CN103467331B - 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 required trace element of animal, be also one of most study and the trace element understanding the darkest needed by human, but body iron deficiency is but one of topmost nutrition problem of the whole world, particularly developing country.Iron is the important composition composition of oxyphorase, and be delivery of oxygen and the important element exchanging oxygen in blood, be also the moiety of many enzymes and the activator of redox reaction enzyme, sideropenia can cause the diseases such as anaemia.
Glycin chelated iron is a kind of iron enriched nutrient being very easy to be included the mankind and absorbing at interior mammalian organism, its have nontoxic non-stimulated, absorb fast, mend the many merits such as iron blood tonification effect is remarkable, be widely used in fodder additives.Research shows that the specific absorption ferrous sulfate of iron ion in glycine chelate molysite exceeds five to six times, has good chemical stability, has both avoided the mutual antagonistic action between mineral, turn eliminated the drawback that inorganic salt are oxidized VITAMIN.
Current glycin chelated iron mainly contains following several preparation method: 1, utilize glycine and ferrous sulfate, adds solid caustic soda reaction, and utilizes membrane sepn to obtain glycine sodium salt, utilize scraper plate thin film evaporation to be concentrated into precipitation epitaxial, final vacuum-drying after continuing reaction; 2, also have a kind of method of Preparation of amino acid ferrous chelate compound, add in organic alcohol solvent by amino acid and soluble ferrite fire crane, 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 it is convenient that its products obtained therefrom stores, and has excellent oxidation-resistance, anti-moisture absorption and water-soluble, thus eliminates defect in above-mentioned background technology.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A crystalline growth method for glycin chelated iron, comprises the steps:
Be dissolved in by glycin chelated iron in the water of 75-85 DEG C, stir with the speed of 20Hz-50Hz, obtained concentration is the glycine chelate ferrous solution of 0.3g/ml;
Progressively lower the temperature with the rate of temperature fall of 35-45 DEG C/h, organic solvent is dripped in solution, this temperature is kept after being cooled to 20 DEG C, continue the dropping of organic solvent at such a temperature, separated out to crystal, grow up, filtering crystals, sieve after oven dry, collect the product of granularity between 20-60 order, thus obtain the crystal of glycin chelated iron
Wherein, described organic solvent is the mixed solution of 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 DEG C.
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, quality and the glycin chelated iron mass ratio of organic solvent are preferably 1:1.
The present invention is through a large amount of test repeatedly of contriver, and just finally determine the selection of organic solvent and the determination of consumption, the determination of stir speed (S.S.), the determination of rate of temperature fall, adds the determination of organic solvent speed.
When crystallization, add organic solvent and mainly contain following reason: after 1. adding organic solvent, the specific inductivity of the aqueous solution can be made to reduce, thus 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 be originally combined with hydrophilic solute, and the hydration layer on its surface is destroyed, and causes the interaction between solute molecule increase and produce gathering, thus crystallization.
Contriver, in order to select suitable organic solvent, carried out a large amount of test 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, and boiling point is low, volatilization loss large, have the shortcomings such as certain toxicity, point of ignition are low to liver, makes him apply not as good as ethanol.The crystallization of methyl alcohol is suitable with ethanol, but has severe toxicity because methyl alcohol is oral, so application is also not as good as ethanol.From outward appearance ethanol as precipitation agent, gained crystal shows slightly white, and crystal grain is full.The organic solvent that acetone is separated out as 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, and as the organic solvent that glycin chelated iron crystal is separated out, gained crystal glassy yellow, granularity is fuller.Therefore the organic solvent that acetone and dehydrated alcohol mixture are by a certain percentage separated out as glycin chelated iron crystal is selected.
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; When acetone, dehydrated alcohol mass ratio are 1:3, color better (for glassy yellow), and particle is comparatively large, is ideal product; When acetone, dehydrated alcohol mass ratio are less than 1:5, although granularity is comparatively large, color starts to turn white.Consider the actual application value of product, select the product that iron level is higher, 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 in the solution completely, when for 1:1, glycin chelated iron is separated out substantially completely, and suitable increase organic solvent concentration is more conducive to crystallization completely, but if more than 2:1, without clear meaning.
It is comparatively suitable that glycine chelate ferrous solution rate of temperature fall is chosen as 40 DEG C/h, and stir speed (S.S.), from the process that 20Hz-50Hz changes, selects 40Hz comparatively suitable.
The selection of organic solvent drop rate, when organic solvent drop rate is crossed slow, the nucleus of formation, owing to lacking the power of growing up, is easily stirred and smashes, and cause nucleus too much, the crystal of growth is many, and granularity is little; Drip the too fast nucleus that also easily causes too much, the crystal size formed is little, and optimum rate of addition is for all to add 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, solution rate of temperature fall 40 DEG C/h, stir speed (S.S.) 40Hz, drips 2 hours organic solvent used times.
Owing to have employed 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 and water-soluble good product.After 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 advantages such as the inventive method has can produce with Small Scale Industryization, and operating procedure is simple, and tooling cost is lower, is convenient to standing storage, convenient application.Can be used for fodder additives, nutrition-fortifying agent, pharmaceutical preparation, for the control of iron microelement deficiency disease.
Accompanying drawing explanation
Fig. 1 is the glycin chelated iron crystal prepared of the present invention and Powdered glycin chelated iron oxidative stability comparing result figure;
Fig. 2 is the glycin chelated iron crystal prepared of the present invention and Powdered glycin chelated iron moisture absorption comparing result figure;
Fig. 3 is the glycin chelated iron crystal prepared of the present invention and the solvability result figure of Powdered glycin chelated iron in 100g water.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
Embodiment 1
Take 90g glycin chelated iron, be dissolved in 300g deionized water, be heated to 75 DEG C, stir speed (S.S.) 20HZ, start cooling, rate of temperature fall 35 DEG C/h, drips mixed organic solvents 180g(wherein acetone 90g, ethanol 90g), this temperature is kept after being cooled to 20 DEG C, and complete solvent dropping, add 2 hours organic solvent used times, crystal is crystallization in reactor.
Get oven dry product, weighing obtains 92g product (moisture 10%, anhydrous glycine chelated iron yield 95.3%) and sieves, collect the product of granularity between 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% from 98.40%, and moisture is containing 8.95%.
Embodiment 2
Take 90g glycin chelated iron, be dissolved in 300g deionized water, be heated to 80 DEG C, stir speed (S.S.) 30HZ, start the rate of temperature fall 40 DEG C/h that lowers the temperature, drip mixed organic solvents 180g(wherein acetone 30g, ethanol 150g), keep this temperature after being cooled to 20 DEG C, and complete solvent dropping, add 2 hours organic solvent used times, crystal is crystallization in reactor.
Get 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 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% from 98.30%, and moisture is containing 8.90%.
Embodiment 3
Take 90g glycin chelated iron, be dissolved in 300g deionized water, be heated to 85 DEG C, stir speed (S.S.) 40HZ, start the rate of temperature fall 45 DEG C/h that lowers the temperature, drip mixed organic solvents 90g(wherein acetone 30g, ethanol 60g), keep this temperature after being cooled to 20 DEG C, and complete solvent dropping, add 3 hours organic solvent used times, crystal is crystallization in reactor.
Get 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 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% from 98.15%, and moisture is containing 9.70%.
Embodiment 4
Take 90g glycin chelated iron, be dissolved in 300g deionized water, be heated to 80 DEG C, stir speed (S.S.) 50HZ, start the rate of temperature fall 43 DEG C/h that lowers the temperature, drip mixed organic solvents 135g(wherein acetone 27g, ethanol 108g), keep this temperature after being cooled to 20 DEG C, and complete solvent dropping, add 2.5 hours organic solvent used times, crystal is crystallization in reactor.
Get oven dry product, product 91g(moisture 9.8% of weighing to obtain, anhydrous glycine chelated iron yield 94.4%) sieve, collect the product of granularity between 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% from 98.35%, and moisture is containing 9.60%.
Embodiment 5
Take 90g glycin chelated iron, be dissolved in 300g deionized water, be heated to 80 DEG C, stir speed (S.S.) 30HZ, starts the rate of temperature fall 40 DEG C/h that lowers the temperature, and drips mixed organic solvents 90g(wherein acetone 22.5g, ethanol 67.5g) be cooled to 20 DEG C after keep this temperature, and complete solvent dropping, add 3 hours organic solvent used times, crystal is crystallization in reactor.
Get 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 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% from 98.37%, and moisture is containing 9.45%.
Comparative example 1
Take 90g glycin chelated iron, be dissolved in 300g deionized water, be heated to 80 DEG C, stir speed (S.S.) 20HZ, starts the rate of temperature fall 40 DEG C/h that lowers the temperature, and drips organic solvent-acetone 90g, add about 0.5 hour organic solvent used time, be cooled to 20 DEG C of crystallizations in reactor.
Get oven dry product, product 85.3g(moisture 1.03% of weighing, anhydrous glycine chelated iron yield 95.2%) product wherein below 100 orders accounts for 80.54% of total product quality, and 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% from 98.37%, and moisture is containing 3.45%.
Comparative example 2
Take 90g glycin chelated iron, be dissolved in 300g deionized water, be heated to 80 DEG C, stir speed (S.S.) 40HZ, starts the rate of temperature fall 40 DEG C/h that lowers the temperature, and drips organic solvent ethanol 90g, add about 0.5 hour organic solvent used time, be cooled to 20 DEG C of crystallizations in reactor.
Get oven dry product, product 86.3g(moisture 2.43% of weighing, anhydrous glycine chelated iron yield 95.5%) quality product below wherein 100 orders 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% from 98.37%, and moisture is containing 3.45%.
Comparative example 3
Take 90g glycin chelated iron, be dissolved in 300g deionized water, be heated to 80 DEG C, stir speed (S.S.) 20HZ, starts the rate of temperature fall 40 DEG C/h that lowers the temperature, and drips organic solvent methyl alcohol 90g, add about 0.5 hour organic solvent used time, be cooled to 20 DEG C of crystallizations in reactor.
Get oven dry product, product 86.3g(moisture 1.75% of weighing, anhydrous glycine chelated iron yield 94.8%) quality product below wherein 100 orders of sieving accounts for 82.52% of total product quality.Product colour is relatively 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% from 98.37%, and moisture is containing 3.95%.
Generally speaking, judge that the standard of glycin chelated iron crystal structure method quality is:
1, crystal yield: anhydrous glycine chelated iron yield is higher, then represent this crystallization method better;
2, crystal color: color is yellow, glassy yellow, illustrates that crystal quality is high, if color is white, illustrates wherein containing impurity;
3, crystal size: granularity is larger, anti-pressure ability, the agglomeration resistance ability of crystal are better, and quality is also higher;
4, the solubleness of crystal: solubleness is higher, illustrates that crystal solvability in water is better, so more easily absorb by animals and plants, quality is higher;
5, moisture absorption: the change of the product after contrast output and after two months product water content, it is more that water content increases, and illustrate that moisture absorption is larger, the quality of crystal is lower;
6, oxidisability: the product after contrast output accounts for total iron content with ferrous iron in product after two months to be changed, and variable quantity is larger, illustrate that oxidisability is higher, and the quality of crystal is also lower.
Contrasted by the product of embodiment 1-5 and comparative example 1-3 from yield, granularity, color, solubleness, moisture absorption (after two months change of moisture content), oxidisability (ferrous iron accounts for total iron content change after two months), result is as following table:
Clearly find out from upper table, adopt the glycin chelated iron crystal that embodiment 1-5 obtains, 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 ratio shared in the product to decline to some extent.The product granularity that embodiment 1-5 obtains in product granularity is larger, and the product of comparative example 1-3 is very thin.The difference of this granularity result in product resistance to compression, and the size of anti-caking ability.The larger resistance to compression of granularity and agglomeration preventing performance better.
The Performance Detection of the glycin chelated iron crystal below prepared for the present invention.
The glycin chelated iron crystal utilizing the inventive method to prepare and Powdered glycin chelated iron oxidative stability contrast:
Crystallization glycin chelated iron and Powdered glycin chelated iron are carried out storage test, 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, iron atom is in the encirclement of water molecules, and this serves certain oxygen barrier effect, so make the good of the more Powdered glycin chelated iron of the oxidative stability of crystallinity glycin chelated iron.
The glycin chelated iron crystal utilizing the inventive method to prepare and Powdered glycin chelated iron moisture absorption contrast:
Glycin chelated iron crystal and Powdered glycin chelated iron are exposed in atmosphere, observes their moisture absorption situation.Result as shown in Figure 2.As can be seen from Figure 2, contrast with Powdered glycin chelated iron, glycine chelate iron product its moisture absorption phenomenon obtained 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, curve trend steadily, possible cause crystalline water molecules is enclosed in glycin chelated iron surrounding molecules, glycin chelated iron adsorbed water molecule may will reach capacity, and 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 curve trend steadily.Due to the space structure that the water molecules in crystalline product is stable, agglomeration resistance is played a good role, glycin chelated iron can better be applied in Food fortification carrier, and extend its shelf-life.
The glycin chelated iron crystal utilizing 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, and crystallization glycin chelated iron is done with the solvability of Powdered glycin chelated iron and compares, 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, is converted into the glycine chelate iron solubility 9.36g/100g 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, well apply as ferrous-fortifier.
The present invention is not limited to above-mentioned embodiment, and all are based on technical conceive of the present invention, and done structural improvement, all falls among protection scope of the present invention.
Claims (4)
1. a crystalline growth method for glycin chelated iron, is characterized in that: comprise the steps:
Be dissolved in by glycin chelated iron in the water of 75-85 DEG C, stir with the speed of 20Hz-50Hz, obtained concentration is the glycine chelate ferrous solution of 0.3g/ml;
Progressively lower the temperature with the rate of temperature fall of 40 DEG C/h, in solution, drip organic solvent, after being cooled to 20 DEG C, keep this temperature, continued the dropping of organic solvent at such a temperature;
Filtering crystals, sieves after oven dry, collects the product of granularity between 20-60 order, thus obtains the crystal of glycin chelated iron,
Wherein, described organic solvent is the mixed solution of acetone and dehydrated alcohol, and the mass ratio of acetone and dehydrated alcohol is 1:1 ~ 1:5;
Quality and the described glycin chelated iron mass ratio of described organic solvent 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, is characterized in that: in described step, stir speed (S.S.) is 30Hz.
3. the crystalline growth method of a kind of glycin chelated iron as claimed in claim 1, is characterized in that: in described organic solvent, and the mass ratio of acetone and dehydrated alcohol is 1:3.
4. the crystalline growth method of a kind of glycin chelated iron as claimed in claim 1, is characterized in that: quality and the described glycin chelated iron mass ratio of described organic solvent are 1:1.
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