CN103467331A - Iron glycine chelate crystal growth method - Google Patents
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Abstract
The invention discloses an iron glycine chelate crystal growth method. The iron glycine chelate crystal growth method comprises the following steps of dissolving iron glycine chelate in water having a temperature of 75-85 DEG C, carrying out stirring at a stirring rate of 20-50Hz to obtain an iron glycine chelate solution having a concentration of 0.3g/ml, carrying out gradual cooling at a cooling rate of 35-45 DEG C/h, dropwisely adding an organic solvent into the iron glycine chelate solution, cooling the mixed solution to a temperature of 20 DEG C, keeping the temperature, sequentially carrying out dropwise addition of the organic solvent at the temperature of 20 DEG C until iron glycine chelate crystals are separated and grow, filtering the iron glycine chelate crystals, drying the iron glycine chelate crystals, screening the dried iron glycine chelate crystals, and collecting the iron glycine chelate crystals having granularity of 20-60 meshes. The iron glycine chelate crystal growth method can prepare the iron glycine chelate crystals having a good color, good oxidation resistance, moisture absorption resistance and good water solubility.
Description
Technical field
The present invention relates to amino-acid trace element iron complex preparing technical field, be specifically related to a kind of crystalline growth method of water-soluble iron chelate of glycine.
Background technology
At present, iron is one of essential trace element of animal, be also one of trace element of the darkest needed by human of most study and understanding, yet the body iron deficiency is but the whole world, particularly one of topmost nutrition problem of developing country.Iron is the important composition composition of oxyphorase, is delivery of oxygen and the important element that exchanges oxygen in blood, is also the moiety of many enzymes and the activator of redox reaction enzyme, and sideropenia can cause the diseases such as anaemia.
Glycin chelated iron is a kind of iron enriched nutrient that the mankind absorb at interior mammalian organism that is very easy to be included, its have nontoxic non-stimulated, absorb fast, mend the many merits such as the iron blood tonification effect is remarkable, be widely used in fodder additives.Research shows that the specific absorption ferrous sulfate of iron ion in the glycine chelate molysite exceeds five to six times, has good chemical stability, has both avoided the mutual antagonistic action between mineral, has eliminated again the drawback of inorganic salt to the VITAMIN oxidation.
Glycin chelated iron mainly contains following several preparation method at present: 1, utilize glycine and ferrous sulfate, add the solid caustic soda reaction, and utilize membrane sepn to obtain glycine sodium salt, after continuing to react, utilize the scraper plate thin film evaporation to be concentrated into and separate out epitaxial, final vacuum-drying; 2, a kind of method that also has Preparation of amino acid ferrous chelate compound, add amino acid and soluble ferrite fire crane in organic alcohol solvent, and after reaction, suction filtration obtains solid.
So far, few people adopt crystallization process to produce glycin chelated iron.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of crystalline growth method of glycin chelated iron, and its products obtained therefrom stores convenient, has good oxidation-resistance, anti-moisture absorption and water-soluble, thereby eliminates defect in the above-mentioned background technology.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of crystalline growth method of glycin chelated iron, comprise the steps:
Glycin chelated iron is dissolved in the water of 75-85 ℃, is stirred with the speed of 20Hz-50Hz, the glycine chelate ferrous solution that to make concentration be 0.3g/ml;
Rate of temperature fall with 35-45 ℃/h is progressively lowered the temperature, drip organic solvent in solution, keep this temperature after being cooled to 20 ℃, continue the dropping of organic solvent at this temperature, to crystal, separated out, grow up, filtered crystal, after oven dry, sieve, collect the product of granularity between the 20-60 order, thereby obtain the crystal of glycin chelated iron
Wherein, the mixed solution that described organic solvent is acetone and dehydrated alcohol, and the mass ratio of acetone and dehydrated alcohol is 1:1～1:5;
The quality of organic solvent and glycin chelated iron mass ratio are 2:1-1:1;
It is 2～3 hours that organic solvent all adds the time used.
In the present invention, rate of temperature fall is preferably 40 ℃.
In the present invention, preferred stir speed (S.S.) is 30Hz.
In the present invention, in organic solvent, the mass ratio of acetone and dehydrated alcohol is preferably 1:3.
In the present invention, the quality of organic solvent and glycin chelated iron mass ratio are preferably 1:1.
The present invention is through a large amount of tests repeatedly of contriver, just finally determined determining of the determining of the selection of organic solvent and consumption, stir speed (S.S.), and determining of rate of temperature fall, add determining of organic solvent speed.
When crystallization, add organic solvent to mainly contain following reason: after 1. adding organic solvent, can make the reduced dielectric constant of the aqueous solution, thereby the electrostatic attraction between solute molecule is increased, impel them to assemble mutually, and crystallize out.2. the wetting ability of water-miscible organic solvent is very strong, and he can grab the free water of originally being combined with hydrophilic solute, and its surperficial hydration layer is destroyed, and causes the interaction between solute molecule increase and produce gathering, thus crystallization.
The contriver, in order to select suitable organic solvent, carried out a large amount of tests repeatedly between methyl alcohol, ethanol, acetone and other multi-solvents.Ethanol is the organic solvent that the most frequently used crystal is separated out, because it has, crystallization is strong, moderate boiling point, the advantage such as nontoxic.The specific inductivity of acetone is less than ethanol, but it has that boiling point is low, volatilization loss large, liver is had to the shortcomings such as certain toxicity, point of ignition are low, and he is applied not as good as ethanol.Crystallization and the ethanol of methyl alcohol are suitable, but severe toxicity is arranged because methyl alcohol is oral, so application is also not as good as ethanol.From outward appearance, use ethanol as precipitation agent, the gained crystal shows slightly white, and crystal grain is full.The organic solvent that acetone is separated out as the glycin chelated iron crystal, gained crystal color glassy yellow, granularity is slightly poor.And other solvents also respectively have its relative merits.Found through experiments, acetone mixes by a certain percentage with ethanol, the organic solvent of separating out as the glycin chelated iron crystal, and gained crystal glassy yellow, granularity is fuller.Therefore the organic solvent of selecting acetone and dehydrated alcohol mixture by a certain percentage to separate out as the glycin chelated iron crystal.
The contriver finds in long-term practice, when acetone and dehydrated alcohol mass ratio are greater than 1:1, and crystalline product color proper (being yellow), but granularity is less; Color better (for glassy yellow) when acetone, dehydrated alcohol mass ratio are 1:3, particle is larger, is ideal product; When acetone, dehydrated alcohol mass ratio are less than 1:5, although granularity is larger, color starts to turn white.Consider the actual application value of product, select the higher product of iron level, so the mass ratio of preferred acetone and dehydrated alcohol is 1:3.
The quality of organic solvent and glycin chelated iron mass ratio are 2:1-1:1, when being less than 1:1, glycin chelated iron is not separated out fully in solution, when being 1:1, glycin chelated iron is separated out substantially fully, and that suitable increase organic solvent concentration is more conducive to crystallization is complete, if but surpass 2:1 without clear meaning.
It is comparatively suitable that glycine chelate ferrous solution rate of temperature fall is chosen as 40 ℃/h, the process that stir speed (S.S.) changes from 20Hz-50Hz, selects 40Hz comparatively suitable.
The selection of organic solvent drop rate, the organic solvent drop rate is crossed when slow, and the nucleus of formation, owing to lacking the power of growing up, easily is stirred and smashes, and causes nucleus too much, and the crystal of growth is many, and granularity is little; Drip the too fast nucleus that also easily causes too much, formed crystal size is little, and optimum rate of addition is for all adding the organic solvent time 2 h.
Therefore, water-soluble iron chelate of glycine crystallization method after optimization of the present invention is: organic solvent-acetone and dehydrated alcohol mass ratio are 1:3, the quality of organic solvent and glycin chelated iron mass ratio are 2:1,40 ℃/h of solution rate of temperature fall, stir speed (S.S.) 40Hz, drip 2 hours organic solvent used times.
Owing to having adopted technique scheme, the invention has the beneficial effects as follows:
Adopt glycin chelated iron crystallization method of the present invention can obtain color, oxidation-resistance, anti-moisture absorption, reach water-soluble good product.After the product crystallization, aminoacids content is 21.35%, and ferrous content is 18.23%, and ferric iron content is 0.38%, and moisture content is 9.8%.The inventive method has can be with Small Scale Industry production, and operating procedure is simple, and tooling cost is lower, is convenient to standing storage, the advantages such as convenient application.Can be used for fodder additives, nutrition-fortifying agent, pharmaceutical preparation, for the control of iron microelement deficiency disease.
The accompanying drawing explanation
Fig. 1 is glycin chelated iron crystal and Powdered glycin chelated iron oxidative stability comparing result figure prepared by the present invention;
Fig. 2 is glycin chelated iron crystal and Powdered glycin chelated iron moisture absorption comparing result figure prepared by the present invention;
Fig. 3 is the glycin chelated iron crystal for preparing of the present invention and the solvability of Powdered glycin chelated iron in 100g water figure as a result.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Take the 90g glycin chelated iron, be dissolved in the 300g deionized water, be heated to 75 ℃, stir speed (S.S.) 20HZ, start cooling, 35 ℃/h of rate of temperature fall, drip wherein acetone 90g of mixed organic solvents 180g(, ethanol 90g), keep this temperature after being cooled to 20 ℃, and complete the solvent dropping, and adding 2 hours organic solvent used times, crystal is crystallization in reactor.
Get the oven dry product, weighing obtains 92g product (moisture 10%, anhydrous glycine chelated iron yield 95.3%) and sieves, collect the product of granularity between the 20-60 order, account for 71.44% of total product quality, product colour is yellow, and the solubleness in water is 116g/100g to the maximum.
Product is placed after two months, and ferrous iron accounts for total iron content and becomes 97.65% by 98.40%, and moisture is containing 8.95%.
Take the 90g glycin chelated iron, be dissolved in the 300g deionized water, be heated to 80 ℃, stir speed (S.S.) 30HZ, 40 ℃/h of rate of temperature fall starts to lower the temperature, drip wherein acetone 30g of mixed organic solvents 180g(, ethanol 150g), keep this temperature after being cooled to 20 ℃, and complete solvent and drip, add 2 hours organic solvent used times, crystal is crystallization in reactor.
Get the oven dry product, weighing obtains 92.8g product (moisture 10.2%, anhydrous glycine chelated iron yield 96.3%) and sieves, collect the product of granularity between the 20-60 order, account for 62.14% of total product quality, product colour is more yellow, maxima solubility 116.5g/100g in water.
Product is placed after two months, and ferrous iron accounts for total iron content and becomes 97.80% by 98.30%, and moisture is containing 8.90%.
Take the 90g glycin chelated iron, be dissolved in the 300g deionized water, be heated to 85 ℃, stir speed (S.S.) 40HZ, 45 ℃/h of rate of temperature fall starts to lower the temperature, drip wherein acetone 30g of mixed organic solvents 90g(, ethanol 60g), keep this temperature after being cooled to 20 ℃, and complete solvent and drip, add 3 hours organic solvent used times, crystal is crystallization in reactor.
Get the oven dry product, weighing obtains 92.1g product (moisture 9.9%, anhydrous glycine chelated iron yield 95.5%) and sieves, collect the product of granularity between the 20-60 order, account for 72.45% of total product quality, product colour is bright orange, maxima solubility 115.7g/100g in water.
Product is placed after two months, and ferrous iron accounts for total iron content and becomes 97.60% by 98.15%, and moisture is containing 9.70%.
Take the 90g glycin chelated iron, be dissolved in the 300g deionized water, be heated to 80 ℃, stir speed (S.S.) 50HZ, 43 ℃/h of rate of temperature fall starts to lower the temperature, drip wherein acetone 27g of mixed organic solvents 135g(, ethanol 108g), keep this temperature after being cooled to 20 ℃, and complete solvent and drip, add 2.5 hours organic solvent used times, crystal is crystallization in reactor.
Get the oven dry product, the product 91g(moisture 9.8% of weighing to obtain, anhydrous glycine chelated iron yield 94.4%) sieve, collect the product of granularity between the 20-60 order, account for 69.14% of total product quality, product colour is bright orange, and in water, maxima solubility is 115.6g/100g.
Product is placed after two months, and ferrous iron accounts for total iron content and becomes 97.55% by 98.35%, and moisture is containing 9.60%.
Take the 90g glycin chelated iron, be dissolved in the 300g deionized water, be heated to 80 ℃, stir speed (S.S.) 30HZ, the 40 ℃/h of rate of temperature fall that starts to lower the temperature, drip wherein acetone 22.5g of mixed organic solvents 90g(, ethanol 67.5g) keep this temperature after being cooled to 20 ℃, and complete the solvent dropping, and adding 3 hours organic solvent used times, crystal is crystallization in reactor.
Get the oven dry product, weighing obtains 93g product (moisture 10.2%, anhydrous glycine chelated iron yield 96.6%) and sieves, collect the product of granularity between the 20-60 order, account for 75.28% of total product quality, product colour glassy yellow, maxima solubility 117.2g/100g in water.
Product is placed after two months, and ferrous iron accounts for total iron content and becomes 97.58% by 98.37%, and moisture is containing 9.45%.
The comparative example 1
Take the 90g glycin chelated iron, be dissolved in the 300g deionized water, be heated to 80 ℃, stir speed (S.S.) 20HZ, the 40 ℃/h of rate of temperature fall that starts to lower the temperature, drip organic solvent-acetone 90g, add approximately 0.5 hour organic solvent used time, be cooled to 20 ℃ of crystallizations in reactor.
Get the oven dry product, the product 85.3g(moisture 1.03% of weighing, anhydrous glycine chelated iron yield 95.2%) wherein the following product of 100 orders account for 80.54% of total product quality, product colour turns white, maxima solubility 92.8g/100g in water.
Product is placed after two months, and ferrous iron accounts for total iron content and becomes 96.58% by 98.37%, and moisture is containing 3.45%.
The comparative example 2
Take the 90g glycin chelated iron, be dissolved in the 300g deionized water, be heated to 80 ℃, stir speed (S.S.) 40HZ, the 40 ℃/h of rate of temperature fall that starts to lower the temperature, drip organic solvent ethanol 90g, add approximately 0.5 hour organic solvent used time, be cooled to 20 ℃ of crystallizations in reactor.
Get the oven dry product, the product 86.3g(moisture 2.43% of weighing, anhydrous glycine chelated iron yield 95.5%) the following quality product of 100 orders wherein of sieving accounts for 86.52% of total product quality, and product colour turns white.Maxima solubility 93.8g/100g in water.
Product is placed after two months, and ferrous iron accounts for total iron content and becomes 96.48% by 98.37%, and moisture is containing 3.45%.
The comparative example 3
Take the 90g glycin chelated iron, be dissolved in the 300g deionized water, be heated to 80 ℃, stir speed (S.S.) 20HZ, the 40 ℃/h of rate of temperature fall that starts to lower the temperature, drip organic solvent methyl alcohol 90g, add approximately 0.5 hour organic solvent used time, be cooled to 20 ℃ of crystallizations in reactor.
Get the oven dry product, the product 86.3g(moisture 1.75% of weighing, anhydrous glycine chelated iron yield 94.8%) the following quality product of 100 orders wherein of sieving accounts for 82.52% of total product quality.Product colour is whiter, and in water, maxima solubility is 92.8g/100g.
Product is placed after two months, and ferrous iron accounts for total iron content and becomes 96.39% by 98.37%, and moisture is containing 3.95%.
Generally speaking, the standard of judgement glycin chelated iron crystal structure method quality is:
1, crystal yield: anhydrous glycine chelated iron yield is higher, represents that this crystallization method is better;
2, crystal color: color is yellow, glassy yellow, illustrates that crystal quality is high, if color is white, illustrates and wherein contains impurity;
3, crystal size: granularity is larger, and the anti-pressure ability of crystal, agglomeration resistance ability are just better, and quality is also higher;
4, the solubleness of crystal: solubleness is higher, illustrates that crystal solvability in water is better, and then easier passive plants absorption, and quality is higher;
5, moisture absorption: product and the variation of product water content after two months after the contrast output, it is more that water content increases, and illustrates that moisture absorption is larger, and the quality of crystal is lower;
6, oxidisability: in the product of contrast after output and product after two months, ferrous iron accounts for total iron content and changes, and variable quantity is larger, illustrate that oxidisability is higher, and the quality of crystal is also lower.
From yield, granularity, color, solubleness, moisture absorption (change of moisture content after two months), oxidisability (ferrous iron account for total iron content change) after two months, the product of embodiment 1-5 and comparative example 1-3 is contrasted, result is as following table:
From table clearly find out, the glycin chelated iron crystal that adopts embodiment 1-5 to obtain, quality is better than glycin chelated iron crystal prepared by traditional crystallization method greatly.The product water content that embodiment 1-5 obtains is all higher, causes ferrous content shared ratio in product to descend to some extent.The product granularity that embodiment 1-5 obtains aspect product granularity is larger, and the product of Comparative Examples 1-3 is very thin.The difference of this granularity has caused the product resistance to compression, and the size of anti-caking ability.The larger resistance to compression of granularity and agglomeration preventing performance are better.
The Performance Detection of the glycin chelated iron crystal below prepared for the present invention.
The glycin chelated iron crystal that utilizes the inventive method to prepare and the contrast of Powdered glycin chelated iron oxidative stability:
Crystallization glycin chelated iron and Powdered glycin chelated iron are stored to experiment, observe their stability, result as shown in Figure 1.As can be seen from Figure 1, the glycin chelated iron of crystallization is due in space structure, in the encirclement of iron atom in water molecules, this has played certain oxygen barrier effect, so that the more Powdered glycin chelated iron of oxidative stability of crystallinity glycin chelated iron good.
The glycin chelated iron crystal that utilizes the inventive method to prepare and the contrast of Powdered glycin chelated iron moisture absorption:
Glycin chelated iron crystal and Powdered glycin chelated iron are exposed in air, observe their moisture absorption situation.Result as shown in Figure 2.As can be seen from Figure 2, with Powdered glycin chelated iron contrast, its moisture absorption phenomenon of glycine chelate iron product made by crystallization processes has had obvious improvement.As can be seen from the figure the weightening finish of crystallization glycine chelate iron product obviously reduces, the curve trend steadily, possible cause crystal water molecule is enclosed in around the glycine chelate iron molecule, the glycin chelated iron adsorbed water molecule may will reach capacity, and the glycin chelated iron Intermolecular Forces is reduced relatively.Powdered glycin chelated iron starts in rising trend, and after the 10th hour, weightening finish obviously reduces, and the curve trend steadily.Because the water molecules in crystalline product is stable space structure, agglomeration resistance is played a good role, glycin chelated iron can better be applied in the Food fortification carrier, and extend its shelf-life.
The glycin chelated iron crystal that utilizes the inventive method to prepare and the water-soluble contrast of Powdered glycin chelated iron:
The water miscible quality of glycin chelated iron directly has influence on its application in feed, the solvability of crystallization glycin chelated iron and Powdered glycin chelated iron is done and compared, and result as shown in Figure 3.As can be seen from Figure 3, in 100g water, two kinds of different product water dissolubilities are similar, Powdered glycine chelate iron solubility 9.31g/100g, crystallization glycine chelate iron solubility 11.88g/100g, be converted into the glycine chelate iron solubility 9.36g/100g that is not with crystal water.As can be seen here, the solvability of crystallization glycin chelated iron is fine, is well suited for and adds in the middle of feed, as ferrous-fortifier, well applies.
The present invention is not limited to above-mentioned embodiment, and all are based on technical conceive of the present invention, and the structural improvement of having done, all fall among protection scope of the present invention.
Claims (5)
1. the crystalline growth method of a glycin chelated iron, is characterized in that: comprise the steps:
Glycin chelated iron is dissolved in the water of 75-85 ℃, is stirred with the speed of 20Hz-50Hz, the glycine chelate ferrous solution that to make concentration be 0.3g/ml;
Rate of temperature fall with 35-45 ℃/h is progressively lowered the temperature, and in solution, drips organic solvent, keeps this temperature after being cooled to 20 ℃, has continued the dropping of organic solvent at this temperature;
Filter crystal, sieve after oven dry, collect the product of granularity between the 20-60 order, thereby obtain the crystal of glycin chelated iron,
Wherein, the mixed solution that described organic solvent is acetone and dehydrated alcohol, and the mass ratio of acetone and dehydrated alcohol is 1:1～1:5;
The quality of described organic solvent and described glycin chelated iron mass ratio are 2:1-1:1;
It is 2～3 hours that described organic solvent all adds the time used.
2. the crystalline growth method of a kind of glycin chelated iron as claimed in claim 1, it is characterized in that: in described step, rate of temperature fall is 40 ℃.
3. the crystalline growth method of a kind of glycin chelated iron as claimed in claim 1, it is characterized in that: in described step, stir speed (S.S.) is 30Hz.
4. the crystalline growth method of a kind of glycin chelated iron as claimed in claim 1, it is characterized in that: in described organic solvent, the mass ratio of acetone and dehydrated alcohol is 1:3.
5. the crystalline growth method of a kind of glycin chelated iron as claimed in claim 1, it is characterized in that: the quality of described organic solvent and described glycin chelated iron mass ratio are 1:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237426A (en) * | 2015-11-12 | 2016-01-13 | 中南大学 | Method for controlling chain type ferrous glycine complex crystal size and uniformity |
| CN112690437A (en) * | 2020-12-28 | 2021-04-23 | 湖北省益欣盐产业技术研究院有限公司 | Anti-caking jujube salt and preparation method thereof |
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| WO2002030948A2 (en) * | 2000-10-11 | 2002-04-18 | Albion International, Inc. | A composition and method for preparing amino acid chelates free of interfering ions |
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| WO2002030948A2 (en) * | 2000-10-11 | 2002-04-18 | Albion International, Inc. | A composition and method for preparing amino acid chelates free of interfering ions |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237426A (en) * | 2015-11-12 | 2016-01-13 | 中南大学 | Method for controlling chain type ferrous glycine complex crystal size and uniformity |
| CN112690437A (en) * | 2020-12-28 | 2021-04-23 | 湖北省益欣盐产业技术研究院有限公司 | Anti-caking jujube salt and preparation method thereof |
| CN112690437B (en) * | 2020-12-28 | 2022-11-08 | 湖北省益欣盐产业技术研究院有限公司 | Anti-caking jujube salt and preparation method thereof |
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