The preparation method of a kind of feed vitamin-beta-schardinger dextrin-or derivatives thereof inclusion compound
Technical field
The present invention relates to field of feed processing, also relate to field of feed additive technology, be specifically related to the preparation method of a kind of feed vitamin-beta-schardinger dextrin-or derivatives thereof inclusion compound.
Background technology
Cyclodextrin inclusion compound is the complex compound of the class unique forms formed by inclusion technique, and the inclusion technique of its different product is also progressively applied in feed, feed addictive.Owing to can be changed the physicochemical property of medicine by inclusion technique, increase medicine stability in the application, improve the solubility of medicine, reduce the excitant of medicine, improve and badly smell taste, reduce toxic and side effect and make liquid medicine powdered, be convenient to the plurality of advantages such as application, its inclusion compound technology is more widely used in feed and feed additive industry.Especially in feed manufacturing process, vitamins is must obligato nutriment, but because consumption is little, uneven, the thermal losses of mixing is brought to feed preparation, and the unstability of vitamins, make finished product quality unstable, even cause product to become batch defective, cause economic loss to enterprise.
The Ministry of Agriculture of China defines the vitamin variety range permitting using to animal husbandry, the Ministry of Agriculture announces No. 2045 " feed addictive kind catalogue (2013) " and specifies that operable vitamins kind has: vitamin A, retinyl acetate, Retinol Palmitate, β-carrot, thiamine hydrochloride (Cobastab
1), thiamine mononitrate (Cobastab
1), riboflavin (Cobastab
2), puridoxine hydrochloride (Cobastab
6), cyanocobalamin (Cobastab
12), L-AA (vitamin C), L-AA calcium, L-AA sodium, L-AA-2-phosphate, L-AP, vitamin D
2, vitamin D
3, 25-hydroxy-vitamin D
3, natural VE, dl-alpha-tocopherol, dl-alpha-tocopherol acetate, menadione sodium bisulfite (vitamin K
3), dimethyl pyrimidine alcohol sulfurous acid menadione, bisulfite niacinamide menadione, nicotinic acid, niacinamide, D-pantothenyl aleohol, D-VB5 calcium, DL-calcium pantothenate, folic acid, Bio etc.But because the use amount of vitamins composition in feed is little, what have is even trace, simultaneously, vitamins product all has unstability to extraneous factors such as heat, light, oxygen, this brings a lot of difficulty with regard to giving the application of vitamin in feed, usually because consumption is uneven, the impact of the unfavorable factor in processing process, causes the content of its vitamin to have very large instability.As in standard GB/T/T18823-2002 " allowable error that feed testing result judges " table 3 feed, vitamin and micronutrient levels testing result judge in allowable error, to the scope of its allowable error (relative error)/(%) all between-10 ~-50, also can therefrom find out, the unstability of the vitamin ingredients content in feed.In order to ensure the effect of vitamin finished product in feed, simultaneously also in order to the cost that economizes in raw materials, feed manufacturing emterprise is also all constantly sought one and is more preferably applied processing method, with the stability of improving product.
The cyclodextrin inclusion compound of vitamins all can play fine beneficial effect to the validity of product and stability undoubtedly, with regard to the preparation method of its inclusion compound, mostly adopt saturated water solution method (i.e. recrystallization or coprecipitation) at present: supercritical ultrasonics technology, polishing, freeze-drying, spray drying process etc.Because saturated water solution method is through refrigeration after the stirring or vibration of uniform temperature and certain hour, filter, dry obtained cyclodextrin inclusion compound, because the operating time is long, large during energy charge, although select supercritical ultrasonics technology to utilize the intensity of sonicator or supersonic wave cleaning machine, the alternative mixing power of ultrasonic appropriate time, but ultrasonic equipment increases the equipment investment of medium-sized and small enterprises, simultaneously to its precipitation, filter and the link of drying also essential, still for enterprise is difficult to acceptance.Although polishing technique is simple, be easy to operation, because output is less, be difficult to form scale production technology.Freeze-drying is to cyclodextrin inclusion compound soluble in water not easily crystallization precipitation, or easily decompose when heat drying, variable color, the method can be adopted, due to apparatus expensive, manufacturing cost is large, only apply preparing in powder-injection product and some biological products at present, be not suitable for feed industry application.Spraying dry is suitable for heat stable in properties, and the product using spray seasoning obtaining inclusion compound soluble in water prepares inclusion compound, and because in process, baking temperature is higher, heated time is short, productive rate is high, applies comparatively extensive in pharmacy, food service industry.Because most vitamins product all has thermolability, so be also difficult to be used widely in feed processing industry.With regard in existing disclosed patent document, the cyclodextrin inclusion compound relating to vitamins mostly relates to employing saturated water solution method and freeze-drying etc.A kind of containing multivitamin livestock and poultry premixed feed and preparation method disclosed in Chinese patent CN101301026A, vitamin E clathrate preparation method and purposes disclosed in CN1568969A, a kind of composite vitamin beta disclosed in CN101318021A-ring sticks with paste the preparation method of inclusion compound, according to the deficiency of the existing preparation method for feeding vitamin cyclodextrin inclusion compound, the present invention adopts existing feed-processing equipment, by adopting beta-schardinger dextrin-or derivatives thereof to carry out inclusion research to vitamins, its experimental result show inclusion rate reach >=95%, there is good stability and dissolution rate simultaneously, not only improve output, saved equipment investment simultaneously, overcome existing full Heshui solwution method, polishing, spray drying process, the method production cycles such as supercritical ultrasonics technology are long, consume energy high, many unfavorable factors such as product is unstable, under making enterprise not increase the condition of equipment investment, Produce on a large scale can be realized, save production cost, expand Business Economic Benefit.Realize self-produced personal, solve the problem for quality assurance of vitamins raw material application.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of feed vitamin-beta-schardinger dextrin-or derivatives thereof inclusion compound, the method can overcome the deficiency of existing preparation method preferably, overcome production equipment input cost large, production is taken a lot of work, time-consuming, the unfavorable factors such as quality cannot ensure, solve convenient processing and the application of vitamins inclusion compound preferably, the quality assurance that vitamins raw material is applied is provided.The mass effect of further lifting feed product.
The invention provides the preparation method of a kind of feed vitamin-beta-schardinger dextrin-or derivatives thereof inclusion compound.
To achieve these goals, present invention employs following technical scheme:
The preparation method of a kind of feed vitamin-beta-schardinger dextrin-or derivatives thereof inclusion compound, it is characterized in that by the vitamin of weight ratio: beta-schardinger dextrin-or derivatives thereof: polyvinylpyrrolidone (PVP) forms for 1:10-50:0.25-0.5 ratio, makes by following processes:
(1) first by the vitamin of weight ratio and polyvinylpyrrolidone (PVP) mixed grinding, sieve, make 150-300 order powder, for subsequent use;
(2) the beta-schardinger dextrin-or derivatives thereof of vitamin powder and weight ratio is mixed by equivalent method of progressively increasing, be placed in twin shaft paddle high efficient mixer, stir 240-480S, make it to stir;
(3) dry granulation machine is adopted to be directly compressed into 10-15 order particle the material stirred;
(4) by obtained 10-15 order particle, inserting counterflow cooler, is 25-33 time/min in vibration frequency, amplitude 30mm, suction air volume 13500-18000m
3/ h, under blast>=200mmHg condition, cool drying 10-15min, makes water content be less than 10.0%;
(5) particle after cool drying, makes grain graininess be 70-85 order by crusher in crushing, obtains vitamin-beta-schardinger dextrin-or derivatives thereof inclusion compound.
Beta-schardinger dextrin-(β-Cyclodextrin described above, be called for short β-CD) derivative is any one in methyl-B-cyclodextrin, DM-β-CD, TM-β-CD, 2-second group-beta-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 3-hydroxyethyl-β-cyclodextrin, HP-β-CD.
Vitamin described above comprises liposoluble vitamin as vitamin A, retinyl acetate, Retinol Palmitate, vitamin D
2, vitamin D
3, 25-hydroxy-vitamin D
3, natural VE, dl-alpha-tocopherol, dl-alpha-tocopherol acetate and water soluble vitamin be as beta carotene, thiamine hydrochloride (Cobastab
1), thiamine mononitrate (Cobastab
1), riboflavin (Cobastab
2), puridoxine hydrochloride (Cobastab
6), cyanocobalamin (Cobastab
12), L-AA (vitamin C), L-AA calcium, L-AA sodium, menadione sodium bisulfite (vitamin K
3), any one in dimethyl pyrimidine alcohol sulfurous acid menadione, bisulfite niacinamide menadione, nicotinic acid, niacinamide, D-pantothenyl aleohol, D-VB5 calcium, DL-calcium pantothenate, folic acid, Bio.
Polyvinylpyrrolidone described above is polyvinylpyrrolidone
k25or polyvinylpyrrolidone
k30.
The equipment that the present invention adopts, is the conventional equipment of compound feed processing.Twin shaft paddle high efficient mixer is the SSHJI high efficient mixer that Zhengchang Foodstuff Machinery Co., Ltd., Jiangsu produces, and this machine is equipped with sealing device, and discharging controls, liquid adding system.The operation principle of this machine is made up of the rotor that two direction of rotation are contrary, and rotor is welded with the paddle of multiple special angle, paddle drives material to be rotated counterclockwise along trough inwall on the one hand.Stir about driving material on the one hand, weightless district is formed at the juxtaposition place of two rotors, in this region, no matter how the shape of material, size and density can make material float be in instantaneous weight loss state, this makes material in trough, form comprehensive continuous circulation to stir, mutually extensively be staggered to form fluidized bed mixing, meanwhile, material is also promoted by paddle, vertically radial motion, thus form comprehensive combined-circulation, reach soft, the inclusion effect that mixes fast.SKLN1-5 counterflow cooler, its principle and the course of work are then that pile up gradually, until reach a certain height, when material contacts upper level detector, the motor of marker gear is started working by the granule materials of heat after rotating feeder and entering intermediate bin.Motor drives discharge fence to move back and forth by decelerator and eccentric stiffener, carries out discharging, the action of discharge fence.This time relay is started working, and by arranging certain time delay discharge time, carries out automatic discharging.The discharging quantity cooling material in storehouse during discharging is greater than inlet amount, in storehouse, material drops to certain controlling level, if the time delay discharge time of the time relay terminates, spacing indicator board now on discharge fence reaccees the horizontal level detector be arranged on base time, motor just stops immediately, and discharge fence just rests on fixing position.
When bed depth reaches upper level detector again, discharge fence is setting in motion, discharging again.Constantly repeat the discharge process continued above.In above-mentioned whole process, cooling blower is open all the time.
Along with the reciprocating motion discharging of discharge fence, material is progressively slowly descending, and cooling air from bottom to top, by cold heating, like this, in the course of the work, what the material of top heat ran into is hot blast, and what what bottom was cold ran into is cold wind, material in descending process through all even sufficient cooling, become hard and solid, further reduce moisture, make particle reach further drying purpose.
Beneficial effect of the present invention
The present invention adopts SSHJl high efficient mixer, utilize the state of weightlessness formed in body, the comprehensive continuous circulation of formation that material can be floated turns over, effectively can reach suspension, impact dynamics, mixture homogeneity coefficient is high, its mixture homogeneity coefficient reaches≤2.0%(CV%≤2.0), granulate through compacting again, cool drying, broken sub-sieve, the inclusion rate of its inclusion compound reaches more than 95%, make the clathrate process saving of labor of vitamin medicaments, save time, reduce power consumption, reduce equipment cost, with short production cycle, reduce production cost, vitamin can be protected to prevent light or thermoinducible decomposition by inclusion, anti-oxidation or and other organic or inorganic material compositions between react, increase solubility, improve dissolution rate, stability is improve to the application of vitamin in feed, Loss reducing, improve the quality of feed product valuably, for vitamins adopts cyclodextrin encapsulated application to obtain a kind of new preparation method, there is provided also a kind of convenient for feed industry enterprise better effectively applies vitamins product, fast, cost-saving, the new approach of increasing the benefit.
Detailed description of the invention
Following examples are only further illustrate of the present invention, but not are all of the present invention.
Embodiment 1
First by thiamine hydrochloride 10 kilograms and PVP
k302.5 kilograms of mixing, insert in ball mill and grind, sieve, and make 150 order powder; Take beta-schardinger dextrin-100 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 240S, make it to stir; Dry granulation machine is adopted to be directly compressed into 10 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 10min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 70 orders, obtained thiamine hydrochloride-Benexate Hydrochloride product.
Embodiment 2
First by 10 kilograms, riboflavin and PVP
k255 kilograms of mixing, insert in ball mill and grind, sieve, and make 180 order powder; Take beta-schardinger dextrin-300 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 300S, make it to stir; Dry granulation machine is adopted to be directly compressed into 10 order particles the material after stirring; The particle made is inserted counterflow cooler, is 25 times/min in vibration frequency, amplitude 30mm, suction air volume 18000m
3/ h, under blast>=200mmHg condition, cool drying 10min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 85 orders, obtained riboflavin-Benexate Hydrochloride product.
Embodiment 3
First by puridoxine hydrochloride 10 kilograms and PVP
k303 kilograms of mixing, insert in ball mill and grind, sieve, and make 150 order powder; Take methyl-B-cyclodextrin 200 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 360S, make it to stir; Dry granulation machine is adopted to be directly compressed into 10 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 10min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 75 orders, obtained puridoxine hydrochloride methyl-B-cyclodextrin inclusion compound product.
Embodiment 4
First by cyanocobalamin 1 kilogram and PVP
k300.5 kilogram of mixing, inserts in ball mill and grinds, sieve, and makes 300 order powder; Take HP-β-CD 48.5 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 480S, make it to stir; Dry granulation machine is adopted to be directly compressed into 15 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 10min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 85 orders, obtained cyanocobalamin hydroxypropyl-beta-cyclodextrin inclusion product.
Embodiment 5
First by L-AA 10 kilograms and PVP
k253.5 kilograms of mixing, insert in ball mill and grind, sieve, and make 150 order powder; Take beta-schardinger dextrin-150 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 240S, make it to stir; Dry granulation machine is adopted to be directly compressed into 10 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 15min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 70 orders, obtained L-AA-Benexate Hydrochloride product.
Embodiment 6
First by menadione sodium bisulfite 10 kilograms and PVP
k303 kilograms of mixing, insert in ball mill and grind, sieve, and make 250 order powder; Take TM-β-CD 350 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 360S, make it to stir; Dry granulation machine is adopted to be directly compressed into 12 order particles the material after stirring; The particle made is inserted counterflow cooler, is 25 times/min in vibration frequency, amplitude 30mm, suction air volume 18000m
3/ h, under blast>=200mmHg condition, cool drying 12min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 80 orders, obtained menadione sodium bisulfite TM-β-CD inclusion compound product.
Embodiment 7
First by 10 kilograms, nicotinic acid and PVP
k252.5 kilograms of mixing, insert in ball mill and grind, sieve, and make 200 order powder; Take 2-hydroxyethyl-β-cyclodextrin 300 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 300S, make it to stir; Dry granulation machine is adopted to be directly compressed into 10 order particles the material after stirring; The particle made is inserted counterflow cooler, is 25 times/min in vibration frequency, amplitude 30mm, suction air volume 18000m
3/ h, under blast>=200mmHg condition, cool drying 12min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 75 orders, obtained nicotinic acid 2-hydroxyethyl-β-cyclodextrin inclusion compound product.
Embodiment 8
First by niacinamide 10 kilograms and PVP
k302.5 kilograms of mixing, insert in ball mill and grind, sieve, and make 150 order powder; Take HP-β-CD 150 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 240S, make it to stir; Dry granulation machine is adopted to be directly compressed into 10 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 12min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 70 orders, obtained niacinamide hydroxypropyl-beta-cyclodextrin inclusion product.
Embodiment 9
First by D-VB5 calcium 10 kilograms and PVP
k302.5 kilograms of mixing, insert in ball mill and grind, sieve, and make 200 order powder; Take 3-hydroxyethyl-β-cyclodextrin 200 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 240S, make it to stir; Dry granulation machine is adopted to be directly compressed into 10 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 10min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 70 orders, obtained D-VB5 calcium 3-hydroxyethyl-β-cyclodextrin inclusion compound product.
Embodiment 10
First by 1 kilogram, folic acid and PVP
k303 kilograms of mixing, insert in ball mill and grind, sieve, and make 300 order powder; Take beta-schardinger dextrin-400 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 480S, make it to stir; Dry granulation machine is adopted to be directly compressed into 12 order particles the material after stirring; The particle made is inserted counterflow cooler, is 25 times/min in vibration frequency, amplitude 30mm, suction air volume 18000m
3/ h, under blast>=200mmHg condition, cool drying 10min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 80 orders, obtained folic acid-Benexate Hydrochloride product.
Embodiment 11
First by Bio 1 kilogram and PVP
k304 kilograms of mixing, insert in ball mill and grind, sieve, and make 300 order powder; Take DM-β-CD 50 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 420S, make it to stir; Dry granulation machine is adopted to be directly compressed into 15 order particles the material after stirring; The particle made is inserted counterflow cooler, is 25 times/min in vibration frequency, amplitude 30mm, suction air volume 18000m
3/ h, under blast>=200mmHg condition, cool drying 10min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 85 orders, obtained Bio DM-β-CD inclusion compound product.
Embodiment 12
First retinol1 kilogram and PVP is taken
k305 kilograms of mixing, insert in ball mill and grind, sieve, and make 250 order powder; Take 2-second group-beta-cyclodextrin 50 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 480S, make it to stir; Dry granulation machine is adopted to be directly compressed into 15 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 15min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 85 orders, obtained dehydroretinol-ethyl-Benexate Hydrochloride product.
Embodiment 13
First vitamin D is taken
31 kilogram and PVP
k35 kilograms of mixing, insert in ball mill and grind, sieve, and make 300 order powder; Take 3-hydroxyethyl-β-cyclodextrin 45 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 480S, make it to stir; Dry granulation machine is adopted to be directly compressed into 15 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 15min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 85 orders, obtained vitamin D
33-hydroxyethyl-β-cyclodextrin inclusion compound product.
Embodiment 14
First dl-alpha-tocopherol 1 kilogram and PVP is taken
k305 kilograms of mixing, insert in ball mill and grind, sieve, and make 250 order powder; Take HP-β-CD 44 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 420S, make it to stir; Dry granulation machine is adopted to be directly compressed into 15 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 15min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 80 orders, obtained dl-alpha-tocopherol hydroxypropyl-beta-cyclodextrin inclusion product.
Embodiment 15
First beta carotene 1 kilogram and PVP is taken
k304 kilograms of mixing, insert in ball mill and grind, sieve, and make 200 order powder; Take HP-β-CD 35 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 420S, make it to stir; Dry granulation machine is adopted to be directly compressed into 14 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 13min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 80 orders, obtained beta carotene hydroxypropyl-beta-cyclodextrin inclusion product.
Embodiment 16
First D-pantothenyl aleohol 1 kilogram and PVP is taken
k35 kilograms of mixing, insert in ball mill and grind, sieve, and make 200 order powder; Take beta-schardinger dextrin-44 kilograms again to progressively increase method premixed by equivalent, then insert in twin shaft paddle high efficient mixer, stir 480S, make it to stir; Dry granulation machine is adopted to be directly compressed into 10 order particles the material after stirring; The particle made is inserted counterflow cooler, is 33 times/min in vibration frequency, amplitude 30mm, suction air volume 13500m
3/ h, under blast>=200mmHg condition, cool drying 12min, makes water content be less than 10.0%; Again the particle disintegrating machine after cool drying is carried out fragmentation, make grain graininess be 85 orders, obtained D-pantothenyl aleohol-Benexate Hydrochloride product.