CN102433225B - 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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- CN102433225B CN102433225B CN 201110448266 CN201110448266A CN102433225B CN 102433225 B CN102433225 B CN 102433225B CN 201110448266 CN201110448266 CN 201110448266 CN 201110448266 A CN201110448266 A CN 201110448266A CN 102433225 B CN102433225 B CN 102433225B
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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 alkaline proteinase coated micro-pill and preparation method thereof.
Background technology
In the past few years, because the water source eutrophication problem that the phosphorus in the washing composition causes is day by day serious, so that without phosphorus or low-phosphorous washing composition more and more receives an acclaim.In low-phosphorous or free phosphate detergent prescription, owing to having cut down phosphorous assistant, the detersive power of cleaning product is descended thereupon.At washing composition under low phosphatization or the trend without phosphatization and cold washing development, 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 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 part population, difference owing to granularity and proportion after enzyme powder and washing powder are mixed causes the component of product inhomogeneous, the easy moisture absorption inactivation of enzyme powder is difficult for preserving etc.For addressing the above problem, adopt carried out Cotton seeds with Sumizyme MP more at present, makes enzyme granulate, thereby reduced dust pollution, improves 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 alkaline proteinase coated micro-pill and preparation method thereof, thus provide a kind of outward appearance be spheroidal, granularity and hardness is preferably, the better alkaline proteinase coated micro-pill of stability, thereby remedy the deficiencies in the prior art.
One aspect of the present invention relates to a kind of alkaline proteinase coated micro-pill, include mass percent and be 50%～90% contain enzyme ball core and be wrapped in and contain on the enzyme ball core, mass percent is 10%～50% coatings, wherein contain enzyme ball core and be comprised of Sumizyme MP, dextrin, starch, bean powder, lactose, sodium laurylsulfonate, Microcrystalline Cellulose and Dried Corn Steep Liquor Powder, coatings is comprised of dextrin, starch, polyvinyl alcohol, sodium laurylsulfonate, sodium sulfate, titanium dioxide 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 that each component of above-mentioned coatings accounts for coatings becomes to be respectively: dextrin 15%～30%, starch 10%～30%, polyvinyl alcohol 5%～15%, sodium laurylsulfonate 1%～6%, sodium sulfate 10%～20%, titanium dioxide 15%～30%, light blue 0.01%～0.1%.
The quality composition that each component of above-mentioned coatings accounts for coatings is preferably: dextrin 21%, starch 20%, polyvinyl alcohol 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, titanium dioxide 22.95%, light blue 0.05%.
Another aspect of the present invention relates to the method for preparing above-mentioned alkaline proteinase coated micro-pill, and step is as follows:
(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 adjusting rotary speed 600rpm～1200rpm, blower fan 10Hz～20Hz, make tackiness agent with water, spray velocity 15rpm～50rpm, pulverulent material are subjected to the acting in conjunction of rotating disk centrifugal force, frictional force and annular space buoyant gas, mix with the water that sprays into, mother has been finished in bonding gathering, granulation, particle are amplified, the 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 inlet temperature, air quantity 100m3/h～180m3/h are set, and is dried to temperature of charge and reaches 35 ℃～70 ℃, shuts down, and finishes the drying that contains enzyme ball core;
(3) parcel coatings: take by weighing in proportion each component of coatings, add water and be mixed with the suspension that mass volume ratio is 5%-8%, and cross 100 mesh standard sieves, namely get coating liquid; Get a certain amount of enzyme ball core that contains and place fluidized-bed, regulate 40 ℃～80 ℃ of inlet temperature, air quantity 80m3/h～180m3/h, atomizing pressure 1.2bar～2.5bar selects 0.8mm～1.5mm spray gun, 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 namely got alkaline proteinase coated micro-pill.
Alkaline proteinase coated micro-pill 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 better than same kind of products at abroad: unit weight is 700g～900g, with washing powder preferably mixture homogeneity is 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, preserves 3 months under 37 ℃, 70% humidity condition, and the enzyme activity loss is about 9%-10%; Clean effect is good.
Embodiment
The present invention all can be selected from any one commercially available product for the preparation of raw material and the equipment of alkaline proteinase coated micro-pill.Further describe the present invention below by specific embodiment, but should not be considered as the restriction to 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 respectively each component of ball core; be total to 25kg; in mixing machine, mix 30min; drop 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 inlet temperature are set, air quantity 100m3/h is dried to 35 ℃ of material temperatures, emits dry good micropill, namely gets to contain enzyme ball core.
Ratio in dextrin 30%, starch 10%, polyvinyl alcohol 15%, sodium laurylsulfonate 1%, sodium sulfate 20%, titanium dioxide 24%, light blue 0.01% takes by weighing respectively each component of coatings, altogether 10kg; Adding water, to make mass volume ratio be 5% suspension liquid, crosses 100 mesh standard sieves, namely gets coating liquid; The enzyme ball core 10kg that contains of preparation is dropped in the fluidized-bed, start fluidized-bed and coating equipment in sugar production line, regulate 40 ℃ of inlet temperature, air quantity 80m3/h, atomizing pressure 1.2bar selects the 0.8mm spray gun, 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 namely gets alkaline proteinase coated micro-pill.
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 respectively each component of ball core; 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 inlet temperature are set, air quantity 120m3/h is dried to 40 ℃ of material temperatures, emits dry good micropill, namely gets to contain enzyme ball core.
Press dextrin 15%, starch 30%, polyvinyl alcohol 5%, sodium laurylsulfonate 6%, sodium sulfate 13.9%, titanium dioxide 30%, the ratio of light blue 0.1% takes by weighing respectively each component of coatings, altogether 7kg; Adding water, to make mass volume ratio be 7% suspension liquid, crosses 100 mesh standard sieves, namely gets coating liquid; The enzyme ball core 10kg that contains of preparation is dropped in the fluidized-bed, start fluidized-bed and coating equipment in sugar production line, 50 ℃ of inlet temperature, air quantity 160m3/h are set, atomizing pressure 2.0bar selects the 1.0mm spray gun, 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 namely gets alkaline proteinase coated micro-pill.
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 respectively each component of ball core; 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 inlet temperature are set, air quantity 160m3/h is dried to 70 ℃ of material temperatures, emits dry good micropill, namely gets to contain enzyme ball core.
Press dextrin 25%, starch 27%, polyvinyl alcohol 13%, sodium laurylsulfonate 5%, sodium sulfate 10%, titanium dioxide 20%, the ratio of light blue 0.02% takes by weighing respectively each component of coatings, altogether 2.5kg; Adding water, to make mass volume ratio be 7% suspension liquid, crosses 100 mesh standard sieves, namely gets coating liquid; The enzyme ball core 10kg that contains of preparation is dropped in the fluidized-bed, start fluidized-bed and coating equipment in sugar production line, regulate 80 ℃ of inlet temperature, air quantity 180m3/h, atomizing pressure 2.5bar selects the 1.5mm spray gun, 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 namely gets alkaline proteinase coated micro-pill.
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 respectively each component of ball core; 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 inlet temperature are set, air quantity 180m3/h is dried to 50 ℃ of material temperatures, emits dry good micropill, namely gets to contain enzyme ball core.
Press dextrin 25%, starch 27%, polyvinyl alcohol 13%, sodium laurylsulfonate 5%, sodium sulfate 10%, titanium dioxide 20%, the ratio of light blue 0.02% takes by weighing respectively each component of coatings, altogether 1112g; Adding water, to make mass volume ratio be 8% suspension liquid, crosses 100 mesh standard sieves, namely gets coating liquid; The enzyme ball core 10kg that contains of preparation is dropped in the fluidized-bed, start fluidized-bed and coating equipment in sugar production line, regulate 65 ℃ of inlet temperature, air quantity 150m3/h, atomizing pressure 2.0bar selects the 1.0mm spray gun, 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 namely gets alkaline proteinase coated micro-pill.
The performance test of alkaline proteinase coated micro-pill of the present invention and comparison:
Get the alkaline proteinase coated micro-pill that makes among above-described embodiment 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 alkaline proteinase coated micro-pill product, numbering Savinase 8.0T; State's exoenzyme 2 is company of outstanding person's energy section alkaline proteinase coated micro-pill product, numbering PuraFast2000HS.
(1) outward appearance and smell: color and rounding situation that naked eyes or use magnifying glass are observed particle.It is blue that alkaline proteinase coated micro-pill of the present invention is, outward appearance spheroidal, even particle size, free from extraneous odour.
(2) granularity: random sampling 1kg, sieve with standard sieve.Alkaline proteinase coated micro-pill size distribution of the present invention is suitable, and 30 orders～60 orders account for more than 99%.
(3) hardness: the sensory measurement, with finger when twisting with the fingers with strength without fragmentation.
(4) unit weight: in the 1L graduated cylinder, add alkaline proteinase coated micro-pill of the present invention to the 1L scale marks, measure the weight of the enzyme that adds, be unit weight.Alkaline proteinase coated micro-pill unit weight of the present invention is between 700g～900g, and (unit weight of state's exoenzyme 1, enzyme 2 is 1100g～1200g), with washing powder preferably mixture homogeneity is arranged to be better than same kind of products at abroad.
(5) enzyme is lived: (QB/T 1803-1993) carries out the detection of enzyme activity according to industrial enzyme preparation universal test method.Alkaline proteinase coated micro-pill of the present invention enzyme activity loss in preparation process is lower than 5%.
(6) solvability: alkaline proteinase coated micro-pill of the present invention and water are put into water with 1: 100 ratio, the magnetic agitation low rate mixing, 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 industrial enzyme preparation universal test method, alkaline proteinase coated micro-pill weight loss on drying of the present invention≤5%.
(8) stability: preserved 6 months under 25 ℃ of conditions, the enzyme activity loss is about 4%-5% in the alkaline proteinase coated micro-pill of the present invention.Preserved 3 months under 37 ℃, 70% humidity condition, the enzyme activity loss is about 9%-10%, all is better than same kind of products at abroad.(when preserving 6 months under 25 ℃ of conditions, the vigor loss of state's exoenzyme 1 and enzyme 2 is about 7%-8%; When preserving 3 months under 37 ℃, 75% humidity condition, the loss of living of state's exoenzyme 1 and enzyme 2 enzymes is about 14%-15%).
(9) alkaline proteinase coated micro-pill of the present invention is tested its clean effect according to GB " GBT 13174-2008 dress material with the mensuration of washing composition detersive power and circulation cleaning performance ", and test result is better than same kind of products at abroad.The detersive power test-results sees the following form:
The detersive power performance of different alkaline proteinase coated micro-pill 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 energy section product, numbering PuraFast2000HS.
In proteolytic enzyme coated micropill technical field, the selection of coatings component and content has important impact for the stability of micropill and the preservation of enzyme activity.Therefore, the proportioning of coatings component is screened.
Embodiment 5
Adopt embodiment 1 described component and explained hereafter alkaline proteinase coated micro-pill, unique different quality that are each component of coatings accounts for coatings form and are adjusted into dextrin 21%, starch 20%, polyvinyl alcohol 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, titanium dioxide 22.95%, light blue 0.05%.The alkaline proteinase coated micro-pill that makes is carried out above-mentioned performance test, and compare with the alkaline proteinase coated micro-pill of embodiment 1.The result shows, the stability of the micropill of the present embodiment preparation is better than the micropill of embodiment 1 preparation, specific as follows: preserved 6 months under 25 ℃ of conditions, the enzyme activity loss is about 3.5% in the alkaline proteinase coated micro-pill of the present embodiment preparation, and embodiment 1 is 4.0%.Preserved 3 months under 37 ℃, 70% humidity condition, the alkaline proteinase coated micro-pill enzyme activity loss of the present embodiment preparation is about 8.6%, and embodiment 1 is 9.0%.
Embodiment 6
Adopt embodiment 2 described components and explained hereafter alkaline proteinase coated micro-pill, unique different quality that are each component of coatings accounts for coatings form and are adjusted into dextrin 21%, starch 20%, polyvinyl alcohol 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, titanium dioxide 22.95%, light blue 0.05%.The alkaline proteinase coated micro-pill that makes is carried out above-mentioned performance test, and compare with the alkaline proteinase coated micro-pill of embodiment 2.The result shows that the stability of the micropill of the present embodiment preparation is better than 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 alkaline proteinase coated micro-pill of the present embodiment preparation, and embodiment 2 is 4.2%.Preserved 3 months under 37 ℃, 70% humidity condition, the alkaline proteinase coated micro-pill enzyme activity loss of the present embodiment preparation is about 8.7%, and embodiment 2 is 9.2%.
Embodiment 7
Adopt embodiment 3 described components and explained hereafter alkaline proteinase coated micro-pill, unique different quality that are each component of coatings accounts for coatings form and are adjusted into dextrin 21%, starch 20%, polyvinyl alcohol 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, titanium dioxide 22.95%, light blue 0.05%.The alkaline proteinase coated micro-pill that makes is carried out above-mentioned performance test, and compare with the alkaline proteinase coated micro-pill of embodiment 3.The result shows that the stability of the micropill of the present embodiment preparation is better than embodiment 3, and concrete outcome is as follows: preserved 6 months under 25 ℃ of conditions, the enzyme activity loss is about 3.8% in the alkaline proteinase coated micro-pill of the present embodiment preparation, and embodiment 3 is 4.6%.Preserved 3 months under 37 ℃, 70% humidity condition, the alkaline proteinase coated micro-pill enzyme activity loss of the present embodiment preparation is about 8.8%, and embodiment 3 is 9.5%.
Embodiment 8
Adopt embodiment 4 described components and explained hereafter alkaline proteinase coated micro-pill, unique different quality that are each component of coatings accounts for coatings form and are adjusted into dextrin 21%, starch 20%, polyvinyl alcohol 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, titanium dioxide 22.95%, light blue 0.05%.The alkaline proteinase coated micro-pill that makes is carried out above-mentioned performance test, and compare with the alkaline proteinase coated micro-pill of embodiment 4.The result shows that the stability of the micropill of the present embodiment preparation is better than embodiment 4, and concrete outcome is as follows: preserved 6 months under 25 ℃ of conditions, the enzyme activity loss is about 4.2% in the alkaline proteinase coated micro-pill of the present embodiment preparation, and embodiment 4 is 5.0%.Preserved 3 months under 37 ℃, 70% humidity condition, the alkaline proteinase coated micro-pill enzyme activity loss of the present embodiment preparation is about 9.4%, and embodiment 4 is 10.0%.
The performance test of above-described embodiment 5-8 and comparative result show: the quality composition that each component of coatings accounts for coatings is preferably dextrin 21%, starch 20%, polyvinyl alcohol 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, titanium dioxide 22.95%, light blue 0.05%.The alkaline proteinase coated micro-pill of preparing like this has obvious advantage than other coatings component proportions in the preservation of stability and enzyme activity.
Claims (3)
1. alkaline proteinase coated micro-pill, include mass percent and be 50% ~ 90% contain enzyme ball core and be wrapped in and contain on the enzyme ball core, mass percent is 10% ~ 50% coatings, wherein contain enzyme ball core and be comprised of Sumizyme MP, dextrin, starch, bean powder, lactose, sodium laurylsulfonate, Microcrystalline Cellulose and Dried Corn Steep Liquor Powder, coatings is comprised of dextrin, starch, polyvinyl alcohol, sodium laurylsulfonate, sodium sulfate, titanium dioxide and light blue; 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%; The quality group that each component of described coatings accounts for coatings becomes to be respectively: dextrin 15% ~ 30%, starch 10% ~ 30%, polyvinyl alcohol 5% ~ 15%, sodium laurylsulfonate 1% ~ 6%, sodium sulfate 10% ~ 20%, titanium dioxide 15% ~ 30%, light blue 0.01% ~ 0.1%.
2. coated micropill as claimed in claim 1 is characterized in that the quality group that each component of described coatings accounts for coatings becomes: dextrin 21%, starch 20%, polyvinyl alcohol 14%, sodium laurylsulfonate 4%, sodium sulfate 18%, titanium dioxide 22.95%, light blue 0.05%.
3. the preparation method of alkaline proteinase coated micro-pill claimed in claim 1, its step is as follows:
(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 adjusting rotary speed 600rpm ~ 1200rpm, blower fan 10Hz ~ 20Hz, make tackiness agent with water, spray velocity 15rpm ~ 50rpm, pulverulent material are subjected to the acting in conjunction of rotating disk centrifugal force, frictional force and annular space buoyant gas, mix with the water that sprays into, mother has been finished in bonding gathering, granulation, particle are amplified, round as a ball process, 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 inlet temperature, air quantity 100m are set
3/ h ~ 180 m
3/ h is dried to temperature of charge and reaches 35 ℃ ~ 70 ℃, shuts down, and finishes the drying that contains enzyme ball core;
(3) parcel coatings: take by weighing in proportion each component of coatings, add water and be mixed with the suspension that mass volume ratio is 5%-8%, and cross 100 mesh standard sieves, namely get coating liquid; Get a certain amount of enzyme ball core that contains and place fluidized-bed, regulate 40 ℃ ~ 80 ℃ of inlet temperature, air quantity 80m
3/ h ~ 180 m
3/ h, atomizing pressure 1.2bar ~ 2.5bar selects 0.8mm ~ 1.5mm spray gun, 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 namely got alkaline proteinase coated micro-pill.
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| CN 201110448266 CN102433225B (en) | 2011-12-29 | 2011-12-29 | Alkaline proteinase coated micro-pill and preparation method thereof |
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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 |
| 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 |
| 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 |
| 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 |
| 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 |
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| DE4322229A1 (en) * | 1993-07-05 | 1995-01-12 | Cognis Bio Umwelt | Enveloped enzyme preparation for detergents and cleaners |
| MXPA01006944A (en) * | 1999-01-08 | 2003-09-10 | Genencor Int | Low-density compositions and particulates including same. |
| CN1386840A (en) * | 2001-05-18 | 2002-12-25 | 刘振民 | Phosphat-free detergent with seqential quadruple detergency for fabrics |
| DE10142124A1 (en) * | 2001-08-30 | 2003-03-27 | Henkel Kgaa | Coated active ingredient preparation for use in particulate detergents and cleaning agents |
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