentration, temperature of reaction, pH and reaction times etc.
At concrete experimentation, for above-mentioned factor, the applicant has done respectively following processing:
(1) selection of ative starch and pre-treatment
The starch of different varieties is very large to the sensitivity differences of acid and enzyme, and even also there is difference in the different zones at same starch small grain.Give birth to amylorrhexis and give birth to the impact that starch generally is subjected to starch plant source and enzyme source, the hydrolysis of cereal starch is easier than piece starchy roots, and the percent hydrolysis of same Starches depends on kind, growth conditions, organized layer etc.As pancreatin to the susceptibility of different starch be sequentially: taro＞purple corn＞rice＞wheat＞conventional corn＞sweet potato＞Japanese chestnut＞lotus seeds＞high amylose corn＞Chinese sweet potato (round)＞ginkgo＞lily＞ripe banana＞living banana＞Chinese sweet potato (elongated)＞potato.This is mainly that difference by distribution of the granularity of the content of amylose starch in these starch, starch and the non-reduced end of particle surface starch molecular chain etc. causes.Amylose is high is unfavorable for that living amylase plays a role; The starch granularity is less, and is easier in enzymic hydrolysis.But macrobead can form vesicular structure sometimes, and small-particle is only in its surface corrosion, and this shows that enzyme is inhomogenous to the effect of particle.
Experiment simultaneously finds, with protein or the compound more difficult hydrolysis of amylose starch and the enzymolysis of lipid, and ative starch improves it to the diastatic susceptibility of life through showing after pre-treatment.As remove protein and lipid in starch small grain, and can increase living amylase near the chance of starch particle, improve its enzymolysis speed, more be conducive to the formation of porous-starch; After wheat starch and yam starch process ball-milling processing and gelatinization, not only solvability improves, and also strengthens giving birth to diastatic susceptibility; Before the saccharifying enzyme enzymolysis, starch is carried out damp and hot pre-treatment, can increase it to the susceptibility of enzyme, and the amyloid effect of cereal is better than tubers starch.
(2) selection of ultrasonic power
Ultrasonic wave is a kind of elastic mechanical ripple, and the ultrasonic wave of some strength is conducive to improve the activity of the enzymes such as cellulase, proteolytic enzyme, saccharifying enzyme, Glycosylase.Hyperacoustic action effect is not only relevant with ultrasound intensity, and is simultaneously also relevant with the ambient conditionss such as concentration of target compound.
(3) selection of acid and acidolysis condition
General acid commonly used is dilute sulphuric acid and dilute hydrochloric acid, and rare nitric acid may make starch produce some unnecessary negative reactions when sex change owing to having certain oxidisability, therefore seldom uses.And other acid is also generally seldom used.
Acidolysis condition mainly comprises consumption, temperature of reaction and the reaction times etc. of acid, and under some conditions, some additives also can produce material impact to acidolysis.As when preparing micropore starch with sulphuric acid hydrolysis, add a certain amount of urea in reaction solution, its acidolysis ability can improve greatly.
(4) selection of enzyme and enzymatic hydrolysis condition
Commonly used diastaticly have: α-amylase, beta-amylase, glucoamylase, isoamylase, debranching enzyme, the blue enzyme in general Shandong, Starch phosphorylase etc., its source is animal, plant and microorganism.The amylase activity difference of different sources is very large, as the vigor general sequence of glucoamylase is: aspergillus niger＞flavus＞Fructus Hordei Germinatus; Alpha-starch enzyme activity order is generally: pancreatic juice＞saliva＞fungi.When selecting to give birth to amylase, generally not give birth to the starch degradation ability except soya-beta amylase, the saccharifying enzyme of bacterium beta-amylase and different sources, α-amylase all have the various farinose abilities of degraded more or less.
Find according to applicant's experiment, the hole that α-amylase produces is back taper, and is interior large outer little, and the Kong Ze that glucoamylase produces is taper, inner small and outside big.Therefore, use separately α-amylase or glucoamylase enzymolysis starch, the micropore that obtains is all undesirable, and if they are mixed with certain proportion use, but can produce result preferably, the effect of the standby porous-starch of prozyme coordinate system is better than using separately a certain enzyme.As α-amylase and the saccharifying enzyme that adds equivalent in W-Gum, process 8h under 5.0,25 ℃ of conditions of pH, what the aperture ratio that enzymolysis makes porous-starch was used alone enzyme all wants large; Adopt α-amylase and glucoamylase combination preparation porous-starch effect better in wheat starch, and both mass ratioes are microscopic pattern structure the best of water-intake rate, oil absorbency and the starch granules of 1: 1～1: 4 o'clock formed porous-starch.
The micropore starch of preparation should make the starch small grain surface be covered with the aperture of certain pore size, keeps again the integrity of particle.The factor that affects amylorrhexis mainly contains diastatic consumption, action time, temperature, pH value etc., and oil absorbency and water-intake rate are the important control indexs of preparation porous-starch, and they can directly reflect the absorption property of micropore starch.For example, when the hydrolysising experiment of W-Gum, the optimum enzymolysis condition that draws is: under the low-frequency pulse ultrasonic wave is induced, and 50 ℃ of temperature of reaction, the reaction times is 20h, enzyme liquid addition (massfraction) is that 1.0%, pH value is in 4.8 left and right; And when the hydrolysising experiment at another W-Gum, the optimum enzymolysis condition that draws is: under the low-frequency pulse ultrasonic wave is induced, and 50 ℃ of temperature of reaction, pH value 5.0, reaction times 12h, prozyme consumption are the required enzyme amount of theoretical hydrolysis 60% starch.
In sum, it is as follows that the sequential acid-enzyme solution that the low-frequency pulse ultrasonic wave is induced prepares the general process of micropore starch: after removing the impurity such as protein in ative starch and lipid and it being carried out gelatinization, at first the starch after pre-gelatinization carries out the acid hydrolysis of limited extent to starch under the low-frequency pulse ultrasonic wave is induced, and then carries out enzymolysis with amylase again under the low-frequency pulse ultrasonic wave is induced.
Experiment is simultaneously also found, starch is carried out this step of preliminary acid hydrolysis, also can save in the preparation process of some micropore starchs.For these starch, be not very large to last resulting micropore starch performance impact like this.
Further illustrate the present invention below by example, but invention is not limited to this.
Embodiment 1: the preparation of wheat micropore starch
The removal of the impurity such as albumen and lipid and pre-gelatinization in wheat starch: wheat ative starch (commercially available) soaks with the sig water of concentration 0.2%, and colloidal mill after soaking is crossed 200 order mesh screens, and is centrifugal, washing, 40 ℃ of dryings.
The pre-gelatinization of starch is that dried starch is mixed with content is 35% starch emulsion (W/V), stir under 70 ℃ of conditions after 10min centrifugal, precipitation, 40 ℃ of crushed after being dried;
The preliminary acid hydrolysis that the low-frequency pulse ultrasonic wave is induced: take starch after the pre-gelatinization of a certain amount of starch in the 200mL beaker, starch emulsion with the HCl solution furnishing starch-containing 38% of concentration 12%, then be 500W at ultrasonic power, ultrasonic pulse is every ultrasonic 10 seconds, interval 15 seconds, the 25kHz pulse ultrasonic wave is induced down in the water-bath of 40 ℃ and is heated, stir with electric blender simultaneously, the mixing speed 220r/min of electric blender, stopped reaction after 4 hours, with in saturated sodium carbonate solution and hydrochloric acid, then filtering and washing.
The amylorrhexis that the low-frequency pulse ultrasonic wave is induced: take the starch after appropriate above-mentioned preliminary acid hydrolysis, damping fluid (the mixing solutions of weak acid and salt thereof with pH5.8, as HAc and NaAc) to be mixed with concentration be 60% starch milk, then under the 25kHz pulse ultrasonic wave is induced in 55 ℃ of thermostat water baths preheating 20min, stir 20min with electric blender, mixing speed is 220r/min; Adding proportioning by theory hydrolysis 50% starch in the starch milk is the amylase (α-amylase and saccharifying enzyme) of 5: 1, stops enzyme reaction after water bath with thermostatic control vibration 24h.Suction filtration, washing repeatedly gets the wet starch sample, puts in baking oven in 50 ℃ to dry to constant weight, pulverizes with pulverizer, is the micropore wheat starch.Ultrasonic power is 500W, and ultrasonic pulse is every ultrasonic 10 seconds, interval 15 seconds.
Above-mentioned process low-frequency pulse ultrasonic wave induces the micropore starch of lower sequential acid-enzyme solution to show with scanning electron microscopic observation, and micropore wheat starch shape is cellular, and the micropore that particle surface distributes is about 0.5/μ m
2, the aperture is about 1.0 μ m, and hole depth differs and the darkest reached at particle center.0.3/μ of the hole density m of prepared micropore wheat starch with only using the double enzymolysis method
2Compare, hole density has improved approximately 67%;
The mensuration of water-absorbent and oil absorbency: water-absorbent or oil absorbency are the water that absorbs of micropore starch or the mass ratio of salad oil and micropore starch.With micropore wheat starch and water or the salad oil mix and blend 30min of certain mass, use the vacuum pump suction filtration after changing sand core funnel under constant temperature, until anhydrous or oil droplet drips, then according to its water-absorbent of the poor calculating of sample quality and oil absorbency before and after absorbing.Result shows, induce water-intake rate and the oil absorbency of the micropore wheat starch of lower sequential acid-enzyme solution method preparation to be about respectively 105% and 95% with above-mentioned low-frequency pulse ultrasonic wave, with only compare with the water-intake rate of the prepared micropore wheat starch 72% of double enzymolysis method and 60% oil absorbency, its water-intake rate and oil absorbency increase respectively 33% and 35%.
Embodiment 2: the preparation of Microporous Maize Starch
Raw material: sulfuric acid, W-Gum, α-amylase (α-amylase gives birth to amylase activity 300IU/ml) and saccharifying enzyme (glucoamylase gives birth to amylase activity 350IU/ml) are commercially available.
In the starch of W-Gum, the removal of the impurity such as albumen and lipid is identical with embodiment 1 with pre-gelatinization.
take the W-Gum of the pre-removal of impurities of a certain amount of warp and pre-gelatinization processing in the 200mL beaker, be the acid solution that 5% sulfuric acid is made into every gram starch 2.0mL with concentration, the low-frequency pulse ultrasonic wave is induced down and is heated in the water-bath of 45 ℃ and stir with electric blender simultaneously, 3.5 stopped reaction after hour, use the saturated sodium carbonate solution neutralizing acid, then filtering and washing, take again 15g starch after acid hydrolysis in the 500ml reaction flask, adding the pH value is that 5.6 Sodium phosphate dibasic-citrate buffer solution 100ml sizes mixing, under the low-frequency pulse ultrasonic wave is induced in the thermostat water bath of 55 ℃ after preheating 10min, (α-amylase and saccharifying enzyme mass ratio are 1: 2 to add the mixed enzyme solution of saccharifying enzyme and α-amylase, enzyme concentration is 50ml), stir and to add 4% sodium hydroxide 5ml stopped reaction after 28h, through G 2 sand core funnel suction filtrations, use again distilled water wash, put in 40 ℃ of vacuum drying ovens and be dried to constant weight, pulverize and sieve, namely get micropore W-Gum goods.Ultrasonic frequency is 25kHz, and power is 500 watts, and ultrasonic pulse is every ultrasonic 10 seconds, interval 15 seconds, the mixing speed 250r/min of electric blender.
Water-intake rate and oil absorbency measurement result show, water-intake rate and the oil absorbency of the micropore W-Gum that the sequential acid-enzyme solution method of inducing with above-mentioned low-frequency pulse ultrasonic wave prepares are about respectively 88% and 80%, with only compare with the water-intake rate of the prepared micropore W-Gum 55% of double enzymolysis method and 45% oil absorbency, its water-intake rate and oil absorbency increase respectively 33% and 35%.
Embodiment 3: the preparation of early rice micropore starch
Raw material: early rice starch, moisture content is about 15% after measured; Saccharifying enzyme, Glucoamylase of Aspergillus niger (enzyme is lived and is 500IU/ml); α-amylase (α-amylase gives birth to amylase activity 300IU/ml) is commercially available.
In the starch of early rice starch, the removal of the impurity such as albumen and lipid is identical with embodiment 1 with pre-gelatinization.
Take early rice starch after a certain amount of removal of impurities and pre-gelatinization in the 200mL beaker, the even starch milk of HCl solution furnishing with concentration 12%, the low-frequency pulse ultrasonic wave is induced down in the water-bath of 40 ℃ and is heated, stir with electric blender simultaneously, about stopped reaction after 2.5 hours, with in saturated sodium carbonate solution and hydrochloric acid, then filtering and washing.
The early rice starch that takes again after the 20g acid hydrolysis is placed in the 200mL beaker, adding 40mL, pH is that 3.5 acetate buffer solution is mixed well, add the required saccharifying enzyme of the starch of theoretical hydrolysis 40% and the mixed solution (volume ratio of saccharifying enzyme and α-amylase is 1: 2) of α-amylase, the low-frequency pulse ultrasonic wave is induced down after constant temperature enzymolysis 18h under 50 ℃ and agitation condition, add 4% sodium hydroxide 5mL stopped reaction, centrifugal (2500r/m, 10min), precipitation, 40 ℃ of drying and crushing, cross 200 mesh sieves, screen underflow is the early rice micropore starch.Ultrasonic frequency is 40kHz, and power is 300W, and ultrasonic pulse is every ultrasonic 10 seconds, interval 15 seconds, the mixing speed 220r/min of electric blender.
Show through water-intake rate and oil absorbency measurement result, water-intake rate and the oil absorbency of the micropore early rice starch that the sequential acid-enzyme solution of inducing with above-mentioned low-frequency pulse ultrasonic wave prepares are about respectively 96% and 85%, with only compare with the water-intake rate of the prepared micropore early rice starch 60% of double enzymolysis method and 50% oil absorbency, its water-intake rate and oil absorbency increase respectively 36% and 35%.
Embodiment 4: the preparation of Potato Porous Starch
Raw material: sulfuric acid, α-amylase (α-amylase gives birth to amylase activity 300IU/ml), saccharifying enzyme (glucoamylase gives birth to amylase activity 350IU/ml) and yam starch are commercially available.
Take a certain amount of with the yam starch after method removal of impurities in embodiment 1 in the 200mL beaker, be the acid solution that 5% sulfuric acid is made into every gram starch 2.0mL with concentration, adding 0.75 gram urea by every gram starch simultaneously joins in acid solution, the low-frequency pulse ultrasonic wave is induced down in the water-bath of 40 ℃ and is heated, and stirs with electric blender simultaneously.Stopped reaction after 4 hours is used the saturated sodium carbonate solution neutralizing acid, then filtering and washing.Accurately take again the yam starch 20g after this acidolysis, be placed in the 250mL iodine flask, add the corresponding damping fluid of 40mL to size mixing, α-amylase and saccharifying enzyme mass ratio are 1: 2, and total enzyme amount is 6% of slurries, the low-frequency pulse ultrasonic wave is induced lower effect 8h, 55 ℃ of temperature, pH6.0, water bath with thermostatic control vibration 24h, hunting speed is 300r/min, is 4% NaOH solution termination reaction at last with massfraction.After reaction stops, with suspension 3000r/min centrifugation 15min, and remaining starch distilled water wash, centrifugation.After so repeating 3 times, gained starch is placed in constant temperature blast drying oven, is dried to constant weight with 40 ℃ of temperature, cross 200 mesh sieves after pulverizing, namely get the potato microporous starch goods.Ultrasonic frequency is 40kHz, and power is 300W, and ultrasonic pulse is every ultrasonic 20 seconds, interval 20 seconds.
Water-intake rate and oil absorbency measurement result show, water-intake rate and the oil absorbency of the potato microporous starch that the sequential acid-enzyme solution method of inducing with above-mentioned low-frequency pulse ultrasonic wave prepares are about respectively 115% and 95%, with only compare with the water-intake rate of the prepared potato microporous starch 70% of double enzymolysis method and 60% oil absorbency, its water-intake rate and oil absorbency increase respectively 45% and 35%.
Embodiment 5: the preparation of Porous Starch From Sweet Potato
Raw material: sweet potato starch, top grade product; α-amylase (α-amylase gives birth to amylase activity 300IU/ml): saccharifying enzyme (glucoamylase gives birth to amylase activity 350IU/ml) is commercially available.
Take the 20g sweet potato starch, be placed in the 500mL beaker, add the acetate buffer solution 100mL of pH4.0, the low-frequency pulse ultrasonic wave is induced down preheating 20min in the thermostat water bath of 50 ℃, stirs with electric blender simultaneously.Accurately take α-amylase and the saccharifying enzyme (ratio of α-amylase and saccharifying enzyme is 2: 1) of sweet potato starch weight 2.5%, be made into mixed enzyme solution with damping fluid, all transfer in starch suspension mixed enzyme solution and accurately timing, stopped reaction after stirring reaction 16h, with suspension centrifugal 5min on the 4000r/min whizzer, and moving into constant volume to be measured in volumetric flask after supernatant liquor accurate measuring volume.Remaining starch, is placed in 40 ℃ of constant temperature blast drying ovens with gained starch and is dried to constant weight after so repeating 3 times with distilled water wash and centrifugal, grinds with mortar.
Take sweet potato starch after the 20g removal of impurities in the 500mL beaker, the even starch milk of acetate buffer solution 100mL furnishing that adds pH4.0, the low-frequency pulse ultrasonic wave is induced down preheating 20min in the water-bath of 50 ℃, stir with electric blender simultaneously, about stopped reaction after 4 hours, use the saturated sodium carbonate solution neutralizing acid, then filtering and washing.
The sweet potato starch that takes again after the 10g acid hydrolysis is placed in the 200mL beaker, required α-amylase and the saccharifying enzyme (ratio of α-amylase and saccharifying enzyme is 2: 1) of starch that adds theoretical hydrolysis 50%, the low-frequency pulse ultrasonic wave is induced down after constant temperature enzymolysis 16h under 50 ℃ and agitation condition, add 4% sodium hydroxide 5mL stopped reaction, with the centrifugal (4000r/m of suspension, 5min), gained starch is placed in 45 ℃ of constant temperature blast drying ovens is dried to constant weight, namely get Porous Starch From Sweet Potato after grinding with mortar.Ultrasonic frequency is 25kHz, and power is 400W, and ultrasonic pulse is every ultrasonic 20 seconds, interval 20 seconds, the mixing speed 250r/min of electric blender.
Water-intake rate and oil absorbency measurement result show, water-intake rate and the oil absorbency of the Porous Starch From Sweet Potato that the sequential acid-enzyme solution of inducing with above-mentioned low-frequency pulse ultrasonic wave prepares are about respectively 97% and 88%, with only compare with the water-intake rate of the prepared Porous Starch From Sweet Potato 65% of double enzymolysis method and 55% oil absorbency, its water-intake rate and oil absorbency increase respectively 32% and 33%.
Claims (2)
1. the preparation method of a microporous starch having high specific surface area, it is characterized in that, the method is take ative starch as raw material, after protein in removing ative starch, lipid and impurity, induce the lower preliminary acid hydrolysis of starch being carried out limited extent in the low-frequency pulse ultrasonic wave, then carry out enzymolysis with amylase again under the low-frequency pulse ultrasonic wave is induced, namely obtain the microporous starch having high specific surface area that the surface is covered with suitable aperture and the degree of depth;
Concrete preparation is carried out as follows:
1) ative starch pre-treatment
The ative starch pre-treatment comprises the pre-gelatinization of protein in ative starch, lipid and Impurity removal and starch;
In ative starch, the process of protein, lipid and Impurity removal is:
The sig water of ative starch with concentration 0.2% soaked 0.5 hour～2.5 hours, carry out colloidal mill after immersion, cross 100-300 order mesh screen after colloidal mill, centrifugal, washing, 40 ℃ of dryings;
The process of the pre-gelatinization of starch is:
It is 15%～55% starch emulsion that dried starch is mixed with content, stirs 5min～25min under 55 ℃～85 ℃ conditions, centrifugal, and precipitation then 25 ℃～50 ℃ dryings, is pulverized;
2) the low-frequency pulse ultrasonic wave is induced the preliminary acid hydrolysis of starch of limited extent
Take starch after the pre-gelatinization of a certain amount of starch in beaker, be that 20%～70% even starch milk is placed in water-bath with sulfuric acid or hydrochloric acid furnishing starch content, carried out limited acid hydrolytic reaction 2 hours～30 hours with the ultrasonic wave of 20kHz～50kHz under room temperature-50 ℃, mixing speed 50r/min～250r/min condition, ultrasonic power is controlled at 100 W～600 W, ultrasonic pulse is every ultrasonic 10 seconds, interval 15 seconds, use saturated sodium carbonate solution neutralisation of sulphuric acid or hydrochloric acid, filtering and washing after hydrolysis reaction;
3) the low-frequency pulse ultrasonic wave amylorrhexis of inducing
Take the starch after appropriate preliminary acid hydrolysis, be that to be mixed with starch content be 30%～75% starch milk for 3.5～7.0 damping fluid with pH, be 100W～600W at ultrasonic power, ultrasonic pulse is every ultrasonic 10 seconds, interval 15 seconds, under the ultrasonic wave successive induction of frequency 20 kHz～50kHz, preheating 5min～40min in the thermostat water bath of 40 ℃～65 ℃, stir 12h～60h with stirrer simultaneously, mixing speed is 50r/min～250r/min; Then the required enzyme amount of starch by theory hydrolysis 20%～80% adds amylase in the starch milk, stop enzyme reaction after water bath with thermostatic control vibration 24h, it is 1%～10% NaOH solution termination reaction with massfraction, suction filtration is washed to get the wet starch sample repeatedly at last, put in baking oven and dry to constant weight under 20 ℃～60 ℃ conditions, pulverize with pulverizer, namely obtain being microporous starch having high specific surface area.
2. the method for claim 1, is characterized in that, described amylase is wherein one or more of α-amylase, saccharifying enzyme, glucoamylase.
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