CN104673560B - Particle based on biological enzymatic compositions and preparation method and application - Google Patents
Particle based on biological enzymatic compositions and preparation method and application Download PDFInfo
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- CN104673560B CN104673560B CN201510130264.3A CN201510130264A CN104673560B CN 104673560 B CN104673560 B CN 104673560B CN 201510130264 A CN201510130264 A CN 201510130264A CN 104673560 B CN104673560 B CN 104673560B
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Abstract
Specifically a kind of particle based on biological enzymatic compositions and preparation method and application, it is to be made up of core and the coating being coated on core, the core and coating are made up of the raw material of following weight percents the present invention relates to biology enzyme compositions field.Particle of the present invention based on biological enzymatic compositions, the composition of enzyme or enzyme is encapsulated in core so that the particulate stain removal ability of the composition produced is strong, dissolubility is good, especially suitable in articles for washing.And the material selected by the present invention is environmental protection, non-hazardous, degradable material, the activity of enzyme will not be not only damaged, and the enzyme in particle can be made to have higher activity within the quite a while.
Description
Technical field
The present invention relates to biology enzyme compositions field, specifically a kind of particle and its preparation side based on biological enzymatic compositions
Method and application.
Background technology
Biological enzyme formulation is a kind of easy to use, green, good raw material of biological degradability.Single-minded catalysis characteristics
And gentle reaction condition so that biological enzyme formulation is more and more used and paid attention in industrial quarters.Biological enzyme formulation exists
Usage amount of the characteristics of application in detergent is more and more extensively and because of its low-carbon and environment-friendly high-efficiency in detergent is also in day
Benefit increases.Detergent containing biological enzyme formulation proportion in whole detergent industry increasingly increases, such as now American-European
The regional detergent ratio containing biological enzyme formulation is up to more than 90%.Detergent of the China containing biological enzyme formulation is enzyme-added at present
Using also having accounted for 50%, and its ratio also has increasingly increased trend.
Biological enzyme formulation is through adding filler and stabilizer that granular enzyme is made, and then outer layer coated, can extend
The storage life of finished product and the intensity of particle.Different industries are because the difference of its application field, the difference of use environment, to used in it
To the requirement of biological enzyme formulation particle be inconsistent.
At present, also there is the stabilization of solid preparaton that technology (200480002906.1) mentions detergent enzyme, but because of enzyme
The three-dimensional structure of preparation, it can all encounter enzyme inactivation, and encapsulation biology in various degree in the special formulation system of detergent
The problem of enzyme content is too low.
The defects of in order to overcome present in prior art, need to be invented a kind of the special applicable of adaptation detergent compositions composition
In the granular recipe and technology of preparing of the biological enzyme formulation of detergent use.
The content of the invention
A kind of the present invention is intended to provide new particle based on biological enzymatic compositions.
The present invention is by the following technical programs:A kind of particle based on biological enzymatic compositions is by core and is coated on
What the coating on core was formed, the core and coating are made up of the raw material of following weight percents,
Filler 1.0~40.0%
Adhesive 0.1~15.0%
Enzymatic protective reagent 0.25~35.0%
The composition 0.01~70.0% of enzyme or enzyme
Coating 0.25~20.0%.
When the present invention is specifically used, filler preferably percentage by weight is 2.0~38.0%, optimal percentage by weight
For 8.0~30.0%;Adhesive preferably percentage by weight is 0.2~13.0%, and optimal percentage by weight is 2.0~12.0%;
Enzymatic protective reagent preferably percentage by weight is 1.0~32.0%, and optimal percentage by weight is 2.0~28.0%;The group of enzyme or enzyme
Compound preferably percentage by weight is 10.0~70.0%, and optimal percentage by weight is 20.0~60.0%;Coating is preferably heavy
It is 1.0~17.0% to measure percentage, and optimal percentage by weight is 2.0~16.0%.
Further, the grain diameter of the composition is the mm of 0.01mm~10.When it is implemented, particle size it is more excellent
It is optimal in the mm of 1 mm~7 between the mm of 0.1 mm~8.
When building particle of the present invention based on biological enzymatic compositions, its filler is converted starch, kaolin, fiber
Element, diatomite or one kind in bentonite or any several mixtures mixed with arbitrary proportion.Converted starch can use crosslinking
Starch(Formaldehyde crosslinking starch, methacrylaldehyde crosslinked starch, phosphoric acid crosslinked starch etc.), graft copolymerization starch(Acrylonitrile graft copolymer
Starch, polyvinyl alcohol graft copolymerized copolymerization starch etc.), acid treated starches, dextrin, cyclodextrin, oxidized starch, starch phosphate(It is single to form sediment
Powder phosphate, double starch phosphates etc.), CMS, HES, cyanoethyl starch.
During further implementation of the invention, the adhesive used is the superelevation degree of polymerization(Molecular weight 25~300,000)Polyvinyl alcohol,
High polymerization degree(Molecular weight 17~220,000)Polyvinyl alcohol, the middle degree of polymerization(Molecular weight 12~150,000)Polyvinyl alcohol, low polymerization degree(Point
Son amount 2.5~3.0 ten thousand)One kind or any several mixing mixed with arbitrary proportion in polyvinyl alcohol or polyvinylpyrrolidone
Thing.The high-molecular compound polyvinylpyrrolidone of polymerization generation is occurred to be optimal using NVP.
When further implementing of the invention, the enzymatic protective reagent is mixed using dihydric alcohol and calcium carbonate with arbitrary proportion
Mixture, or the mixture that trihydroxylic alcohol and sodium sulphate are mixed with arbitrary proportion.The dihydric alcohol can be ethylene glycol, 1,2- third
Glycol, 1,3-PD, 1,2- butanediol, 1,3-BDO, BDO, 1,5-PD etc., the trihydroxylic alcohol can be with
It is glycerine, 1,2,4- butantriols, the triols of 1,2,5- penta.
Invention further provides enzyme and the composition of enzyme, the enzyme is selected from protease, pectase, cellulase, fat
Fat enzyme, hemicellulase, lipase, Novi's letter enzyme, novel subtilases;The composition of enzyme be protease, pectase, cellulase,
The mixture mixed in lipase, hemicellulase, lipase, Novi's letter enzyme or novel subtilases with arbitrary proportion.
In addition, the coating is one kind or any several with any in titanium dioxide, zinc oxide, lithopone or sodium silicoaluminate
The mixture of ratio mixing.
Secondary purpose of the present invention is to provide a kind of method for preparing above-mentioned particle, and its step is:Each material of core is by setting
Standby bottom mixing slurry is sufficiently mixed into moistening softwood, and then crushing oar by high speed cuts into uniform wet granular;Coating compound applies
Spread on wet granular.It is 6~12 that reaction pH is prepared in its step, and the reaction time is 1~24h, and reaction temperature is 0~80 DEG C.Tool
, can be in blender, agglomeration former, spray dryer, spray fluidizer, high-speed mixing granulating machine or extrusion when body is implemented
Prepared in machine and spheronizator.It is 7~11 more excellent that pH is reacted in the preparation method, and 8~10 is optimal;Reaction temperature be 5~70 DEG C compared with
Excellent, 10~50 DEG C optimal.Preparation method of the present invention compared to other current biological enzyme formulation preparation methods it is advantageous that:
According to particle made from preparation method of the present invention, it can more keep the stability of enzyme for a long time.
The three of the object of the invention are to provide application of the above-mentioned particle in articles for washing.It is of the present invention when specifically used
Particle can be configured to the laundry detergents hand-washed or machine-washed(The enzyme or the composition of enzyme added according to spot type selecting), including it is suitable
In the cleaning additive composition or fabric softener composition of the stained fabric of pretreatment;Either it is generally used for the hard table of family
The detergent composition of face clean operation(The enzyme or the composition of enzyme added according to spot type selecting)Or for hand-washing, machine-washing
The composition of dishes operation(The enzyme or the composition of enzyme added according to spot type selecting).Specifically used method is by weight ratio
Laundry detergents are made an addition to for 2% particle of the present invention(Or in other detergent compositions), the laundry detergents can be made to specific spot
Dirt-removing power improves more than 10%, and the biology enzyme used in the present invention is the enzyme very friendly to environment, and ammonia is generated after decomposition
Base acid and water, it is the environmentally friendly auxiliary agent done washing in agent prescription.
Particle of the present invention based on biological enzymatic compositions, the composition of enzyme or enzyme is encapsulated in core so that system
The particulate stain removal ability of the composition taken is strong, dissolubility is good, especially suitable in articles for washing.And the material selected by the present invention
It is environmental protection, non-hazardous, degradable material, will not only damages the activity of enzyme, and the enzyme in particle can be made suitable one
There is higher activity in the section time.
Embodiment
Each all characteristics of particle are obtained using this area conventional method measure in embodiment.
Embodiment 1
A kind of particle based on biological enzymatic compositions, it is made up of core and the coating being coated on core, the core
Portion and coating are made up of the raw material of following weight percents,
Crosslinked starch 1.0%
The superelevation degree of polymerization(Molecular weight 25~300,000)Polyvinyl alcohol 10.0%
Ethylene glycol and calcium carbonate(Mass ratio 1:2) 2.0%
Protease(Or pectase or cellulase) 70.0%
Titanium dioxide 17.0%.
The method for preparing above-mentioned particle, its step are:Each material of core is sufficiently mixed into moistening by device bottom mixing slurry
Softwood, oar is then crushed by high speed and cuts into uniform wet granular;For coating compound coated on wet granular, it is 5mm that particle diameter, which is made,
Particle.It is 6 that reaction pH is prepared in its step, reaction time 7h, and reaction temperature is 10 DEG C.When it is implemented, the crosslinking
Starch can use formaldehyde crosslinking starch, methacrylaldehyde crosslinked starch or phosphoric acid crosslinked starch, and above-mentioned preparation method is made in a mixer
It is standby.
Above-mentioned granzyme motility characteristics are shown in Table 1.
Embodiment 2
A kind of particle based on biological enzymatic compositions, it is made up of core and the coating being coated on core, the core
Portion and coating are made up of the raw material of following weight percents,
Kaolin 2.0%
High polymerization degree(Molecular weight 17~220,000)Polyvinyl alcohol 15.0%
1,2- propane diols(Or 1,3- propane diols)And calcium carbonate(Mass ratio 2:1) 28.0%
Lipase and hemicellulase(Mass ratio 1:1) 53.0%
Zinc oxide 2.0%.
The method for preparing above-mentioned particle, its step are:Each material of core is sufficiently mixed into moistening by device bottom mixing slurry
Softwood, oar is then crushed by high speed and cuts into uniform wet granular;For coating compound coated on wet granular, it is 7mm that particle diameter, which is made,
Particle.It is 7 that reaction pH is prepared in its step, reaction time 9h, and reaction temperature is 30 DEG C.When it is implemented, agglomerating into
Prepared in type machine.
Above-mentioned granzyme motility characteristics are shown in Table 1.
Embodiment 3
A kind of particle based on biological enzymatic compositions, it is made up of core and the coating being coated on core, the core
Portion and coating are made up of the raw material of following weight percents,
Cellulose 8.0%
The middle degree of polymerization(Molecular weight 12~150,000)Polyvinyl alcohol 13.0%
1,2- butanediols(Or 1,3 butylene glycol or 1,4- butanediols)And calcium carbonate(Mass ratio 1:1) 35.0%
Lipase 28.0%
Lithopone 16.0%.
The method for preparing above-mentioned particle, its step are:Each material of core is sufficiently mixed into moistening by device bottom mixing slurry
Softwood, oar is then crushed by high speed and cuts into uniform wet granular;For coating compound coated on wet granular, it is 8mm that particle diameter, which is made,
Particle.It is 8 that reaction pH is prepared in its step, reaction time 10h, and reaction temperature is 50 DEG C.It is when it is implemented, dry in spraying
Prepared in dry device.
Above-mentioned granzyme motility characteristics are shown in Table 1.
Embodiment 4
A kind of particle based on biological enzymatic compositions, it is made up of core and the coating being coated on core, the core
Portion and coating are made up of the raw material of following weight percents,
Diatomite 30.0%
Low polymerization degree(Molecular weight 2.5~3.0 ten thousand)Polyvinyl alcohol 0.1%
1,5- pentanediols and calcium carbonate(Mass ratio 1:2) 9.65%
Novi believes enzyme 60.0%
Sodium silicoaluminate 0.25%.
The method for preparing above-mentioned particle, its step are:Each material of core is sufficiently mixed into moistening by device bottom mixing slurry
Softwood, oar is then crushed by high speed and cuts into uniform wet granular;For coating compound coated on wet granular, it is 10mm that particle diameter, which is made,
Particle.It is 9 that reaction pH is prepared in its step, reaction time 14h, and reaction temperature is 70 DEG C.When it is implemented, it can spray
Prepared in fluidized bed plant.
Above-mentioned granzyme motility characteristics are shown in Table 1.
Embodiment 5
A kind of particle based on biological enzymatic compositions, it is made up of core and the coating being coated on core, the core
Portion and coating are made up of the raw material of following weight percents,
Bentonite 40.0%
Polyvinylpyrrolidone 12.0%
Glycerine and sodium sulphate(Mass ratio 2:1) 8.0%
Novel subtilases 20.0%
Titanium dioxide and lithopone(Mass ratio 3:1) 20.0%.
The method for preparing above-mentioned particle, its step are:Each material of core is sufficiently mixed into moistening by device bottom mixing slurry
Softwood, oar is then crushed by high speed and cuts into uniform wet granular;Coated on wet granular, obtained particle diameter is coating compound
0.01mm particle.It is 10 that reaction pH is prepared in its step, reaction time 20h, and reaction temperature is 80 DEG C.When it is implemented,
It can be prepared in high-speed mixing granulating machine.
Above-mentioned granzyme motility characteristics are shown in Table 1.
Embodiment 6
A kind of particle based on biological enzymatic compositions, it is made up of core and the coating being coated on core, the core
Portion and coating are made up of the raw material of following weight percents,
Graft copolymerization starch and cellulose(Mass ratio 3:1) 26.75%
High polymerization degree(Molecular weight 17~220,000)Polyvinyl alcohol and polyvinylpyrrolidone(Mass ratio 2:1) 2.0%
1,2,4- butantriols and sodium sulphate(Mass ratio 1:1) 0.25%
Protease, pectase and lipase(Mass ratio 1:1:2) 70.0%
Zinc oxide and sodium silicoaluminate(Mass ratio 2:1) 1%.
The method for preparing above-mentioned particle, its step are:Each material of core is sufficiently mixed into moistening by device bottom mixing slurry
Softwood, oar is then crushed by high speed and cuts into uniform wet granular;Coated on wet granular, obtained particle diameter is coating compound
0.1mm particle.It is 11 that reaction pH is prepared in its step, reaction time 24h, and reaction temperature is 0 DEG C.When it is implemented, institute
Acrylonitrile graft copolymer starch or polyvinyl alcohol graft copolymerized copolymerization starch can be used by stating graft copolymerization starch, and above-mentioned preparation method is being squeezed
Go out in machine and prepare.
Above-mentioned granzyme motility characteristics are shown in Table 1.
Embodiment 7
A kind of particle based on biological enzymatic compositions, it is made up of core and the coating being coated on core, the core
Portion and coating are made up of the raw material of following weight percents,
CMS(Or HES or cyanoethyl starch)And bentonite(Mass ratio 1:3) 10.0%
Middle degree of polymerization polyvinyl alcohol and polyvinyl alcohol with low degree of polymerization(Mass ratio 1:1) 0.2%
The triols of 1,2,5- penta and sodium sulphate(Mass ratio 2:1) 1.0%
Lipase, Novi's letter enzyme and novel subtilases(Mass ratio 2:2:1) 70%
Titanium dioxide and zinc oxide(Mass ratio 3:1) 18.8%.
The method for preparing above-mentioned particle, its step are:Each material of core is sufficiently mixed into moistening by device bottom mixing slurry
Softwood, oar is then crushed by high speed and cuts into uniform wet granular;For coating compound coated on wet granular, it is 1mm that particle diameter, which is made,
Particle.It is 12 that reaction pH is prepared in its step, reaction time 1h, and reaction temperature is 5 DEG C.When it is implemented, can be round as a ball
Prepared in machine.
Above-mentioned granzyme motility characteristics are shown in Table 1.
Embodiment 8
A kind of particle based on biological enzymatic compositions, it is made up of core and the coating being coated on core, the core
Portion and coating are made up of the raw material of following weight percents,
Dextrin(Or cyclodextrin or oxidized starch) 38.0%
The superelevation degree of polymerization(Molecular weight 25~300,000)Polyvinyl alcohol 14.0%
Ethylene glycol and calcium carbonate(Mass ratio 1:2) 32.0%
Protease(Or pectase or cellulase) 0.01%
Titanium dioxide 15.99%.
The method for preparing above-mentioned particle, its step are:Each material of core is sufficiently mixed into moistening by device bottom mixing slurry
Softwood, oar is then crushed by high speed and cuts into uniform wet granular;For coating compound coated on wet granular, it is 5mm that particle diameter, which is made,
Particle.It is 12 that reaction pH is prepared in its step, reaction time 1h, and reaction temperature is 10 DEG C.When it is implemented, above-mentioned preparation
Method is prepared in a mixer.
Above-mentioned granzyme motility characteristics are shown in Table 1.
Embodiment 9
A kind of particle based on biological enzymatic compositions, it is made up of core and the coating being coated on core, the core
Portion and coating are made up of the raw material of following weight percents,
Acid treated starches(Or starch phosphate) 20.0%
The middle degree of polymerization(Molecular weight 12~150,000)Polyvinyl alcohol 15.0%
1,2- butanediols(Or 1,3 butylene glycol or 1,4- butanediols)And calcium carbonate(Mass ratio 1:1) 35.0%
Lipase 10.0%
Lithopone 20.0%.
The method for preparing above-mentioned particle, its step are:Each material of core is sufficiently mixed into moistening by device bottom mixing slurry
Softwood, oar is then crushed by high speed and cuts into uniform wet granular;For coating compound coated on wet granular, it is 5mm that particle diameter, which is made,
Particle.It is 6 that reaction pH is prepared in its step, reaction time 7h, and reaction temperature is 10 DEG C.When it is implemented, it can spray
Prepared in fluidized bed plant.
Above-mentioned granzyme motility characteristics are shown in Table 1.
Each embodiment granzyme motility characteristics result of table 1
It is real Apply Example | Enzyme contained by particle | Initial enzyme activity in particle Power(U/g) | It is formulated and is measured when washing powder Enzyme activity(U/g) | It is formulated the surrounding in washing powder Enzyme activity afterwards(U/g) |
1 | Protease | 14.25 ten thousand | 14.10 ten thousand | 14.10 ten thousand |
2 | Lipase and half fibre Tie up plain enzyme | Respectively 25.23 ten thousand, 4009.00 | Respectively 25.22 ten thousand, 4001.09 | Respectively 24.20 ten thousand, 4001.05 |
3 | Cellulase | 3674.01 | 3673.25 | 3673.10 |
4 | Amylase | 34.01 ten thousand | 33.75 ten thousand | 33.70 ten thousand |
5 | Novel subtilases | 24.01 ten thousand | 23.75 ten thousand | 23.70 ten thousand |
6 | Protease, pectase And lipase | Respectively 24.23 ten thousand, 6008.00,20.50 ten thousand | Respectively 24.22 ten thousand, 6001.09,20.09 ten thousand | Respectively 24.20 ten thousand, 6001.05,20.09 ten thousand |
7 | Lipase, amylase and Novel subtilases | Respectively 28.3 ten thousand, 37.6 ten thousand and 27.3 ten thousand | Respectively 28.1 ten thousand, 37.4 Ten thousand and 27.2 ten thousand | Respectively 28.0 ten thousand, 37.4 ten thousand With 27.2 ten thousand |
8 | Cellulase | 2407.0 | 2405.0 | 2401.0 |
9 | Lipase | 26.01 ten thousand | 25.75 ten thousand | 25.70 ten thousand |
Claims (2)
- A kind of 1. method for preparing the particle based on biological enzymatic compositions, it is characterised in that its step is:Each material of core is by height Fast mixing granulation motor spindle mixing oar is sufficiently mixed into moistening softwood, and then crushing oar by high speed cuts into uniform wet granular; Coating compound is coated on wet granular;It is 6~12 to prepare reaction pH, and the reaction time is 1~24h, and reaction temperature is 0~80 DEG C;The core and coating are made up of the raw material of following weight percents,Filler 1.0~40.0%Adhesive 0.1~15.0%Enzymatic protective reagent 0.25~35.0%The composition 0.01~70.0% of enzyme or enzymeCoating 0.25~20.0%;The grain diameter of the biological enzymatic compositions is 0.01mm~10mm;The filler is one kind or any several with any in converted starch, kaolin, cellulose, diatomite or bentonite The mixture of ratio mixing;Described adhesive is super polyvinyl alcohol of high degree of polymerization, polyvinyl alcohol of high degree of polymerization, middle degree of polymerization polyvinyl alcohol, low polymerization degree One kind or any several mixtures mixed with arbitrary proportion in polyvinyl alcohol or polyvinylpyrrolidone;The enzymatic protective reagent is the mixture that dihydric alcohol and calcium carbonate are mixed with arbitrary proportion, or trihydroxylic alcohol and sodium sulphate are to appoint The mixture of meaning ratio mixing;The enzyme is selected from protease, pectase, cellulase, lipase, hemicellulase;The composition of enzyme is protease, fruit The mixture mixed in glue enzyme, cellulase, lipase or hemicellulase with arbitrary proportion;The coating is one kind in titanium dioxide, zinc oxide, lithopone or sodium silicoaluminate or any several mixed with arbitrary proportion Mixture.
- 2. application of the particle of biological enzymatic compositions in articles for washing described in claim 1.
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CN105925399A (en) * | 2016-04-28 | 2016-09-07 | 山西勇宁记科技有限公司 | High-efficiency complex lipase for detergents |
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CN108148827B (en) * | 2016-12-02 | 2022-09-23 | 丰益(上海)生物技术研发中心有限公司 | Immobilized enzyme and preparation method and application thereof |
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WO2019125683A1 (en) * | 2017-12-21 | 2019-06-27 | Danisco Us Inc | Enzyme-containing, hot-melt granules comprising a thermotolerant desiccant |
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CN108277117A (en) * | 2018-02-11 | 2018-07-13 | 山西勇宁记科技有限公司 | A kind of laundry cleansing soap ferment particle and the preparation method and application thereof |
CN111513194A (en) * | 2020-04-15 | 2020-08-11 | 浙江惠嘉生物科技股份有限公司 | High-temperature-resistant cyclodextrin inclusion enzyme preparation and preparation method thereof |
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