CN108794764A - A kind of controllable regeneration cold water soluble corn starch preparation method of size - Google Patents
A kind of controllable regeneration cold water soluble corn starch preparation method of size Download PDFInfo
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- CN108794764A CN108794764A CN201810711137.6A CN201810711137A CN108794764A CN 108794764 A CN108794764 A CN 108794764A CN 201810711137 A CN201810711137 A CN 201810711137A CN 108794764 A CN108794764 A CN 108794764A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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Abstract
The present invention relates to the development and application of native starch, more particularly to a kind of controllable regeneration cold water soluble corn starch preparation method of size stirs evenly alkali, formamide, water, starch in proportion, and it is 10% mixed solution to be configured to mixed solvent total mass fraction；Magnetic agitation 30min at normal temperatures obtains transparent starch solution, is neutralized with 1.0mol/L HCl, and different concentration ethanol is added and carries out water extraction and alcohol precipitation method to solution, up to no Cl‑Until；It obtains ethyl alcohol starch solution and prepares the different renewable cold water soluble cornstarch of size with spray drying.Starch dissolution process of the present invention is simple, easily controllable, is suitable for the dissolving of different compositions, different types of native starch.
Description
Technical field
The present invention relates to the development and application of native starch, more particularly to a kind of controllable regeneration cold water soluble corn of size
Starch preparation method.
Background technology
Starch is as abundance, cheap, degradable, nontoxic natural resources on a kind of earth, except for food
Outside industry, with non-edible increase, it is developing progressively as starch industry.Common cornstarch, linear fraction account for 28%, branch portion
Divide and account for 72%, average molecular mass is (0.3~3.0) × 106, be constituted with glucose unit a kind of polyhydroxy (2,
3,6 carbon potentials) macromolecule.A large amount of intramolecular, intermolecular hydrogen bonding, make starch not dissolved in cold water, generally require heating
It is reused after being allowed to gelatinization.But starch there is also retrogradation (retrogradation) during storage after gelatinization, this is not
Only increase energy consumption, also brings inconvenience to production application.From the point of view of thermodynamics, the retrogradation trend of gelatinized starch is not only difficult
It avoids, also inhibits the utilization of starch.Overcoming the retrogradation of starch will then solve in starch molecule or intermolecular hydrogen bond
Problem, regeneration cold water soluble corn starch (GCWSS) can improve starch dissolution degree, not change starch primary characteristic, can be one
Determine to overcome the problems, such as starch retrogradation in degree.
GCWSS preparations both at home and abroad mainly have at present：1) double flowing nozzle spray drying process.The method has 80% starch to keep former
Starch granules state.But severe reaction conditions when prepared by this method, need special double flowing nozzle, high equipment cost to need high temperature
Hyperbaric heating steam, energy consumption are larger；2) high temperature and pressure alcohol method.For the condition of same high temperature and pressure to equipment requirement height, energy consumption is big, and
The method is to high amylopectin starch and is not suitable for；3) normal pressure polyol process.The method overcomes the technological requirement of high pressure, but is wanted to temperature
Ask particularly harsh, the GCWSS nature differences otherwise obtained are larger.These three methods are both needed to carry out under high temperature or condition of high voltage,
High energy consumption, equipment investment cost are big.Ethyl alcohol alkaline process is the external relatively new process for developing GCWSS in recent years, has room temperature normal
Pressure carries out the features such as reaction and product quality easy to control, is to prepare the comparatively ideal methods of GCWSS, and development prospect is wide, domestic
This aspect research at present is less.The surfaces GCWSS prepared by the method have certain toughness, are conducive to keep starch particle shapes, glue
Degree significantly improves, performance is more stablized.Its principle is as follows：Largely-OH dissociates to make this weak ion-exchanger band of starch
Negative electricity.Repulsive interaction between negative electrical charge promotes starch granules swell.As alkali concentration increases, this repulsive interaction enhancing, most
The expansion in double helix area is caused to become single-screw eventually, crystalline texture is destroyed, and crystalline sequence changes.Meanwhile ethyl alcohol is deposited
Inhibit granules swell, maintains the integrality of particle, and this integrity is the inhibition destroyed to hydrogen bond so that ethyl alcohol alkali
Method is inadequate to starch degree for the treatment of, while simple separation of ethanol keeps regeneration GCWSS sizes uncontrollable, keeps its application limited.
Invention content
The present invention is to overcome defect described in the above-mentioned prior art, provides a kind of dissolving starch method, prepares size controllably again
Raw cooling water (RCW) soluble corn starch.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of controllable regeneration cold water soluble corn starch preparation method of size, includes the following steps：
(1) alkali, formamide, water, starch are stirred evenly in proportion, it is 10% mixed to be configured to mixed solvent total mass fraction
Close solution；
(2) magnetic agitation 30min at normal temperatures, obtains transparent starch solution, is neutralized with 1.0mol/LHCl, is added not
Water extraction and alcohol precipitation method is carried out to solution with concentration ethanol, up to no Cl-Until；
(3) it obtains ethyl alcohol starch solution and prepares the different renewable cold water soluble cornstarch of size with spray drying.
Inventor has found, under these conditions, can realize being completely dissolved for starch within a short period of time, and pass through reality
Verify bright, starch does not change in the front and back structure of dissolving.
Preferably step (1) described alkali is one kind in sodium hydroxide, potassium hydroxide and lithium hydroxide.
Preferably step (1) the in the mixed solvent alkali quality is starch dosage 14%, and formamide quality is starch quality
12%.
Preferably step (1) described starch is cornstarch, wheaten starch, one kind in starch from sweet potato starch.
Preferably step (2) described mixing time is 30min, mixing speed 500r/min.
Preferably step (2) described room temperature is 0-25 DEG C.
Preferably step (2) described different concentration ethanol is 60% ethyl alcohol of first time mass concentration, and addition is starch
2 times of liquor capacity is quickly stood for 24 hours after stirring；It is starch solution volume 2 that second, which is used 75% ethyl alcohol of mass concentration, addition,
Times, quickly stood for 24 hours after stirring；Third time absolute ethyl alcohol, addition are starch solution same volume, are quickly stood after stirring
For 24 hours, this method is water extraction and alcohol precipitation method, secondary use after used ethyl alcohol is collected.
Preferably step (3) the adverse current tubule spray drying drying tower is special 304 stainless steel sprayed suitable for ethyl alcohol
Closed drying tower, wherein dry inlet temperature is 160-180 DEG C；Outlet temperature is 80-100 DEG C；Jet size is 1.5mm,
One kind in 1.25mm, 0.75mm.
Compared with prior art, the beneficial effects of the invention are as follows：
1. starch dissolution process of the present invention is simple, easily controllable, it is not required to, by sulfonation, activation, oxidation, be suitable for
The dissolving of difference composition, different types of native starch, raw material is adjustable, and range is wide；
2. the starch dissolution method mild condition of the present invention, temperature requirement is not high, and solvent nature is stablized, and Environmental Safety is honest and clean
Valence is easy to get, and does not need special safe practice investment, does not need high temperature high voltage resistant equipment, investment of production is few, at low cost；
3. the present invention obtains regeneration cold water soluble corn starch using spray drying, size is controllable, is conducive to starch into one
Step application.
4. the starch solvent performance of the present invention is stablized, non-corrosive, recyclable processing, non-pollution discharge can save raw material,
It is highly practical, easily realize industrialization promotion.
Description of the drawings
Fig. 1 is 1 raw material cornstarch of embodiment and the renewable cold water soluble cornstarch FT-IR curves of product, a in figure
The FT-IR curves of the renewable cold water soluble cornstarch of product of the present invention；B is raw material cornstarch FT-IR curves；
Fig. 2 is 1 raw material cornstarch of embodiment and the renewable cold water soluble cornstarch XRD spectrum of product, a sheets in figure
The XRD curves of the renewable cold water soluble cornstarch of invention product；B is raw material cornstarch XRD curves in figure；
Fig. 3 a are 1 raw material cornstarch SEM curves of embodiment,
Fig. 3 b are the renewable cold water soluble cornstarch SEM curves of 1 product of embodiment,
Fig. 4 is 1 raw material cornstarch of embodiment and the renewable cold water soluble cornstarch DSC curve of product, and a is in figure
Raw material cornstarch DSC curve；Scheme the DSC curve of the renewable cold water soluble cornstarch of b products of the present invention；
Fig. 5 a are 1 raw material cornstarch petrographic microscope image of embodiment；
Fig. 5 b are the renewable cold water soluble cornstarch petrographic microscope image of 1 product of embodiment.
Specific implementation mode
With reference to embodiment, the present invention will be further described.These embodiments are retouched to the typical case of the present invention
It states, however, the present invention is not limited thereto.Experimental method as used in the following examples unless otherwise specified, is conventional method, is made
Raw material, reagent etc., no specified otherwise can raw materials and reagents obtained from commercial sources such as regular market purchases.
Embodiment 1
Being configured to mass fraction after 5g cornstarch, 0.6g formamides, 56.88g water, 0.72g sodium hydroxides are mixed is
10% mixed solution, 500r/min stir 30min, obtain transparent starch solution, neutralized with 1.0mol/LHCl, add for the first time
Enter 60% ethanol water 120ml, is quickly stood for 24 hours after stirring；Second of 75% ethanol water 120ml of addition, is quickly stirred
It is stood for 24 hours after mixing；Absolute ethyl alcohol 60ml is added in third time, is quickly stood for 24 hours after stirring.Spray drying, inlet temperature 160
DEG C, outlet temperature is 80 DEG C, jet size 1.5mm, and renewable cold water soluble cornstarch is obtained after spray drying.
It is solvable to raw material cornstarch and the product regeneration of this fact Example using Fourier Transform Infrared Spectrometer (FT-IR)
Property cold water cornstarch analyzed, gained FT-IR spectrograms as shown in Figure 1, in figure a be raw material cornstarch FT-IR curves, b
For the FT-IR curves of product regeneration cold water soluble corn starch.As can be seen from the figure solution treatment of the present invention is again
Raw cooling water (RCW) corn starch structure is consistent substantially with former corn starch structure, illustrates former cornstarch in the method for the invention
It is directly dissolved in solution.
Raw material cornstarch and product regeneration cold water soluble corn starch to the present embodiment carry out solubility test, molten
Solution degree test method is as follows：Take 1g samples or ative starch in 100ml distilled water, room temperature 500r/min electric stirring 10min, so
4000rpm centrifuges 10min afterwards, draws 25ml supernatant liquors in evaporating dish, 45 DEG C of dry 48h or more, weighing is recorded as W1, meter
Calculate solubility.
W in formula1：Starch quality in supernatant liquor, g；Ws：Starch sample gross mass, g.
It is 3.63% to measure former cornstarch solubility, and it is 92.05% to obtain renewable starch dissolution degree.
X-ray diffraction analysis is carried out, gained XRD spectra is as shown in Fig. 2, a is the XRD spectral lines of raw material cornstarch, b in figure
For the XRD spectral lines of the renewable cold water soluble cornstarch of product.From diffraction peak intensity and the position of Fig. 2 it is found that former corn forms sediment
It is one unimodal that powder in 2 θ is that 17.02 ° and 19.49 ° places have, at the same 2 θ for 22.09 ° with 23.85 ° at have be connected it is bimodal, then
2 θ are that the characteristic peak crystallized at 22 °, 23 ° and 17 ° all disappears cornstarch in the methods of the invention in Treatment XRD diagram
Dissolving and regenerative process crystal structure in the solution are changed, and crystallinity reduces, with hydrogen inside and outside destruction starch molecule
The solution principle saying of key is almost the same.
Raw material cornstarch and product regeneration cold water soluble corn starch to the present embodiment carry out SEM and grain size point
Analysis, gained SEM spectrograms are as shown in Figure 3a and Figure 3b shows, and Fig. 3 a are that the SEM of raw material cornstarch schemes, and Fig. 3 b are the renewable cold water of product
The SEM of soluble corn starch schemes.From the SEM of Fig. 2 it is found that the cornstarch dissolving in the solution in the methods of the invention and
Regenerative process grain structure is changed, and corn starch granules become smaller but maintain integrality.By granularmetric analysis
Former cornstarch average grain diameter is 24.682 μm, and regeneration soluble corn starch average grain diameter is 13.203 μm.
Raw material cornstarch and product regeneration cold water soluble corn starch to the present embodiment carry out dsc analysis, gained
For DSC spectrograms as shown in figure 4, a is the DSC spectral lines of raw material cornstarch in figure, b is the renewable cold water soluble cornstarch of product
DSC spectral lines.As can be seen from Figure 4, former cornstarch glass transition temperature is 140 DEG C, renewable cold water soluble cornstarch glass
It is 110 DEG C to change temperature, and decomposition temperature reduces after illustrating its dissolving.
Raw material cornstarch and product regeneration cold water soluble corn starch solution to the present embodiment carry out polarized light microscopy
Analysis, gained skin petrographic microscope are imaged as shown in figure 5 a and 5b, and Fig. 5 a are the polarized light microscopy image of raw material cornstarch,
Fig. 5 b are the polarized light microscopy image of the renewable cold water soluble cornstarch of product.It can be seen that from Fig. 5 b in cornstarch
After middle addition sodium hydroxide/formyl amine aqueous solution, polarisation " ten " word of corn starch granules is destroyed, in the solution starch with
NaOH, formamide are formed forms inclusion compound by H-bonding self-assembly, and starch is dissolved completely in sodium hydroxide/formamide, aqueous solution
In, and form transparent starch solution.
Embodiment 2
Being configured to mass fraction after 5g cornstarch, 0.6g formamides, 56.88g water, 0.72g sodium hydroxides are mixed is
10% mixed solution, 500r/min stir 30min, obtain transparent starch solution, neutralized with 1.0mol/LHCl, add for the first time
Enter 60% ethanol water 120ml, is quickly stood for 24 hours after stirring；Second of 75% ethanol water 120ml of addition, is quickly stirred
It is stood for 24 hours after mixing；Absolute ethyl alcohol 60ml is added in third time, is quickly stood for 24 hours after stirring.Spray drying, inlet temperature 160
DEG C, outlet temperature is 80 DEG C, jet size 1.25mm, and renewable cold water soluble cornstarch is obtained after spray drying.It obtains
It is 10.236 μm to obtain renewable cold water soluble corn starch molecules average grain diameter.
Embodiment 3
Being configured to mass fraction after 5g cornstarch, 0.6g formamides, 56.88g water, 0.72g sodium hydroxides are mixed is
10% mixed solution, 500r/min stir 30min, obtain transparent starch solution, neutralized with 1.0mol/LHCl, add for the first time
Enter 60% ethanol water 120ml, is quickly stood for 24 hours after stirring；Second of 75% ethanol water 120ml of addition, is quickly stirred
It is stood for 24 hours after mixing；Absolute ethyl alcohol 60ml is added in third time, is quickly stood for 24 hours after stirring.Spray drying, inlet temperature 160
DEG C, outlet temperature is 80 DEG C, jet size 0.75mm, and renewable cold water soluble cornstarch is obtained after spray drying.It obtains
It is 3.58 μm to obtain renewable cold water soluble corn starch molecules grain size.
Claims (7)
1. a kind of controllable regeneration cold water soluble corn starch preparation method of size, which is characterized in that include the following steps：
(1) alkali, formamide, water, starch are stirred evenly in proportion, it is 10% mixed solution to be configured to total mass fraction；
(2) magnetic agitation 30min at normal temperatures, obtains transparent starch solution, is neutralized with HCl solution, sequentially adds different dense
It spends ethyl alcohol and water extraction and alcohol precipitation method is carried out to solution, up to no Cl-Until；
(3) it obtains ethyl alcohol starch solution and prepares the different renewable cold water soluble cornstarch of size with spray drying.
2. the controllable regeneration cold water soluble corn starch preparation method of a kind of size according to claim 1, feature exist
In：According to mass ratio, the alkali is starch dosage 14%, and formamide dosage is starch quality 12%.
3. the controllable regeneration cold water soluble corn starch preparation method of a kind of size according to claim 1, feature exist
In：Step (1) described alkali is one kind in sodium hydroxide, potassium hydroxide and lithium hydroxide.
4. the controllable regeneration cold water soluble corn starch preparation method of a kind of size according to claim 1, feature exist
In：Step (1) described starch is cornstarch, wheaten starch, one kind in starch from sweet potato starch.
5. the controllable regeneration cold water soluble corn starch preparation method of a kind of size according to claim 1, feature exist
In：Step (2) described mixing time is 30min, mixing speed 300-500r/min.
6. the controllable regeneration cold water soluble corn starch preparation method of a kind of size according to claim 1, feature exist
In：Step (2) described water extraction and alcohol precipitation method, different concentration ethanol are 60% ethanol solution of first time mass concentration, and addition is
2 times of starch solution volume is quickly stood for 24 hours after stirring；It is that starch is molten that second, which is used 75% ethanol solution of mass concentration, addition,
Liquid accumulates 2 times, is quickly stood for 24 hours after stirring；Third time absolute ethyl alcohol, addition are starch solution same volume, are quickly stirred
It is stood after mixing for 24 hours, secondary use after used ethyl alcohol is collected.
7. the controllable regeneration cold water soluble corn starch preparation method of a kind of size according to claim 1, feature exist
In：Step (3) described spray drying, drying tower are the closed drying tower of 304 stainless steels sprayed suitable for ethyl alcohol, wherein it is dry into
Mouth temperature is 160-180 DEG C；Outlet temperature is 80-100 DEG C；Jet size is one kind in 1.5mm, 1.25mm, 0.75mm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807462A (en) * | 2005-12-08 | 2006-07-26 | 中国科学院长春应用化学研究所 | Cool water soluble starch preparation method |
| US20060189516A1 (en) * | 2002-02-19 | 2006-08-24 | Industrial Technology Research Institute | Method for producing cross-linked hyaluronic acid-protein bio-composites |
| CN101824165A (en) * | 2010-05-04 | 2010-09-08 | 西南大学 | Granular cold water soluble porous starch |
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2018
- 2018-07-03 CN CN201810711137.6A patent/CN108794764A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060189516A1 (en) * | 2002-02-19 | 2006-08-24 | Industrial Technology Research Institute | Method for producing cross-linked hyaluronic acid-protein bio-composites |
| CN1807462A (en) * | 2005-12-08 | 2006-07-26 | 中国科学院长春应用化学研究所 | Cool water soluble starch preparation method |
| CN101824165A (en) * | 2010-05-04 | 2010-09-08 | 西南大学 | Granular cold water soluble porous starch |
Non-Patent Citations (1)
| Title |
|---|
| 段久芳: "《天然高分子材料》", 30 September 2016, 华中科技大学出版社 * |
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