Background technology
Glycin chelated iron is that a kind of very easy quilt comprises the iron enriched nutrient that human mammalian organism absorbs, its have nontoxic non-stimulated, absorb fast, mend numerous advantages such as the iron blood tonification effect is remarkable, be widely used in feed addictive.In recent years, some researchers of the Britain and the U.S. increase as the research that iron enriched nutrient is applied in the food gradually to amino acid chelated iron.
In China, last century, the mid-80 microelements aminophenol chelated that begins one's study and was obtained remarkable progress at chelating amino acids aspect ferrous.It is ferrous that Yang WenBing and Yao Fenying have reported that in the early 1990s the Moriamin S that obtains with the acidolysis soya-bean cake and ferrous sulfate chelatropic reaction prepare composite aminoacid chelating.People such as Qin Weidong (2003) have studied with the defatted soybean meal enzymolysis and have become Moriamin S on this basis, prepare the ferrous technology of composite aminoacid chelating with the ferrous salt chelating.Xu Haiqing and Ming Xia (2001) have introduced with the chicken feather to be raw material, to use hydrochloric acid hydrolysis, prepare the method for compound amino acid iron complex then with the molysite complexing.
The patent of invention CN1280260C " a kind of preparation method of food enrichment Ferrous glycinate " of inventor application can prepare Ferrous glycinate content and surpass 80%, and the Ferrous glycinate reconstitution rate is greater than 95% glycin chelated iron.The product glycin chelated iron is a kind of water-soluble substances, and its oxidation stability and aqueous stability are higher than ferrous sulfate far away, but also has easy moisture absorption, the defective of partial oxidation during long preservation.Therefore, the synthetic glycin chelated iron of this method need be handled the product of easily being preserved through super-dry, can guarantee the water-soluble of dried product simultaneously, is beneficial to the fortification of food liquids such as dairy products, soy sauce, grease, conveniently processes and uses.Adopt boulton process drying glycine chelated iron, can reach above-mentioned specification requirement, but its technology is intermittently operated, grow arid cycle, yields poorly, product particle is big needs pulverizing, be not easy to serialization production, and dried product still has stronger hygroscopicity.
Summary of the invention
The spray drying process that the purpose of this invention is to provide a kind of food enrichment water-soluble iron chelate of glycine can be realized industrial-scale production with this method, and is with low cost, and products obtained therefrom has non-oxidizability, resistance to water soak and good water-soluble.Obviously be better than the product that boulton process obtains.
Technical scheme of the present invention: with glycine and frerrous chloride is raw material, synthetic glycin chelated iron, in ferrous chloride aqueous solution, add maltodextrin, anti-caking agent and composite antioxidant, homogeneous under certain pressure, spray-drying in spray drying tower at last.
(1) mass ratio of maltodextrin and glycin chelated iron is 1.25: 1-1: 1.25;
(2) antioxidant is selected ascorbic acid for use, and its consumption is the 1.15%-1.35% of glycine chelate weight of iron;
(3) anti-caking agent is selected microcrystalline cellulose for use, and its consumption is 1% of a glycine chelate weight of iron;
(4) selected solid content in glycin chelated iron and maltodextrin total quality is 20%-30%;
(5) homogenization pressure is 20-30MPa, twice of homogeneous;
(6) spray-drying: EAT is 170-190 ℃, and leaving air temp is 80-90 ℃.
The research of water-soluble iron chelate of glycine spray drying process comprises the determining of selection, homogenization pressure of selection, the EAT of selection, the solid content of selection, the anti-caking agent consumption of the determining of the selection of packing agent and consumption, antioxidant consumption.
Spray-dired packing agent is selected between the maltodextrin of cyclodextrin and low DE value (DE value 8-15).From outward appearance, cyclodextrin is khaki as the glycin chelated iron dry products color of packing agent, good fluidity, and maltodextrin also is a khaki as the glycin chelated iron dry products color of packing agent, flowability is poor slightly.But find that by soluble test the former water-soluble is on duty mutually, very easily hydrolysis in water, and maltodextrin is transparent limpid as the product aqueous solution of packing agent, SOLUTION PROPERTIES is very stable.Therefore packing agent is selected the maltodextrin of DE value 8-15, and considers to add some anti-caking agents to improve the flowability of product.
Determining of spray-drying packing agent maltodextrin consumption selects for use maltodextrin and glycin chelated iron (in the definite butt quality of oven method) mass ratio to be respectively 2: 11: 2,1: 1.5,1: 1,1.5: 1 respectively.Found that maltodextrin: glycin chelated iron is darker less than 1: 1 o'clock product colour, for application is made troubles; Maltodextrin: glycin chelated iron is that 1: 1 o'clock color is more shallow, and good water solubility is desirable product; Maltodextrin: glycin chelated iron was greater than 1.5: 1 o'clock, though of light color, facile hydrolysis can not use as additive.Consider the actual value of product simultaneously, select the iron content high product, so preferred maltodextrin: the mass ratio of glycin chelated iron is 1: 1.
Antioxidant is selected ascorbic acid for use, the selection of its consumption, the process that antioxidant consumption (accounting for the ratio of glycine chelate weight of iron) from 0.5% to 2% changes, when the antioxidant consumption less than 1.25% the time, the value of ferrous/total iron is lower, and after 1.25%, ferrous/total iron is very big difference not, and the preferred anti-oxidants consumption is 1.25% of a glycine chelate weight of iron.
Anti-caking agent is selected microcrystalline cellulose for use, and its consumption is the 1% comparatively suitable of glycine chelate weight of iron.
Determining of solid content, when solid content was low more, retention rate ferrous in the product was low more, and when solid content was higher, ferrous oxidized degree was lower, took place but have wall sticking phenomenon.Taking all factors into consideration the each side factor preferably adds up to the solid content 20% of quality for suitable in glycin chelated iron and packing agent.
It is serious that insufficient wall sticking phenomenon that causes is crossed when low because feed liquid is heated in the selection of EAT, EAT, and the product yield is low; Can influence ferrous stability when temperature is too high, reduce ferrous content, optimized EAT is 180 ℃.
Water-soluble iron chelate of glycine spray drying process after the optimization of the present invention is: the mass ratio of maltodextrin and glycin chelated iron is 1: 1, the antioxidant consumption is 1.25% of a glycine chelate weight of iron, anti-caking agent is 1% of a glycine chelate weight of iron, solid content is 20%, homogenization pressure is 30MPa, homogeneous twice, EAT are 180 ℃, and leaving air temp is 80 ℃-90 ℃.
The glycin chelated iron oxidation stability contrast of different dry drying process condition preparation
The pure product of glycin chelated iron that make under compound glycin chelated iron that drying process with atomizing is made and the vacuum drying condition carry out storage experiment, observe their stability, and the result as shown in Figure 1.As can be seen from Figure 1, compound glycin chelated iron is owing to add a certain amount of maltodextrin as packing agent, this part packing agent has played certain oxygen barrier effect, simultaneously also because before spray-drying, added a certain amount of antioxidant again, so that the oxidation stability of compound glycin chelated iron good than the pure product of glycin chelated iron.
Getting damp property of the product moisture absorption contrast of different dry drying process preparation
The pure product of glycin chelated iron that make under compound glycin chelated iron that drying process with atomizing is made and the vacuum drying condition are exposed in the air, observe their moisture absorption situation.The result as shown in Figure 2.As can be seen from Figure 2, with the pure product contrast of glycin chelated iron that vacuum drying makes, compound its hygroscopic effect of glycine chelate iron product that makes by drying process with atomizing has had tangible improvement.Uncovered placement 1 hour, the moisture absorption rate of body weight gain of joint product is littler by 63.46% than the moisture absorption rate of body weight gain of pure product, little by 47.64% than pure product of the moisture absorption rate of body weight gain of 10th hour joint product, both anti-moisture absorption curve shapes are similar, be linear ascendant trend during beginning, after the 10th hour, weightening finish obviously reduces, the curve trend is steady, and at this time the moisture absorption weightening finish is near saturated.After placing 48 hours, the moisture absorption rate of body weight gain of final joint product is littler by 41.81% than pure product.The maltodextrin that adds in this explanation spray-drying and the anti-caking agent of minute quantity have played good anti-hygroscopic effect, make glycin chelated iron can be applied to better in the Food fortification carrier (as flour), and prolong its shelf life.
The water-soluble contrast of product of different dry drying process preparation
The water miscible quality of glycin chelated iron directly has influence on its application in flour, so the dissolubility of the pure product of glycin chelated iron that obtain in this compound glycin chelated iron that spray-drying is obtained and vacuum drying once compares, the result as shown in Figure 3.As can be seen from Figure 3, in 100mL water, water-soluble being more or less the same of product of two kinds of different dry drying process preparations, the pure product solubility of glycin chelated iron of vacuum drying method preparation is approximately 9.73g/100mL, and the compound glycin chelated iron solubility of spray drying process preparation is approximately 9.05g/100mL.This shows that the dissolubility of compound glycin chelated iron is fine, be well suited for and add in the food, well utilized as ferrous-fortifier.
Beneficial effect of the present invention: adopt glycin chelated iron spray drying process of the present invention can obtain color and luster, water-soluble, non-oxidizability and the equal good quality production of resistance to water soak.Amino acid content is 31.30% after the product spray-drying, and total iron content is 7.17%, and ferrous content is 5.89%, does not almost have free iron.The non-oxidizability of product, resistance to water soak and water-solublely take all factors into consideration the glycine chelate iron product that is better than after the vacuum drying.Moisture is 3.1% in the product after the spray-drying, and other composition (dextrin, composite antioxidant etc.) content is 58.43%.The inventive method has can be with commercial scale continuous production, and operating procedure is simple, and processing cost is lower, and constant product quality is convenient to long preservation, advantages such as convenient application.The compound glycine chelate iron product that obtains has characteristics such as stable chemical performance, biological value height, nontoxic nonirritant, good palatability, enhancing immune function of human body, amino-acid chelate is very little to vitamin, antibiotic isoreactivity composition influence, also can reduce the antagonism micro-with other, can be used as feed addictive, nutrition fortifier, pharmaceutical preparation, be used for the control of trace element deficiencies such as iron zinc.
The specific embodiment
Embodiment 1
Take by weighing the 50g water-soluble iron chelate of glycine, be dissolved in the 500mL deionized water, add the 50g maltodextrin, 0.65g antioxidant, 0.5g anti-caking agent, solid content is 20%, homogenization pressure 20MPa, homogeneous twice, 180 ℃ of EATs, leaving air temp is 80 ℃-90 ℃, spray-drying in spray drying tower.
Get the 5g product and be dissolved in the 100ml ultra-pure water, the transparent nothing precipitation of system, ferrous content accounts for 81.77% of total iron content, and product is dry, favorable solubility.
Embodiment 2
Take by weighing the 50g water-soluble iron chelate of glycine, be dissolved in the 1000mL deionized water, add the 50g maltodextrin, 0.625g antioxidant, 0.5g anti-caking agent, solid content is 10%, homogenization pressure 20MPa, homogeneous twice, 180 ℃ of EATs, leaving air temp is 80 ℃-90 ℃, spray-drying in spray drying tower.
Get the 5g product and be dissolved in the 100ml ultra-pure water, the transparent nothing precipitation of system, ferrous content accounts for 79.10% of total iron content, product drying, favorable solubility.
Embodiment 3
Take by weighing the 50g water-soluble iron chelate of glycine, be dissolved in the 500mL deionized water, add the 50g maltodextrin, 0.625g antioxidant, 0.5g anti-caking agent, solid content is 20%, homogenization pressure 20MPa, homogeneous twice, 160 ℃ of EATs, leaving air temp is 80 ℃-90 ℃, spray-drying in spray drying tower.
Get the 5g product and be dissolved in the 100ml ultra-pure water, the transparent nothing of system precipitation, ferrous content accounts for 84.12% of total iron content, and it is poor that product flows, and wall sticking phenomenon is very serious, may EAT is lower causes.
Embodiment 4
Take by weighing the 50g water-soluble iron chelate of glycine, be dissolved in the 500mL deionized water, add the 50g maltodextrin, 0.625g antioxidant, 0.5g anti-caking agent, solid content is 20%, homogenization pressure 30MPa, homogeneous twice, 180 ℃ of EATs, leaving air temp is 80 ℃-90 ℃, spray-drying in spray drying tower.
Get the 5g product and be dissolved in the 100ml ultra-pure water, the transparent nothing precipitation of system, ferrous content accounts for 82.03% of total iron content, and the product dissolubility is fine, and solution is limpid.