CN105400768B - Using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as compound depilation enzyme of the immobilization of carrier and preparation method thereof - Google Patents
Using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as compound depilation enzyme of the immobilization of carrier and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to tanning chemistries and field of engineering technology,It provides a kind of using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as compound depilation enzyme of the immobilization of carrier and preparation method thereof,Described using porous carboxymethyl cellulose-polyvinyl alcohol microparticles is the compound depilation enzyme of the immobilization of carrier using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as immobilised enzymes carrier,The carrier good hydrophilic property,And there is higher mechanical strength,Gap is more,Porosity imparts microballoon has good physical adsorption property to enzyme,It can effectively realize enzyme immobilizatio,Promote the supported quantity and vigor of enzyme,And with good stability and reusability,It will be the compound depilation enzyme of the immobilization of carrier for dehairing of hides using porous carboxymethyl cellulose-polyvinyl alcohol microparticles and disperse collagenous fibres,Working condition is mild,The controllability of the separation loosening degree of collagen hydrolytic process and collagenous fibres is improved,It can be to avoid the fluctuation of product quality in production.
Description
Technical field
The present invention relates to technical fields prepared by process hides dedicated immobilized enzyme, more particularly to one kind is with porous carboxymethyl cellulose
Element-polyvinyl alcohol microparticles are the compound depilation enzyme of immobilization and preparation method thereof of carrier.
Background technology
Depilation is so that hair is detached from corium or dissolved process by the method for a series of physical, chemistry.Traditional ash alkali is de-
Mao Fa, hair removal effect is good, clean and rapid, easy to operate, is easy to control, but loosely make good use of collagenous fibres, and to skin
It destroys less, depilation pelt graining is clear.But sulfide is seriously polluted, and a large amount of keratin hydrolysis make have in waste water
Machine object content greatly improves, while generating a large amount of alkaline sludges, it is difficult to handle.Enzyme unhairing method and traditional ash alkali unhairing method phase
Than biggest advantage is that enzyme unhairing is Bao Maofa depilations, can recycle the hair of high quality, not generate nontoxic nothing in epilation process
Evil gas, pollutes very little, not only eliminates sulphide staining, can also reduce BOD and solid suspension content in waste water.
But the enzyme unhairing method used in leather industry at present has the following disadvantages：（1）The stabilization of enzyme preparation
Property it is poor, be easy inactivation；（2）Enzyme preparation is usually used with other materials in same system, and the certain materials used in process are easy
Lead to the inactivation of enzyme；（3）The catalytic activity of enzyme is excessively high, and process controllability is poor.Therefore, it is necessary to study immobilised enzymes in process hides
Application in field, forming the benefits of protecting and being sustained fruit, enhancing the durability of process hides special enzyme preparation and extending enzymatic reaction
Time, but in enzyme immobilization technology, the selection of carrier has vital work to the activity of immobilised enzymes and using characteristic
With, have that good catalytic, carrying capacity be high, immobilised enzymes at low cost in order to obtain, the prior art be utilized it is cheap, easily
The natural polymer obtained, such as：Activated carbon, diatomite, alum, chitosan and calcium alginate etc. are used as fixation support,
In, chitosan, calcium alginate as fixation support research than wide, but use these natural polymers as immobilization
When zymophore, since they are limited with the compatibility and compatibility of enzyme, the supported quantity and vigor of the enzyme in obtained immobilised enzymes
It is relatively low.And standard enzymatic loses hair or feathers, and most of enzyme that loses hair or feathers, can be big while depilation to the no specific aim of the effect of intradermal component
Hydrolytic collagen is measured, is difficult to control in condition, misoperation can make skin loose side, rotten face, and hair generally can not remove completely.
Invention content
Therefore, for above-mentioned problem, the present invention proposes one kind with porous carboxymethyl cellulose-polyvinyl alcohol microparticles for load
Compound depilation enzyme of immobilization of body and preparation method thereof.It is described using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as carrier
The compound depilation enzyme of immobilization is using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as immobilised enzymes carrier, the carrier hydrophily
It is good, and have higher mechanical strength, gap is more, and porosity imparts microballoon has good physical adsorption property to enzyme, Neng Gouyou
Effect realizes enzyme immobilizatio, promotes the supported quantity and vigor of enzyme, and uses described with porous carboxymethyl cellulose-polyvinyl alcohol
Microballoon is that the compound depilation enzyme of immobilization of carrier lose hair or feathers that treated that pelt surface is pure white, and grain pore is clear, has lost hair or feathers
Entirely, and the epilation process is simple to operation, and practicability is high.And it is described with porous carboxymethyl cellulose-polyvinyl alcohol microparticles
For the preparation method easy realization simple for process of the compound depilation enzyme of immobilization of carrier, it is suitble to quantitatively produce and use.
To realize above-mentioned technical problem, the solution that the present invention takes is：
Using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation enzyme of the immobilization of carrier, there is following property：
（1）Appearance：Beige white powder；
（2）PH value：5.0-7.5；
（3）Loss on drying：≤8%；
（4）Enzyme activity：20000u/g；
（5）Enzyme activity residual rate：≥99%；
（6）Arsenic content：0.001%；
（7）Content of beary metal：0.001%.
It is above-mentioned using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the immobilization of carrier it is compound depilation enzyme preparation side
Method includes the following steps：
Step 1 prepares porous carboxymethyl cellulose-polyvinyl alcohol microparticles；
Step 2, the periodic acid that the porous carboxymethyl cellulose-polyvinyl alcohol microparticles of 100 parts by weight are soaked in 1% at room temperature
60-240min in solution, after fully oxidized, is filtered, and washing is soaked in 100ml distilled water, adds 10-15 parts by weight 1-
Ethyl-(3- dimethylaminopropyls) carbodiimides, and the oscillating reactions 60-120min in 20-30 DEG C of water-bath, filtering are used in combination
Deionized water washes away remaining carbodiimides on carrier；
Step 3, accurate to weigh 10g complex enzymes to be dissolved in 1000 ml pH value be 5.0-8.0, ionic strength 0.1-
In the buffer solution of 0.5mol/L, compound depilation enzyme solutions are configured to, then centrifuge 15min under 5 DEG C, 1500r/min, in collection
Layer clear liquid；
Porous carboxymethyl cellulose-polyvinyl alcohol microparticles of step 2 are added in compound depilation enzyme solutions by step 4, are made
Enzyme is 1 with porous carboxymethyl cellulose-polyvinyl alcohol microparticles mass ratio：1, the oscillating reactions 30-90min in 15-40 DEG C of water-bath,
It filters and remaining compound depilation enzyme is washed with deionized water on carrier to get to porous carboxymethyl cellulose-polyvinyl alcohol
Microballoon is the compound depilation enzyme of immobilization of carrier.
Further, it includes in 50-65 parts by weight that complex enzyme described in step 3, which is in every 100 parts by weight complex enzyme,
Property protease, the alpha amylase of 10-15 parts by weight, 5-10 parts by weight carbohydrase, the pancreatin of 10-15 parts by weight, 5-8 parts by weight
The elastoser of lipase, 5 parts by weight of 2-.
Further, step 1 includes the following steps：Step 1., under the conditions of 90 DEG C by the polyvinyl alcohol of 100 parts by weight
It is dissolved in distilled water and prepares poly-vinyl alcohol solution, the ratio of the polyvinyl alcohol and distilled water is 1g:20ml；Step 2., in 40-
The carboxymethyl cellulose of 100 parts by weight is dissolved in solvent under conditions of 50 DEG C, rotating speed 200r/min, mixing time 60min and being made
Standby cmc soln, the solvent can be in sodium hydroxide solution, methyl morpholine, urea liquid or ammonium hydroxide extremely
The ratio of few one kind, the carboxymethyl cellulose and solvent is 1g:20ml；Step 3., by step 2. gained carboxymethyl cellulose
Plain solution is dissolved in oil phase, and the cmc soln is 1 with oil phase volume ratio:1, the emulsification of 10-20 parts by weight is added
After fully emulsified 90min, it is 1. accurate that step is added with the speed of 5ml/min under conditions of 40-60 DEG C, rotating speed 600r/min in agent
The poly-vinyl alcohol solution got ready, after persistently stirring 120min, salt acid for adjusting pH to 3-5 keeps rotating speed constant, stirs 30min；Step
Suddenly 4., be added 3-10 parts by weight of crosslinking agent, under conditions of 40-60 DEG C, rotating speed 600r/min, stir 180min；Step 5., plus
Enter deionized water, for deionized water as curing agent, the volume ratio of cmc soln and deionized water is 1: 3, is added
Rotating speed 150r/min is reduced after ionized water, continues to stir 10-30min；Step 6., liquid separation remove upper layer grease, lower layer filter, according to
Secondary washed with distilled water, acetone, ethyl alcohol is achieved with porous carboxymethyl cellulose-polyvinyl alcohol microparticles.
Further, step 3. in oil phase can be castor oil, at least one of paraffin olive oil；Step 3. in
Emulsifier can be that emulsifier can be at least one of Span 80, Span 20, polysorbas20, Tween 80；Step 4. in crosslinking agent
For glutaraldehyde.
By using preceding solution, the beneficial effects of the invention are as follows：That designs as described above is fine with porous carboxymethyl
Dimension element-polyvinyl alcohol microparticles have following excellent compared to the prior art for the compound depilation enzyme of immobilization and preparation method of carrier
Gesture：
1, it is of the present invention using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation enzyme of the immobilization of carrier with
Porous carboxymethyl cellulose-polyvinyl alcohol microparticles are immobilised enzymes carrier, the carrier good hydrophilic property, and have higher machinery strong
Degree, gap is more, on the one hand free on the carboxyl and enzyme molecule of porous carboxymethyl cellulose-polyvinyl alcohol microparticles through peroxidating
Amino has there are the hydroxyl on certain covalent bond, porous carboxymethyl cellulose-polyvinyl alcohol microparticles and between enzyme molecule
The effects that covalent linkage of a degree of affinity and carbodiimides, realizes that enzyme immobilizatio, another aspect porosity are assigned
Given microballoon has good physical adsorption property to enzyme, therefore, it is possible to effectively realize enzyme immobilizatio, promotes the supported quantity of enzyme
And vigor, enzyme is with good stability and reusability therefore will be described with porous carboxymethyl cellulose-polyethylene
Alcohol microballoon is the compound depilation enzyme of immobilization of carrier for dehairing of hides and disperses collagenous fibres, and working condition is mild, to hide glue
The controllability of the separation loosening degree of raw water solution preocess and collagenous fibres improves, can to avoid the fluctuation of product quality in production,
Avoid skin loose side, rotten face, the incomplete problem of depilation caused by the low misoperation of controllability；And cellulose be most it is cheap most
One of abundant natural macromolecular material, it is easy to be modified, while being easily degraded, and the feature of environmental protection is good.
2, of the present invention using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation enzyme of the immobilization of carrier
Complex enzyme used includes neutral proteinase, alpha amylase, carbohydrase, pancreatin, lipase, elastoser in preparation method；Its
In, neutral proteinase is conducive to the removing of dermatan sulfate, promotes the cyclic protein polysaccharide of constraint collagenous fibres to be opened, makes fibre
Dimension dispersion, makes the flexibility of finished leather, intensity dramatically increase;Addition carbohydrase, amylase can remove proteoglycan, glycoprotein,
Low-fiber adherence is dropped, dermatan sulfate is made to be separated from proteoglycan, removing interfibrillar substance, loose collagenous fibres,
And the connection function between destruction papilla and hair；Lipase acts on intradermal fat, adipose gland, free adipocyte, reaches
To the effect of degreasing and auxiliary depilation；Elastoser, can appropriate hydrolyzed elastin fiber, destroy elastomer to collagenous fibres
And hair follicle " tension " effect so that fiber can be easily separated and loosely, therefore, described with the poly- second of porous carboxymethyl cellulose-
Enol microballoon is that various enzymes are used in mixed way by the compound depilation enzyme of immobilization of carrier, can have the function that complementary, collaboration, to
The comprehensive performance for greatly increasing enzymatic depilation uses described using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as carrier
The compound depilation enzyme of immobilization carries out depilation, and treated that pelt surface is pure white, and grain pore is clear, and depilation is complete.
3, described using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the preparation side of the compound depilation enzyme of the immobilization of carrier
Method easy realization simple for process is suitble to quantitatively produce and use.
Description of the drawings
The influence result schematic diagram of Fig. 1, PF value depilation enzyme and free enzyme activity compound to immobilization.
The influence result schematic diagram of Fig. 2, temperature depilation enzyme and free enzyme activity compound to immobilization.
Fig. 3, after using using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation enzymatic depilation of the immobilization of carrier
Pelt schematic diagram.
Fig. 4, after using using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation enzymatic depilation of the immobilization of carrier
Finished leather microscope figure.
Specific implementation mode
The present invention is specifically described below by specific embodiment, it is necessary to which indicated herein is the present embodiment
It is used to further illustrate the present invention, should not be understood as limiting the scope of the invention, which is skilled in technique
Personnel can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
It should be noted that it includes in 50-65 parts that complex enzyme involved in following embodiment, which is every 100 parts of complex enzymes,
The bullet of property protease, 10-15 parts of alpha amylase, 5-10 parts of carbohydrase, 10-15 parts of pancreatin, 5-8 parts of lipase, 5 parts of 2-
Property protease.
Using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the preparation method of the compound depilation enzyme of the immobilization of carrier：
Step 1 prepares porous carboxymethyl cellulose-polyvinyl alcohol microparticles, includes the following steps：Step 1., in 90 DEG C of items
5g polyvinyl alcohol is dissolved in the distilled water of 100ml under part and prepares poly-vinyl alcohol solution；Step 2., at 50 DEG C, rotating speed 200r/
5g carboxymethyl celluloses are dissolved in 100ml solvents under conditions of min, mixing time 60min and prepare cmc soln,
The solvent is sodium hydroxide solution；Step is 3., by step, 1. gained cmc soln is added in 100ml castor oil,
1g Spans 80 are added, under conditions of 60 DEG C, rotating speed 600r/min, emulsify 60min, 1. step is added with the speed of 5ml/min
Ready poly-vinyl alcohol solution, after 120min, salt acid for adjusting pH to 3.5 keeps rotating speed constant, keeps 30min；Step 4.,
0.5g glutaraldehydes are added, under conditions of 40-60 DEG C, rotating speed 600r/min, act on 180min；Step 5., be added 300ml ions
Water, and rotating speed is reduced to 150r/min, continue to stir 10-30min；Step 6., liquid separation remove upper layer grease, lower layer filter, according to
Secondary washed with distilled water, acetone, ethyl alcohol is achieved with porous carboxymethyl cellulose-polyvinyl alcohol microparticles.
The volume fraction that the porous carboxymethyl cellulose-polyvinyl alcohol microparticles of 2g are soaked in 100ml at room temperature is by step 2
120min in 1% periodic acid solution after fully oxidized, is filtered, washing, and the carbonization two for being soaked in the mass fraction 5% of 100ml is sub-
In amine aqueous solution, and the oscillating reactions 60min in 30 DEG C of water-baths, it filters and remaining carbonization two on carrier is washed with deionized water
Imines；
The pH value that step 3, the accurate compound depilation enzyme for weighing 10g are dissolved in 1000ml be 6.5, ionic strength be
In the buffer solution of 0.3mol/L, compound depilation enzyme solutions are configured to, then centrifuge 15min under 5 DEG C, 1500r/min, in collection
Layer clear liquid；
Step 4, the composite enzyme solution that porous carboxymethyl cellulose-polyvinyl alcohol microparticles of step 2 are added to 200ml
In, the oscillating reactions 60min in 15 DEG C of water-baths, filter and be washed with deionized water on carrier remaining complex enzyme to get to
Porous carboxymethyl cellulose-polyvinyl alcohol microparticles are the compound depilation enzyme of immobilization of carrier.
It is obtained above to have by the compound depilation enzyme of the immobilization of carrier of porous carboxymethyl cellulose-polyvinyl alcohol microparticles
Following property：
（1）Appearance：Beige white powder；
（2）PH value：5.0-7.5；
（3）Loss on drying：≤8%；
（4）Enzyme activity：20000u/g；
（5）Enzyme activity residual rate：≥99%；
（6）Arsenic content：0.001%；
（7）Content of beary metal：0.001%.
The case where being kept for the enzyme supported quantity and vigor of investigating the compound depilation enzyme of immobilization prepared by the present invention, this hair
It is bright choose above method prepare using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation enzyme of the immobilization of carrier,
And respectively according to the assay method of immobilized enzyme（Chen Qing, Zhang little Wei, Lin Mei wait response phase methods to optimize sodium alginate
Research [J] Chemical Industry in Guangzhou of fixed alpha-amylase, 2015, (6) the People's Republic of China light industry standard QB/T
1803-1993 [S] industrial enzyme preparation GENERAL EXPERIMENTATIONs, 1993.）The measurement that enzyme supported quantity and vigor are kept is carried out.It surveys
Determine as a result, using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the fixation of the compound depilation enzyme preparation enzyme of the immobilization of carrier
Change efficiency >=67.48%, enzymatic activity recovery >=57.93%.
Secondly, the present invention has also investigated pH, environment temperature to preparation with porous carboxymethyl cellulose-polyvinyl alcohol microparticles
For the influence degree of the compound depilation enzyme activity of immobilization of carrier.PH is being investigated to porous carboxymethyl cellulose-polyvinyl alcohol
It, will be poly- with porous carboxymethyl cellulose-under the conditions of 40 DEG C when microballoon is the influence of the compound depilation enzyme activity of the immobilization of carrier
Vinyl alcohol microballoon is that the compound depilation enzyme of the immobilization of carrier is respectively placed in the buffer solution that pH value is 6.0-9.0 with free enzyme and keeps the temperature
Its enzyme activity is measured after 10min, has then obtained pH value to consolidating as carrier using porous carboxymethyl cellulose-polyvinyl alcohol microparticles
Surely change the influence of compound depilation enzyme and free enzyme activity, the result is shown in Figure 1.As seen from Figure 1, with the poly- second of porous carboxymethyl cellulose-
Enol microballoon be carrier the compound depilation enzyme of immobilization investigate pH value range in freer enzyme show it is higher relatively
Vigor, complex enzyme reduce the sensibility of pH after the method for the present invention is fixed, and higher urge can be played within the scope of broader pH
Change vigor.
Environment temperature is being investigated to using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation of the immobilization of carrier
It, will be using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation enzyme of the immobilization of carrier and certainly when the influence of enzyme activity
It is placed at 5-75 DEG C by enzyme, measures its enzyme activity after heat preservation 10min in the phosphate buffer that pH value is 7.5, then obtain
Temperature is to using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the shadow of the compound depilation enzyme and free enzyme activity of the immobilization of carrier
It rings, as a result sees Fig. 2.From Figure 2 it can be seen that using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation of the immobilization of carrier
Enzyme freer enzyme within the temperature range of investigated shows higher relative activity, and complex enzyme is after the method for the present invention is fixed
The sensibility of temperature is reduced, and higher catalysis activity can be played in wider temperature range.
Finally, the present invention also investigated prepare using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the fixation of carrier
Change the application effect of compound depilation enzyme.This will be used using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the immobilization of carrier
Compound depilation enzyme preparation depilation gained pelt, the liquid caustic soda through 1.0% vulcanized sodium and 0.7%（The sodium hydroxide that mass fraction is 30%
Solution）Supplement depilation, routinely finished leather is made in technique thereafter, and use is to carry with porous carboxymethyl cellulose-polyvinyl alcohol microparticles
Pelt after the compound depilation enzymatic depilation of the immobilization of body is taken pictures figure, such as Fig. 3.Meanwhile using stereomicroscope observation finished leather sample
Grain, as a result see Fig. 4.As seen from Figure 3, it uses using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the immobilization of carrier
Cattle hide surface after compound depilation enzymatic depilation is pure white, and grain pore is clear, almost only exists a small amount of short and small villus and new life is small
Hair.From fig. 4, it can be seen that using using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the compound depilation enzyme processing of the immobilization of carrier
Obtained cattle hide upper leather, grain is smooth, smooth, and pore is more complete.Therefore with porous carboxymethyl cellulose-polyvinyl alcohol microparticles
It is different from standard biologic enzyme for the compound depilation enzyme of immobilization of carrier, the leather quality that it does not obtain processing is brought very significantly
Negative effect, there is tight security, technique and resultant leather quality stability are high, have the ability mildly lost hair or feathers.
In conclusion of the present invention compound as the immobilization of carrier using porous carboxymethyl cellulose-polyvinyl alcohol microparticles
Depilation enzyme is using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as immobilised enzymes carrier, the carrier good hydrophilic property, and has higher
Mechanical strength, gap is more, and porosity imparts microballoon has good physical adsorption property to enzyme, can effectively realize consolidating for enzyme
Fixedization, promotes the supported quantity and vigor of enzyme, and uses described using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as carrier
The compound depilation enzyme of immobilization carries out depilation, and treated that pelt surface is pure white, and grain pore is clear, and depilation is complete, and the depilation
Process is simple to operation, and practicability is high.And it is described using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the immobilization of carrier
The preparation method easy realization simple for process of compound depilation enzyme, is suitble to quantitatively produce and use.
The foregoing descriptions are merely the embodiment using this origination techniques content, any those skilled in the art use this wound
Make done modifications and changes, all belong to the scope of the claims of this creation opinion, and is not limited to those disclosed embodiments.
Claims (3)
1. special using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as the preparation method of the compound depilation enzyme of the immobilization of carrier
Sign is, includes the following steps：
Step 1 prepares porous carboxymethyl cellulose-polyvinyl alcohol microparticles：
Step 1., the polyvinyl alcohol of 100 parts by weight be dissolved in distilled water under the conditions of 90 DEG C prepare poly-vinyl alcohol solution, it is described
The ratio of polyvinyl alcohol and distilled water is 1g:20ml；
Step 2., under conditions of 40-50 DEG C, rotating speed 200r/min, mixing time 60min by the carboxymethyl of 100 parts by weight fibre
Dimension element, which is dissolved in solvent, prepares cmc soln, and the solvent can be sodium hydroxide solution, methyl morpholine, urea
The ratio of at least one of solution or ammonium hydroxide, the carboxymethyl cellulose and solvent is 1g:20ml；
Step 3., by step 2. gained cmc soln be dissolved in oil phase, the cmc soln with oil
The volume ratio of phase is 1:1, the emulsifier of 10-20 parts by weight is added, it is fully newborn under conditions of 40-60 DEG C, rotating speed 600r/min
After changing 90min, step 1. ready poly-vinyl alcohol solution, after persistently stirring 120min, hydrochloric acid are added with the speed of 5ml/min
PH to 3-5 is adjusted, keeps rotating speed constant, stirs 30min；
Step 4., be added 3-10 parts by weight of crosslinking agent, under conditions of 40-60 DEG C, rotating speed 600r/min, stir 180min；Its
In, crosslinking agent is glutaraldehyde；
Step 5., be added deionized water, deionized water is as curing agent, the volume ratio of cmc soln and deionized water
It is 1: 3, rotating speed 150r/min is reduced after adding deionized water, continues to stir 10-30min；
Step 6., liquid separation remove upper layer grease, lower layer filter, washed with distilled water, acetone, ethyl alcohol be achieved with porous carboxylic successively
Methylcellulose-polyvinyl alcohol microparticles；
Step 2, the periodic acid solution that the porous carboxymethyl cellulose-polyvinyl alcohol microparticles of 100 parts by weight are soaked in 1% at room temperature
Middle 60-240min, after fully oxidized, is filtered, and washing is soaked in 100ml distilled water, adds 10-15 parts by weight 1- ethyls-
(3- dimethylaminopropyls) carbodiimides, and the oscillating reactions 60-120min in 20-30 DEG C of water-bath, filter and spend from
Remaining carbodiimides on carrier is removed in son washing；
Step 3, accurate to weigh 10g complex enzymes to be dissolved in 1000 ml pH value be 5.0-8.0, ionic strength 0.1-0.5mol/L
Buffer solution in, be configured to compound depilation enzyme solutions, then centrifuge 15min under 5 DEG C, 1500r/min, collect supernatant liquor；
The compound depilation enzyme solutions are neutral proteinase, 10 weights for including 50 parts by weight in the compound depilation enzyme solutions of every 100 parts by weight
Measure the alpha amylase of part, 5-10 parts by weight carbohydrase, the pancreatin of 10 parts by weight, the lipase of 5-8 parts by weight, 5 parts by weight of 2-
Elastoser；
Porous carboxymethyl cellulose-polyvinyl alcohol microparticles of step 2 are added in compound depilation enzyme solutions by step 4, make enzyme with
Porous carboxymethyl cellulose-polyvinyl alcohol microparticles mass ratio is 1：1, the oscillating reactions 30-90min in 15-40 DEG C of water-bath, filtering
And remaining compound depilation enzyme is washed with deionized water on carrier to get to porous carboxymethyl cellulose-polyvinyl alcohol microparticles
For the compound depilation enzyme of immobilization of carrier.
2. according to claim 1 compound de- by the immobilization of carrier of porous carboxymethyl cellulose-polyvinyl alcohol microparticles
The preparation method of hair enzyme, it is characterised in that：Step 3. in oil phase be castor oil, at least one of paraffin olive oil；Step
3. emulsifier in is at least one of Span 80, Span 20, polysorbas20, Tween 80.
3. it is a kind of obtained by any preparation methods of claim 1-2 with porous carboxymethyl cellulose-polyvinylalcohol microsphere
Ball is the compound depilation enzyme of immobilization of carrier, which is characterized in that has following property：
（1）Appearance：Beige white powder；
（2）PH value：5.0-7.5；
（3）Loss on drying：≤8%；
（4）Enzyme activity：20000u/g；
（5）Enzyme activity residual rate：≥99%；
（6）Arsenic content：0.001%；
（7）Content of beary metal：0.001%.
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| CN107326022A (en) * | 2017-03-29 | 2017-11-07 | 东北林业大学 | A kind of method of silanization magnetic cellulose microsphere fixed fat enzyme |
| CN109007512A (en) * | 2018-08-06 | 2018-12-18 | 福建保安康保健食品有限公司 | A kind of rock sugar fructus arctii algae solid beverage |
| CN109007513A (en) * | 2018-08-06 | 2018-12-18 | 福建保安康保健食品有限公司 | A kind of brown sugar fructus lycii algae solid beverage |
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