CN102433225A - Alkaline proteinase coated micro-pill and preparation method thereof - Google Patents
Alkaline proteinase coated micro-pill and preparation method thereof Download PDFInfo
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- CN102433225A CN102433225A CN2011104482669A CN201110448266A CN102433225A CN 102433225 A CN102433225 A CN 102433225A CN 2011104482669 A CN2011104482669 A CN 2011104482669A CN 201110448266 A CN201110448266 A CN 201110448266A CN 102433225 A CN102433225 A CN 102433225A
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Abstract
The invention relates to an alkaline proteinase coated micro-pill and a preparation method thereof. The alkaline proteinase coated micro-pill comprises 50-90 wt% of enzyme-containing pill core and 10-50 wt% of coating layer coated on the enzyme-containing pill core, wherein the enzyme-containing pill core is prepared from alkaline proteinase, dextrin, starch, bean flour, lactose, sodium dodecylsulfate, microcrystalline cellulose and corn steep liquor dry powder; and the coating layer is prepared from dextrin, starch, polyvinyl alcohol, sodium dodecylsulfate, sodium sulfate, titanium white and brilliant blue. The alkaline proteinase coated micro-pill has the advantages of round and complete particles, no peculiar smell and uniform size; the 30-60 mesh particles account for more than 99%; and the main properties of the alkaline proteinase coated micro-pill are superior to those of like products abroad: compared with washing powder, the alkaline proteinase coated micro-pill has better mixing uniformity, higher dissolution rate and longer storage time.
Description
Technical field
The invention belongs to proteolytic enzyme coated micropill technical field, be specifically related to a kind of Sumizyme MP coated micropill and preparation method thereof.
Background technology
In the past few years,, make without phosphorus or low-phosphorous washing composition more and more receive an acclaim because the water source eutrophication problem that the phosphorus in the washing composition causes is serious day by day.In low-phosphorous or free phosphate detergent prescription,, the detersive power of cleaning product is descended thereupon owing to cut down phosphorous assistant.Washing composition towards low phosphatization or do not have phosphatization and the cold washing Development Trend under; Enzyme-added is that one of effective way of usefulness is washed in the raising of generally acknowledging, washing develops into the crucial or conventional component that has status of equal importance with tensio-active agent, auxiliary agent from general auxiliary ingredients with enzyme.Enzyme for detergent mainly is a Sumizyme MP, often adds in the washing powder with the form of solid preparation.But directly in washing powder, add enzyme and also have some problems; Sumizyme MP has peculiar smell; The dust of enzyme can cause the anaphylaxis of contact to the part crowd; The mixed back of enzyme powder and washing powder is difficult for preserving etc. because the difference of granularity and proportion causes the component of product inhomogeneous, and the enzyme powder is prone to the moisture absorption inactivation.For addressing the above problem, the at present employing carried out Cotton seeds with Sumizyme MP more, processes enzyme granulate, thereby reduced dust pollution, improves the stability and the homogeneity of product.But existing coating type basic protein enzyme product ubiquity enzyme activity is low, coarse irregular, the problem such as roundness is poor, wet-hot aging performance is poor, preservation period is short of particle.
Summary of the invention
The purpose of this invention is to provide a kind of Sumizyme MP coated micropill and preparation method thereof, thereby provide a kind of outward appearance to be spherical, granularity and hardness better Sumizyme MP coated micropill preferably, stable, thereby remedy the deficiency of prior art.
One aspect of the present invention relates to a kind of Sumizyme MP coated micropill; Including mass percent and be 50%～90% the enzyme ball core that contains contains on the enzyme ball core with being wrapped in; Mass percent is 10%～50% coatings; Wherein contain enzyme ball core and be made up of Sumizyme MP, dextrin, starch, bean powder, lactose, sodium laurylsulfonate, Microcrystalline Cellulose and Dried Corn Steep Liquor Powder, coatings is made up of dextrin, starch, Z 150PH, sodium laurylsulfonate, sodium sulfate, white titanium pigment and light blue.
The above-mentioned quality group that contains each component of enzyme ball core becomes to be respectively: Sumizyme MP 20%-60%, dextrin 5%～15%, starch 10%～30%, bean powder 10%～30%, lactose 1%～5%, sodium laurylsulfonate 0.1%～3%, Microcrystalline Cellulose 5%～10%, Dried Corn Steep Liquor Powder 4%～10%.
The quality group of each ingredients constitute coatings of above-mentioned coatings becomes to be respectively: dextrin 15%～30%, starch 10%～30%, Z 150PH 5%～15%, sodium laurylsulfonate 1%～6%, sodium sulfate 10%～20%, white titanium pigment 15%～30%, light blue 0.01%～0.1%.
The quality composition of each ingredients constitute coatings of above-mentioned coatings is preferably: dextrin 21%, starch 20%, Z 150PH 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, white titanium pigment 22.95%, light blue 0.05%.
Another aspect of the present invention relates to the method for preparing above-mentioned Sumizyme MP coated micropill, and step is following:
(1) preparation contains enzyme ball core: take by weighing in proportion and contain each component of enzyme ball core, sieve, mix; Drop in the centrifugal granulator machine, regulate rotating speed 600rpm～1200rpm, blower fan 10Hz～20Hz; Make tackiness agent with water, spray velocity 15rpm～50rpm, pulverulent material receive the acting in conjunction of rotating disk cf-, frictional force and annular space buoyant gas; Mix with the water that sprays into, mother has been accomplished in bonding gathering, granulation, particle are amplified, process such as round as a ball, form to contain enzyme ball core;
(2) drying contains enzyme ball core: the enzyme ball core that contains that will prepare places fluidized-bed, and 40 ℃～80 ℃ of EATs, air quantity 100m3/h～180m3/h are set, and is dried to temperature of charge and reaches 35 ℃～70 ℃, shuts down, and accomplishes the drying that contains enzyme ball core;
(3) parcel coatings: take by weighing each component of coatings in proportion, add water and be mixed with the suspension that mass volume ratio is 5%-8%, and cross 100 mesh standard sieves, promptly get coating liquid; Get a certain amount of enzyme ball core that contains and place fluidized-bed, regulate 40 ℃～80 ℃ of EATs, air quantity 80m3/h～180m3/h, atomizing pressure 1.2bar～2.5bar selects 0.8mm～1.5mm spray gun for use, evenly sprays coating liquid with the speed of 8rpm～20rpm; After dressing finished, continuing to be heated to temperature of charge was 35 ℃～70 ℃, shut down, and promptly got the Sumizyme MP coated micropill.
Sumizyme MP coated micropill particle rounding of the present invention, free from extraneous odour, size is even, and 30-60 purpose particle accounts for more than 99%, and salient features all is superior to external like product: unit weight is 700g～900g, with washing powder mixture homogeneity is preferably arranged; Dissolution rate is fast; Long preservative period was preserved 6 months under 25 ℃ of conditions, and the enzyme activity loss is about 4%-5%; Wet-hot aging performance is good, under 37 ℃, 70% humidity condition, preserves 3 months, and the enzyme activity loss is about 9%-10%; Clean effect is good.
Embodiment
Raw material and equipment that the present invention is used to prepare the Sumizyme MP coated micropill all can be selected from any one commercially available product.Further describe the present invention through specific embodiment below, but should not be regarded as restriction invention scope.
Embodiment 1
Ratio in Sumizyme MP powder 20%, dextrin 15%, starch 15%, bean powder 30%, lactose 1%, sodium laurylsulfonate 3%, Microcrystalline Cellulose 6%, Dried Corn Steep Liquor Powder 10% takes by weighing each component of ball core respectively; 25kg mixes 30min in mixing machine altogether, drops in the centrifugal granulator machine; Rotating speed 600rpm is set; Blower fan 10Hz uses water as tackiness agent, spray velocity 15rpm.Behind the 40min, emit micropill, place fluidized-bed, 40 ℃ of EATs are set, air quantity 100m3/h is dried to 35 ℃ of material temperature, emits dry good micropill, promptly gets to contain enzyme ball core.
Ratio in dextrin 30%, starch 10%, Z 150PH 15%, sodium laurylsulfonate 1%, sodium sulfate 20%, white titanium pigment 24%, light blue 0.01% takes by weighing each component of coatings respectively, altogether 10kg; Adding water, to process mass volume ratio be 5% suspension liquid, crosses 100 mesh standard sieves, promptly gets coating liquid; The enzyme ball core 10kg that contains of preparation is dropped in the fluidized-bed, start fluidized-bed and dressing equipment, regulate 40 ℃ of EATs, air quantity 80m3/h, atomizing pressure 1.2bar selects the 0.8mm spray gun for use, evenly sprays coating liquid with the speed of 8rpm; After dressing finished, continuing to be heated to temperature of charge was 35 ℃, shut down, and blowing promptly gets the Sumizyme MP coated micropill.
Embodiment 2
Ratio in Sumizyme MP powder 60%, dextrin 5%, starch 10%, bean powder 10%, lactose 3%, sodium laurylsulfonate 1%, Microcrystalline Cellulose 7%, Dried Corn Steep Liquor Powder 4% takes by weighing each component of ball core respectively; Be total to 25kg; In mixing machine, mix 30min, drop in the centrifugal granulator machine, rotating speed 800rpm, blower fan 14Hz are set; Use water as tackiness agent, spray velocity 20rpm.Behind the 30min, emit micropill, place fluidized-bed, 50 ℃ of EATs are set, air quantity 120m3/h is dried to 40 ℃ of material temperature, emits dry good micropill, promptly gets to contain enzyme ball core.
Press dextrin 15%, starch 30%, Z 150PH 5%, sodium laurylsulfonate 6%, sodium sulfate 13.9%, white titanium pigment 30%, the ratio of light blue 0.1% takes by weighing each component of coatings respectively, altogether 7kg; Adding water, to process mass volume ratio be 7% suspension liquid, crosses 100 mesh standard sieves, promptly gets coating liquid; The enzyme ball core 10kg that contains of preparation is dropped in the fluidized-bed, start fluidized-bed and dressing equipment, 50 ℃ of EATs, air quantity 160m3/h are set, atomizing pressure 2.0bar selects the 1.0mm spray gun for use, evenly sprays coating liquid with the speed of 15rpm; After dressing finished, continuing to be heated to temperature of charge was 42 ℃, shut down, and blowing promptly gets the Sumizyme MP coated micropill.
Embodiment 3
Ratio in Sumizyme MP powder 30%, dextrin 10%, starch 30%, bean powder 12%, lactose 2%, sodium laurylsulfonate 1%, Microcrystalline Cellulose 10%, Dried Corn Steep Liquor Powder 5% takes by weighing each component of ball core respectively; Be total to 25kg; In mixing machine, mix 30min, drop in the centrifugal granulator machine, rotating speed 1000rpm, blower fan 17Hz are set; Use water as tackiness agent, spray velocity 40rpm.Behind the 25min, emit micropill, place fluidized-bed, 80 ℃ of EATs are set, air quantity 160m3/h is dried to 70 ℃ of material temperature, emits dry good micropill, promptly gets to contain enzyme ball core.
Press dextrin 25%, starch 27%, Z 150PH 13%, sodium laurylsulfonate 5%, sodium sulfate 10%, white titanium pigment 20%, the ratio of light blue 0.02% takes by weighing each component of coatings respectively, altogether 2.5kg; Adding water, to process mass volume ratio be 7% suspension liquid, crosses 100 mesh standard sieves, promptly gets coating liquid; The enzyme ball core 10kg that contains of preparation is dropped in the fluidized-bed, start fluidized-bed and dressing equipment, regulate 80 ℃ of EATs, air quantity 180m3/h, atomizing pressure 2.5bar selects the 1.5mm spray gun for use, evenly sprays coating liquid with the speed of 20rpm; After dressing finished, continuing to be heated to temperature of charge was 70 ℃, shut down, and blowing promptly gets the Sumizyme MP coated micropill.
Embodiment 4
Ratio in Sumizyme MP powder 40%, dextrin 10%, starch 20%, bean powder 15%, lactose 5%, sodium laurylsulfonate 0.1%, Microcrystalline Cellulose 4.9%, Dried Corn Steep Liquor Powder 5% takes by weighing each component of ball core respectively; Be total to 25kg; In mixing machine, mix 30min, drop in the centrifugal granulator machine, rotating speed 1200rpm, blower fan 20Hz are set; Use water as tackiness agent, spray velocity 50rpm.Behind the 20min, emit micropill, place fluidized-bed, 60 ℃ of EATs are set, air quantity 180m3/h is dried to 50 ℃ of material temperature, emits dry good micropill, promptly gets to contain enzyme ball core.
Press dextrin 25%, starch 27%, Z 150PH 13%, sodium laurylsulfonate 5%, sodium sulfate 10%, white titanium pigment 20%, the ratio of light blue 0.02% takes by weighing each component of coatings respectively, altogether 1112g; Adding water, to process mass volume ratio be 8% suspension liquid, crosses 100 mesh standard sieves, promptly gets coating liquid; The enzyme ball core 10kg that contains of preparation is dropped in the fluidized-bed, start fluidized-bed and dressing equipment, regulate 65 ℃ of EATs, air quantity 150m3/h, atomizing pressure 2.0bar selects the 1.0mm spray gun for use, evenly sprays coating liquid with the speed of 13rpm; After dressing finished, continuing to be heated to temperature of charge was 55 ℃, shut down, and blowing promptly gets the Sumizyme MP coated micropill.
The performance test of Sumizyme MP coated micropill according to the invention and comparison:
Get the Sumizyme MP coated micropill that makes among the foregoing description 1-4 and carry out performance test, and compare with external two kinds of like products, following: state's exoenzyme 1 is Novozymes Company's Sumizyme MP coated micropill product, numbering Savinase 8.0T; State's exoenzyme 2 is company of an outstanding person's ability section Sumizyme MP coated micropill product, numbering PuraFast2000HS.
(1) outward appearance and smell: naked eyes or use reading lens are observed particulate color and rounding situation.It is blue that Sumizyme MP coated micropill according to the invention is, outward appearance spheroidal, even particle size, free from extraneous odour.
(2) granularity: random sampling 1kg, sieve with standard sieve.Sumizyme MP coated micropill size distribution according to the invention is suitable, and 30 orders～60 orders account for more than 99%.
(3) hardness: the sensory measurement, do not have fragmentation with finger when twisting with the fingers with strength.
(4) unit weight: in the 1L graduated cylinder, add Sumizyme MP coated micropill according to the invention to the 1L scale marks, measure the weight of the enzyme that adds, be unit weight.Sumizyme MP coated micropill unit weight according to the invention is between 700g～900g, and (unit weight of state's exoenzyme 1, enzyme 2 is 1100g～1200g), with washing powder mixture homogeneity is preferably arranged to be superior to external like product.
(5) enzyme is lived: (QB/T 1803-1993) carries out the detection of enzyme activity according to the general TP of industrial enzyme preparation.Sumizyme MP coated micropill according to the invention enzyme activity loss in the preparation process is lower than 5%.
(6) solvability: Sumizyme MP coated micropill according to the invention and water are put into water with 1: 100 ratio, and magnetic agitation stirs at a slow speed, and at ambient temperature, micropill can dissolve in 3min fully; And state's exoenzyme 1, enzyme 2 dissolution times are all greater than 3min.
(7) weight loss on drying: (QB/T 1803-1993) carries out the detection of weight loss on drying according to the general TP of industrial enzyme preparation, Sumizyme MP coated micropill weight loss on drying according to the invention≤5%.
(8) stability: under 25 ℃ of conditions, preserved 6 months, the enzyme activity loss is about 4%-5% in the Sumizyme MP coated micropill according to the invention.Under 37 ℃, 70% humidity condition, preserved 3 months, the enzyme activity loss is about 9%-10%, all is superior to external like product.(when under 25 ℃ of conditions, preserving 6 months, the vigor loss of state's exoenzyme 1 and enzyme 2 is about 7%-8%; When under 37 ℃, 75% humidity condition, preserving 3 months, the loss of living of state's exoenzyme 1 and enzyme 2 enzymes is about 14%-15%).
(9) Sumizyme MP coated micropill of the present invention is according to the mensuration of National Standard GBT 13174-2008 dress material with washing composition detersive power and circulation cleaning performance " test its clean effect, test result is superior to external like product.The detersive power test-results sees the following form:
The detersive power performance of different Sumizyme MP coated micropill products in standard washing powder
Annotate: state's exoenzyme 1: Novi's letter product, numbering Savinase 8.0T; State's exoenzyme 2: outstanding person's ability section product, numbering PuraFast2000HS.
In proteolytic enzyme coated micropill technical field, the selection of coatings component and content has significant effects for the stability of micropill and the preservation of enzyme activity.Therefore, the proportioning of coatings component is screened.
Embodiment 5
Adopt embodiment 1 said component and explained hereafter Sumizyme MP coated micropill, unique different be that the quality composition of each ingredients constitute coatings of coatings is adjusted into dextrin 21%, starch 20%, Z 150PH 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, white titanium pigment 22.95%, light blue 0.05%.The Sumizyme MP coated micropill that makes is carried out above-mentioned performance test, and compare with the Sumizyme MP coated micropill of embodiment 1.The result shows; The stability of the micropill of present embodiment preparation is superior to the micropill of embodiment 1 preparation; Specific as follows: under 25 ℃ of conditions, preserved 6 months, the enzyme activity loss is about 3.5% in the Sumizyme MP coated micropill of present embodiment preparation, and embodiment 1 is 4.0%.Under 37 ℃, 70% humidity condition, preserved 3 months, the Sumizyme MP coated micropill enzyme activity loss of present embodiment preparation is about 8.6%, and embodiment 1 is 9.0%.
Embodiment 6
Adopt embodiment 2 said components and explained hereafter Sumizyme MP coated micropill, unique different be that the quality composition of each ingredients constitute coatings of coatings is adjusted into dextrin 21%, starch 20%, Z 150PH 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, white titanium pigment 22.95%, light blue 0.05%.The Sumizyme MP coated micropill that makes is carried out above-mentioned performance test, and compare with the Sumizyme MP coated micropill of embodiment 2.The result shows that the stability of the micropill of present embodiment preparation is superior to the micropill of embodiment 2 preparations; Specific as follows: as under 25 ℃ of conditions, to preserve 6 months; The enzyme activity loss is about 3.8% in the Sumizyme MP coated micropill of present embodiment preparation, and embodiment 2 is 4.2%.Under 37 ℃, 70% humidity condition, preserved 3 months, the Sumizyme MP coated micropill enzyme activity loss of present embodiment preparation is about 8.7%, and embodiment 2 is 9.2%.
Embodiment 7
Adopt embodiment 3 said components and explained hereafter Sumizyme MP coated micropill, unique different be that the quality composition of each ingredients constitute coatings of coatings is adjusted into dextrin 21%, starch 20%, Z 150PH 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, white titanium pigment 22.95%, light blue 0.05%.The Sumizyme MP coated micropill that makes is carried out above-mentioned performance test, and compare with the Sumizyme MP coated micropill of embodiment 3.The result shows that the stability of the micropill of present embodiment preparation is superior to embodiment 3, and concrete outcome is following: under 25 ℃ of conditions, preserved 6 months, the enzyme activity loss is about 3.8% in the Sumizyme MP coated micropill of present embodiment preparation, and embodiment 3 is 4.6%.Under 37 ℃, 70% humidity condition, preserved 3 months, the Sumizyme MP coated micropill enzyme activity loss of present embodiment preparation is about 8.8%, and embodiment 3 is 9.5%.
Embodiment 8
Adopt embodiment 4 said components and explained hereafter Sumizyme MP coated micropill, unique different be that the quality composition of each ingredients constitute coatings of coatings is adjusted into dextrin 21%, starch 20%, Z 150PH 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, white titanium pigment 22.95%, light blue 0.05%.The Sumizyme MP coated micropill that makes is carried out above-mentioned performance test, and compare with the Sumizyme MP coated micropill of embodiment 4.The result shows that the stability of the micropill of present embodiment preparation is superior to embodiment 4, and concrete outcome is following: under 25 ℃ of conditions, preserved 6 months, the enzyme activity loss is about 4.2% in the Sumizyme MP coated micropill of present embodiment preparation, and embodiment 4 is 5.0%.Under 37 ℃, 70% humidity condition, preserved 3 months, the Sumizyme MP coated micropill enzyme activity loss of present embodiment preparation is about 9.4%, and embodiment 4 is 10.0%.
The performance test of the foregoing description 5-8 and comparative result show: the quality composition of each ingredients constitute coatings of coatings is preferably dextrin 21%, starch 20%, Z 150PH 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, white titanium pigment 22.95%, light blue 0.05%.The Sumizyme MP coated micropill of preparing like this has tangible advantage than other coatings set of dispense ratios in the preservation of stability and enzyme activity.
Claims (5)
1. Sumizyme MP coated micropill; Including mass percent and be 50%～90% the enzyme ball core that contains contains on the enzyme ball core with being wrapped in; Mass percent is 10%～50% coatings; Wherein contain enzyme ball core and be made up of Sumizyme MP, dextrin, starch, bean powder, lactose, sodium laurylsulfonate, Microcrystalline Cellulose and Dried Corn Steep Liquor Powder, coatings is made up of dextrin, starch, Z 150PH, sodium laurylsulfonate, sodium sulfate, white titanium pigment and light blue.
2. coated micropill as claimed in claim 1; It is characterized in that the described quality group that contains each component of enzyme ball core becomes to be respectively: Sumizyme MP 20%-60%, dextrin 5%～15%, starch 10%～30%, bean powder 10%～30%, lactose 1%～5%, sodium laurylsulfonate 0.1%～3%, Microcrystalline Cellulose 5%～10%, Dried Corn Steep Liquor Powder 4%～10%.
3. coated micropill as claimed in claim 1 is characterized in that the quality group of each ingredients constitute coatings of described coatings becomes to be respectively: dextrin 15%～30%, starch 10%～30%, Z 150PH 5%～15%, sodium laurylsulfonate 1%～6%, sodium sulfate 10%～20%, white titanium pigment 15%～30%, light blue 0.01%～0.1%.
4. coated micropill as claimed in claim 3 is characterized in that the quality group of each ingredients constitute coatings of described coatings becomes: dextrin 21%, starch 20%, Z 150PH 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, white titanium pigment 22.95%, light blue 0.05%.
5. the preparation method of the described Sumizyme MP coated micropill of claim 1, its step is following:
(1) preparation contains enzyme ball core: take by weighing in proportion and contain each component of enzyme ball core, sieve, mix; Drop in the centrifugal granulator machine, regulate rotating speed 600rpm～1200rpm, blower fan 10Hz～20Hz; Make tackiness agent with water, spray velocity 15rpm～50rpm, pulverulent material receive the acting in conjunction of rotating disk cf-, frictional force and annular space buoyant gas; Mix with the water that sprays into, mother has been accomplished in bonding gathering, granulation, particle are amplified, process such as round as a ball, form to contain enzyme ball core;
(2) drying contains enzyme ball core: the enzyme ball core that contains that will prepare places fluidized-bed, and 40 ℃～80 ℃ of EATs, air quantity 100m3/h～180m3/h are set, and is dried to temperature of charge and reaches 35 ℃～70 ℃, shuts down, and accomplishes the drying that contains enzyme ball core;
(3) parcel coatings: take by weighing each component of coatings in proportion, add water and be mixed with the suspension that mass volume ratio is 5%-8%, and cross 100 mesh standard sieves, promptly get coating liquid; Get a certain amount of enzyme ball core that contains and place fluidized-bed, regulate 40 ℃～80 ℃ of EATs, air quantity 80m3/h～180m3/h, atomizing pressure 1.2bar～2.5bar selects 0.8mm～1.5mm spray gun for use, evenly sprays coating liquid with the speed of 8rpm～20rpm; After dressing finished, continuing to be heated to temperature of charge was 35 ℃～70 ℃, shut down, and promptly got the Sumizyme MP coated micropill.
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Cited By (6)
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| CN103555706A (en) * | 2013-10-17 | 2014-02-05 | 青岛蔚蓝生物集团有限公司 | Production method of coated enzyme granules |
| CN104673560A (en) * | 2015-03-25 | 2015-06-03 | 山西勇宁记科技有限公司 | Granule based on biological enzyme composition as well as preparation method and application thereof |
| CN106318666A (en) * | 2016-08-23 | 2017-01-11 | 余姚市德派日用品有限公司 | Infant clothing laundry condensate bead and preparing method thereof |
| CN106318667A (en) * | 2016-08-23 | 2017-01-11 | 余姚市德派日用品有限公司 | Excellent bactericidal washing laundry condensate bead and preparing method thereof |
| CN106350270A (en) * | 2016-08-23 | 2017-01-25 | 余姚市德派日用品有限公司 | Undesirable odor removing type laundry condensate bead and preparation method thereof |
| CN106381234A (en) * | 2016-08-23 | 2017-02-08 | 余姚市德派日用品有限公司 | Brightening laundry bead and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103555706A (en) * | 2013-10-17 | 2014-02-05 | 青岛蔚蓝生物集团有限公司 | Production method of coated enzyme granules |
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| CN104673560B (en) * | 2015-03-25 | 2017-12-29 | 山西勇宁记科技有限公司 | Particle based on biological enzymatic compositions and preparation method and application |
| CN106318666A (en) * | 2016-08-23 | 2017-01-11 | 余姚市德派日用品有限公司 | Infant clothing laundry condensate bead and preparing method thereof |
| CN106318667A (en) * | 2016-08-23 | 2017-01-11 | 余姚市德派日用品有限公司 | Excellent bactericidal washing laundry condensate bead and preparing method thereof |
| CN106350270A (en) * | 2016-08-23 | 2017-01-25 | 余姚市德派日用品有限公司 | Undesirable odor removing type laundry condensate bead and preparation method thereof |
| CN106381234A (en) * | 2016-08-23 | 2017-02-08 | 余姚市德派日用品有限公司 | Brightening laundry bead and preparation method thereof |
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|---|---|
| CN102433225B (en) | 2013-02-20 |
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