CN105061244A - Preparation method of glycine iron zinc complex - Google Patents
Preparation method of glycine iron zinc complex Download PDFInfo
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- CN105061244A CN105061244A CN201510593208.3A CN201510593208A CN105061244A CN 105061244 A CN105061244 A CN 105061244A CN 201510593208 A CN201510593208 A CN 201510593208A CN 105061244 A CN105061244 A CN 105061244A
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Abstract
A preparation method of a glycine iron zinc complex used for an animal feed additive comprises the following steps: adding glycine, a zinc raw material, a ferrous salt and a solvent into a reaction device, wherein the molar ratio of zinc elements in the zinc raw material to iron elements in the ferrous salt is controlled to be 1: 5-5: 1, and the ratio of the molar number of the glycine to the total molar number of the zinc elements and the iron elements is 1: 1-2.2: 1; after stirring evenly, controlling the reaction temperature and pH value in the whole process, after full reaction, discharging, cooling, crystallizing, separating, washing crystal, drying, crushing and sieving to obtain the finished product of the glycine iron zinc complex. The preparation method has the advantages of simple process steps, low cost, environmental protection, high product purity, stable quality, difficult color change in the production and processing processes and the like.
Description
Technical field
The present invention relates to a kind of preparation method of aminoacetic acid complex, particularly relate to a kind of preparation method of ferrous glycine Zn complex.
Background technology
Iron, zinc are the required trace elements of the animals such as poultry and livestock, they are present in humans and animals with the form of protein and metalloenzyme, there is accelerating growth grow, promote that blood-hemoglobin generates, improve the sense of taste, regulate immunity of organism, protect from infection and promote the functions such as wound healing.Therefore, iron and zinc confession animal normal growth should be added in feed.
For a long time, the trace element such as zinc, iron compound all is in various different formats joined in mixed feed by the mode of simple mixing.The organic or inorganic trace element of such form is easy to cause following problem: the antinutritional factor of mineral sulfates easily with feed in existed in the glycine ferrous 1. announced in ferrous sulfate and zinc sulfate and standard GB/T/T21996-2008 is combined the biology utilization ratio decline causing organic trace element iron, zinc and inorganic microelement iron, zinc.Fe
2+, Zn
2+by competition absorption and transport, passage DMT-1Fe
2+, Zn
2+ratio meet physiology optimal proportions and then can realize collaborative absorption, otherwise cause Fe
2+, Zn
2+transport vehicle competitive inhibition and antagonism.If just by simple mixing, Fe
2+, Zn
2+local environment residing is in animal body inconsistent, causes absorbable Fe
2+, Zn
2+proportional imbalance affect the absorption of animal body, thus impact absorbs the amount of iron and the zinc entered in body, causes iron zinc metabolic imbalance, thus affects the biological value of iron and zinc.
Along with the raising of people's living standard and the development of aquaculture, glycine, as foodstuff additive, medicine, cosmetics additive and feed amino acid, has been widely used in food, medicine, makeup and pig starter feed, boar food, broiler fodder, prawn feed and eel feed etc.Glycine is used as animal feedstuff additive and has following characteristics: can be used for producing protein fodder; Can be used as the phagostimulant (attractive substance) in fodder additives, improve animal feed intake; Bacillus subtilus and colibacillary breeding can be suppressed, play important preservative activity, reduce the diarrhea rate that piglet is caused because daily ration goes mouldy.Therefore, in animal diets, add glycine and can improve efficiency of feed utilization to greatest extent.
Aminoacetic acid complex is an important class in food and feed additive, it has been applied in the processing industries such as food, medicine, household chemicals, makeup, daily seasonings, feed, it is different from general industrial chemicals, not only there is its distinctive physiological function, but also very high purity and the absolute safety to human body, animal will be had.In recent years along with the fast development of food and feeds industry, the industry that synthon eats aminoacetic acid complex series product also obtains considerable raising, but the aminoacetic acid complex fodder additives of synthesis at present also exists following problems:
1) aminoacetic acid complex product is mainly based on monomer, even if occur ferrous glycine Zn complex product, it is also only glycine ferrous and zinc glycinate two kinds of products are simply mixed, and not only production cost is higher for this, complicated component, and mixture homogeneity is poor; In addition, existing part mixes product also can affect by its mixed carrier, there are pit, Huang Dian, affect the market sale of product, often metal and Glycine Levels can only be detected in these simple mixtures products, can not measure its structure and definite component concentration, quality product is also wayward;
2) in the synthetic reaction process of existing routine, by the impact of raw material and by product, even if ferrous glycine Zn complex adopts crystallization, the mode of wash crystallization thing carries out purifying, still there is the byproduct of reaction of insoluble impurities, larger molecular organics and association crystallization in product, the purity aspect of product need to improve;
3) in the preparation process of the copper of existing routine, zinc aminoacetic acid complex, processing step by its grinding operation, washing operation affects, not only the output of product is less, be unfavorable for suitability for industrialized production, and in product, also may there is the raw material that part unreacted completes, affect product quality and process costs;
4) glycine ferrous monomer is easy to be become ferrous glycine by the dioxygen oxidation in air in production and the course of processing, and then causes variable color; And animal is extremely low to the ferric absorption rate in ferrous glycine;
5) problems such as zinc glycinate product exists bad dispersibility, easy moisture absorption caking.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, provide that a kind of processing step is simple, cost is low, environmental protection, product purity are high, steady quality, the preparation method of not allochroic ferrous glycine Zn complex in production and the course of processing.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of preparation method of ferrous glycine Zn complex, comprises the following steps:
Glycine, zinc raw material, ferrous salt and solvent is added in reaction unit, in described zinc raw material, in zinc element and ferrous salt, the mol ratio of ferro element controls to be 1: 5 ~ 5: 1, and the mole number of described glycine is 1: 1 ~ 2.2: 1 with the ratio of the total mole number of aforementioned zinc element, ferro element; After stirring, whole-process control temperature of reaction and pH value, after fully reacting completely, blowing crystallisation by cooling, separation, wash crystallization thing, dry, pulverize and sieve, and obtains finished product ferrous glycine Zn complex.
In the technical scheme of the invention described above, we are groped by a large amount of theoretical investigationes and experiment repeatedly, sum up glycine ferrous and zinc glycinate can obtain a kind of product of crystal formation and steady quality by crystallization simultaneously under specific ratio, and taken into account animal to different contribution ratios that are ferrous and zinc, determine the feed ratio of reaction raw materials in the present invention.By chemical means, iron, zinc and glycine to be combined problems such as solving residual inorganic salt, ligand are unstable, the impact of antinutritional factor according to specific ratio; Our physiological condition different according to animal designs the ferrous glycine Zn complex of optimal proportions, thus make that iron, zinc are stable in animal body remains iron zinc optimal absorption ratio, thus avoid the problem that competition absorbs the metabolic imbalance suppressed and cause due to ratio imbalance in animal body, to play iron zinc biological value in animal body better.
In above-mentioned preparation method, preferred: described when adding glycine, zinc raw material, ferrous salt and solvent in reaction unit, first add glycine, zinc raw material, ferrous salt mixing, then add solvent.Feeding intake again by first raw material being mixed, can guarantee that the product that two kinds of reactions generate generates according to certain ratio better, being conducive to regulating and controlling the component concentration in product.
In above-mentioned preparation method, preferred: described when adding glycine, zinc raw material, ferrous salt and solvent in reaction unit, first in reaction unit, add solvent, open and stir, then drop into zinc raw material and ferrous salt, then drop into glycine itself and aforementioned zinc raw material and ferrous salt are reacted.
In above-mentioned preparation method, consider that the ferrous glycine Zn complex product prepared is mainly used in feed, therefore its product not only will meet general target level of product quality, also will meet hygienic standard.First we screen raw material, to determine the source of pollution that there is not harm animal health in raw material, secondly we can avoid producing new hazardness impurity in preparation process, finally can remove the most impurity existed in raw material in preparation and purge process.Based on such thought, preferred glycine is the glycine of purity more than 98%, pass through our detection and repeatedly analyze, not only metal content is all extremely low for the higher glycine of these purity, and in product polychlorobiphenyl, dioxin etc. to larger very little containing benzene organic content of harm.Preferred: described zinc raw material is zinc sulfate, basic zinc salt, zinc chloride or zinc oxide, and described ferrous salt is ferrous sulfate or iron protochloride.These raw materials can be anhydrous compound or the compound with crystal water.
In above-mentioned preparation method, preferred: described solvent is water or water-organic solvent mixed system, more preferably water-organic solvent mixed system.Organic solvent in described water-organic solvent mixed system is at least one in methyl alcohol, ethanol, acetone, propyl alcohol, ethylene glycol, glycerol, ethyl acetate, butanone; In described water-organic solvent mixed system, water is 1: 5 ~ 5: 1 with organic solvent volume ratio.Described solvent is generally disposable adding in reaction system.In reaction system of the present invention, preferred water-organic solvent mixed system has following advantage: 1. organic solvent dissolved oxygen is lower, can avoid ferrous oxidation; 2. solubleness is lower than water in organic solvent for zinc raw material, ferrous salt, by controlling the ratio of water-organic solvent mixed system, indirectly can control speed of reaction and crystallization rate and crystal formation; 3. the boiling point of organic solvent is lower, volatile, contributes to material and accelerates rate of drying, and the space of storeroom is increased, keep the loft of material, prevent from hardening and false conglomeration.
In above-mentioned preparation method, preferred: an airtight reaction cavity volume in described reaction unit, can be formed, described reaction cavity volume comprises interior room and mistress, and interior room and mistress are separated by a semi-permeable membranes, and described interior room and mistress are respectively equipped with interior room dog-house and mistress's dog-house; Also be provided with whipping appts, temperature control unit and pH value self-con-tained unit in described reaction cavity volume, in described pH value self-con-tained unit, add alkali lye in advance, alkali lye can be dripped by the pH value in assaying reaction at any time, reach the object of whole-process control pH value.Membrane separation technique is have employed in above-mentioned preferred reaction unit, the major advantage of nanofiltration membrane separation is except isolating comparatively except macromole from technical process, can also from solution, extract solute and be purified, thus reach the object of purifying and reclaiming product, greatly improve purity and the quality of product, this is also significant as the security risk of fodder additives for reducing product.
In above-mentioned preparation method, preferred: described interior room is surrounded by described mistress, and described whipping appts is arranged in interior room, described pH value self-con-tained unit is communicated in mistress.In reaction process, whipping appts not only can controls local temperature of reaction, reaction uniformity coefficient and speed of response, can also by the effect of current constantly by the glycine ferrous that generates near semi-permeable membranes and zinc glycinate molecule away from semi-permeable membranes, prevent glycine ferrous and zinc glycinate from depositing on semi-permeable membranes and blocking semi-permeable membranes space; In crystallisation process, because whipping appts is located at interior room, mistress has flow action but can not produce the factor that eddy current etc. is unfavorable for crystallization, can reach the object of uniform settling crystallization.
In above-mentioned preparation method, preferred: described semi-permeable membranes is fixed on the cylinder body support of reaction unit removably; Described semi-permeable membranes is preferably the one in cellulose acetate composite film, aromatic polyamide membrane, Polyphenylene Sulfone terephthalamide film, polybenzimidazole membrane, sulfonated poly (phenylene oxide) film, sulfonated polysulfone membrane, tetrafluoroethylene graft copolymer membrane.The aperture of described semi-permeable membranes is preferably 100-200pm.
In above-mentioned preparation method, preferred: the feed postition of described solvent is any one in following two kinds, be more preferably following and 2. plant mode:
1. in described interior room dog-house or mistress's dog-house, add solvent, leave standstill the osmotic balance to inside and outside room;
2. in described interior room dog-house and mistress's dog-house, add solvent respectively, leave standstill the osmotic balance to inside and outside room.
In above-mentioned preparation method, preferred, the feed way of described glycine, zinc raw material, ferrous salt is: drop into zinc raw material and ferrous salt at described interior room dog-house, dropping into glycine again at described mistress's dog-house makes itself and aforementioned zinc raw material and ferrous salt react, room dog-house and mistress's dog-house in finally closing.Described interior room dog-house and mistress's dog-house are formula able to turn on or off, forming closed environment, reaching the object of insulation, starvation in reaction process by closing inside and outside room dog-house; In crystallisation by cooling process after completion of the reaction, closed environment can realize uniform decrease in temperature, drops to minimum by the interference in the external world, it also avoid ferrous oxidising problem.
In above-mentioned preparation method, preferably, described temperature control unit comprises is located at temp probe in interior room and heating component, and described heating component is formed primarily of the chuck layer being coated on described mistress, and in described chuck layer, logical hot water or hot steam heat.Preferred, described reaction process and crystallisation by cooling process are all carried out in the airtight reaction cavity volume of described reaction unit, in described reaction process, in chuck layer, logical hot water or hot steam carry out homogeneous heating, pass into water coolant and carry out uniform decrease in temperature in described crystallisation by cooling process in chuck layer.Collect crystallization by the sampling valve opened bottom reaction unit after crystallisation by cooling and be deposited in the ferrous glycine Zn complex product bottom reaction unit.Crystallized product is deposited in bottom reactor, observes crystal formation and the crystallization situation of product, discharged, dig the labour intensity of material after avoiding crystallization by baiting valve by take-off valve sampling.
In above-mentioned preparation method, preferably, described reaction whole-process control temperature of reaction is 20 DEG C ~ 65 DEG C, and the pH value controlling reaction system is 3.0-7.0 (more preferably 5-7); Feed intake and admittedly contain than being about 10% ~ 50% (Gu containing the mass ratio accounting for raw material and solvent sum than the raw material for not containing crystal water); Controlling the described reaction times is 15min ~ 5h.We show in experiment repeatedly, the aforementioned better Parameter Conditions for generating ferrous glycine Zn complex, if pH value is too high or under alkaline environment, ferrous iron is easy to generate ferric iron with the oxidizing substance reaction in water, cause product to turn yellow, have a strong impact on product appearance and quality; This pH value of also producing upper preferred raw material sulphuric acid ferrous iron with us adapts simultaneously.
Compared with prior art, the invention has the advantages that:
(1) the present invention is based on glycine ferrous similar with the physico-chemical property of zinc glycinate, under the prerequisite of same synthesis technique can be adopted, by repeatedly repetition test, find that glycine ferrous and zinc glycinate can with ferrous glycine Zn complex co-crystallization out under specified proportion, in crystal, zinc glycinate and glycine ferrous are spatially staggered, solve the large technical barrier of three in the actual production course of processing: 1. ferrous glycine Zn complex considerably reduces glycine ferrous and exposes aerial position, glycine ferrous be chronically exposed to ferrous iron in air be easily oxidized to ferric iron cause variable color and utilization ratio low, 2. solve higher, the easy moisture absorption caking of zinc glycinate product bad dispersibility, viscosity, be not easy to the problem of Product processing and storage, 3. in ferrous glycine Zn complex of the present invention, glycine ferrous and zinc glycinate are evenly distributed and constitute an entirety, compare traditional glycine ferrous and the mixture of zinc glycinate, its mixture homogeneity is high, and reduce this step of batching mixing, reduce production cost and labour intensity, it also avoid the huge noise in mixing process and dust simultaneously, improve employee's production operation environment, also environmental protection more.
(2) semi-permeable membranes is creatively adopted to be separated in interior room and mistress in reaction unit of the present invention, have the following advantages: 1. control speed of response: zinc raw material, ferrous salt and glycine are separately fed intake, glycine can not pass semi-permeable membranes because of sterically hindered relation enter interior room, and zinc raw material and ferrous salt can enter into mistress by semi-permeable membranes in the form of an ion; By regulating the speed of agitator, the ionic concn of control osmotic pressure and solution itself, reaches inorganic zinc raw material and ferrous salt reacts through semi-permeable membranes and glycine in the close mode at the uniform velocity spread.2. semi-permeable membranes has filteration, suitably can reduce the purity of starting material inorganic ferrous salt and zinc raw material, expands buying scope, reduces raw material supply shortage risk and reduces raw materials cost; There is different impurity because of the impact of different production technique in inorganic zinc raw material and ferrous salt, as insolubles, the poisonous and harmful larger molecular organicses etc. such as the heavy metals such as lead, bismuth, thallium and polychlorobiphenyl, dioxin, have a strong impact on the purity of subsequent product, security and crystal formation homogeneity.To drop into from interior room dog-house at inorganic zinc raw material and ferrous salt, under agitation, inorganic zinc raw material and ferrous salt arrive mistress with ionic condition by semi-permeable membranes, play the effect that a membrane filtration removal of impurities is purified.
(3) after the zinc raw material mixed and ferrous salt put into solvent, can dissolve simultaneously and discharge zine ion and ferrous ion, with react through the glycine outside semi-permeable membranes and film by stirring together with the current that produce, generate a certain proportion of zinc glycinate and glycine ferrous simultaneously, and form the crystallite with certain space structure.During crystallisation by cooling, zinc glycinate and glycine ferrous can form mixed crystal according to a certain percentage, wrap quilt mutually, avoid glycine ferrous to be too much exposed in air and are oxidized.If local zinc raw material and ferrous salt ratio inconsistent, can generate zinc glycinate and the glycine ferrous of different ratios, the space structure of crystallite is different, and the mixed crystal of formation is also different, finally can affect the quality of product.
(4) after last consignment of ferrous glycine Zn complex blowing of the present invention, appropriate solvent can be supplemented, again raw material reaction is dropped into, can serialization scale production be carried out, not need to rejoin solvent, simplify production stage, reduce labour intensity, reduce production cost, improve production environment, enhance productivity.Only need the purity of looking raw material, periodic replacement semi-permeable membranes and cleaning reaction still.
(5) the ferrous glycine Zn complex that the inventive method is obtained, by chemical means, iron, zinc and glycine are combined according to specific ratio, solve the problems such as residual inorganic salt, ligand are unstable, the impact of antinutritional factor, not only processing step is simple, cost is low for preparation method of the present invention, environmental protection, and product grain evenly, good dispersity, easily dry, product purity is not high, steady quality, easy to change in production and the course of processing; Reacted rear cooling and obtained mixed crystal, sold lover, be more conducive to the market sale promoting product, and product structure composition can detect, quality product is easily controlled.
(6) the present invention can design the ferrous glycine Zn complex of optimal proportions thus makes iron, zinc stably remain iron zinc optimal absorption ratio in animal body by the physiological condition different according to animal, thus avoid the problem that competition absorbs the metabolic imbalance suppressed and cause due to ratio imbalance in animal body, thus play iron zinc biological value in animal body better.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of the reaction unit used in the embodiment of the present invention 5,6.
Fig. 2 is the XRD diffracting spectrum of preparation-obtained ferrous glycine Zn complex in the embodiment of the present invention 2.
Fig. 3 is the XRD diffracting spectrum of preparation-obtained ferrous glycine Zn complex in the embodiment of the present invention 4.
Fig. 4 is the XRD diffracting spectrum of preparation-obtained ferrous glycine Zn complex in the embodiment of the present invention 5.
Marginal data
1---pH value self-con-tained unit;
2---temp probe;
3---whipping appts;
4---interior room dog-house;
5---mistress's dog-house;
6---mistress;
7---semi-permeable membranes;
8---interior room;
9---chuck layer;
10---baiting valve;
11---sampling valve.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various starting material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.The raw material below related to is commercial diet level.
Embodiment 1:
The preparation method that can be used for the ferrous glycine Zn complex of animal feedstuff additive of the present invention, comprises the following steps:
Take the glycine that 50.5g purity is 98%, 143.5g purity is the iron vitriol of 97%, 29.6g purity be 97% Zinc Sulphate Heptahydrate put in reactor, in Zinc Sulphate Heptahydrate, in zinc element and iron vitriol, the mol ratio of ferro element controls as about 1: 5, the mole number of glycine and aforementioned zinc element, the ratio of the total mole number of ferro element is about 1.1: 1, then stir, add 300mL water, temperature of reaction is regulated to be 20 DEG C, pH value in reaction is regulated to be 3.0, stirring reaction 15 minutes, centrifugation after cooling and stirring crystallization, wash crystallization thing, vacuum-drying, pulverize and sieve, obtain ferrous glycine Zn complex 183.0g.
Analyze through detecting, Fe in the ferrous glycine Zn complex that the present embodiment obtains
2+content is 13.9%, Fe
3+content is 0.1%, Zn
2+content is 3.3%, SO
4 2-content is 28.5%, and total Glycine Levels is 22.1%, and the percentage of water loss of product at 280 DEG C is 26.5%.I.e. Fe
2+: Zn
2+=5: 1, NH
2cH
2cOO
-: (Fe
2++ Zn
2+)=1: 1, products molecule formula is:
ZnFe
5(NH
2cH
2cOO
-)
6(SO
4)
630H
2o, yield is 91%, and purity is 97%.
Percentage of water loss at 280 DEG C in above-mentioned analytical procedure: through repetitious experimental verification, find product constant weight after dry 3h in 280 DEG C of baking ovens, find that its volatile substances is the crystal water contained in product after testing, and all volatilize (following examples are identical all therewith).
Embodiment 2:
The preparation method that can be used for the ferrous glycine Zn complex of animal feedstuff additive of the present invention, comprises the following steps:
Take the glycine that 38.3kg purity is 98%, 56.1kg purity is the ferrous sulfate monohydrate of 91%, 38.1kg purity be 94% Zinc Sulphate Monohydrate put in reactor, in Zinc Sulphate Monohydrate, in zinc element and ferrous sulfate monohydrate, the mol ratio of ferro element controls as about 2: 3, the mole number of glycine and aforementioned zinc element, the ratio of the total mole number of ferro element is about 1: 1, then stir, add water-ethyl acetate mixed solvent (water: ethyl acetate volume ratio is 1: 2) 120kg, temperature of reaction is regulated to be 45 DEG C, pH value in reaction is regulated to be 4.5, stirring reaction 45 minutes, centrifugation after cooling and stirring crystallization, wash crystallization thing, vacuum-drying, pulverize and sieve, obtain ferrous glycine Zn complex 153.7kg.
Analyze through detecting, Fe in the ferrous glycine Zn complex that the present embodiment obtains
2+content is 10.1%, Fe
3+content is 0.1%, Zn
2+content is 7.8%, SO
4 2-content is 29.1%, and total Glycine Levels is 22.7%, and as shown in Figure 2, the percentage of water loss of product at 280 DEG C is 27.2% to the XRD diffracting spectrum of product.I.e. Fe
2+: Zn
2+=3: 2, NH
2cH
2cOO
-: (Fe
2++ Zn
2+)=1: 1, products molecule formula is: Zn
2fe
3(NH
2cH
2cOO
-)
5(SO
4)
525H
2o, yield is 93%, and purity is 97%.
Embodiment 3:
The preparation method that can be used for the ferrous glycine Zn complex of animal feedstuff additive of the present invention, comprises the following steps:
Take the glycine that 48.3kg purity is 98%, 14.0kg purity is the iron protochloride of 91%, 70.1kg purity be 97% zinc chloride put in reactor, in zinc chloride, in zinc element and iron protochloride, the mol ratio of ferro element controls as about 5: 1, the mole number of glycine and aforementioned zinc element, the ratio of the total mole number of ferro element is about 1.05: 1, then stir, add water-ethanol mixed solvent (water: ethanol contend ratio is 5: 1) 200Kg, temperature of reaction is regulated to be 35 DEG C, pH value in reaction is regulated to be 5.0, stirring reaction 50 minutes, centrifugation after cooling and stirring crystallization, wash crystallization thing, vacuum-drying, pulverize and sieve, obtain ferrous glycine Zn complex 166.1kg.
Analyze through detecting, Fe in the ferrous glycine Zn complex that the present embodiment obtains
2+content is 2.9%, Fe
3+content is 0.1%, Zn
2+content is 17.4%, Cl
-content is 22.8%, and total Glycine Levels is 23.8%, and the percentage of water loss of product at 280 DEG C is: 29.5%.I.e. Fe
2+: Zn
2+=1: 5, NH
2cH
2cOO
-: (Fe
2++ Zn
2+)=1: 1, products molecule formula is:
Zn
5fe (NH
2cH
2cOO
-)
6cl
1230H
2o, yield is 89%, and purity is 96%.
Embodiment 4:
The preparation method that can be used for the ferrous glycine Zn complex of animal feedstuff additive of the present invention, comprises the following steps:
Take the glycine that 38.6kg purity is 98%, 37.4kg purity is the ferrous sulfate monohydrate of 91%, 55.0kg purity be 98% Zinc Sulphate Monohydrate put in reactor, in Zinc Sulphate Monohydrate, in zinc element and ferrous sulfate monohydrate, the mol ratio of ferro element controls as about 3: 2, the mole number of glycine and aforementioned zinc element, the ratio of the total mole number of ferro element is about 1: 1, then stir, add boiling mixed solvent (water: methyl alcohol volume ratio is 4: 1) 485Kg, temperature of reaction is regulated to be 40 DEG C, pH value in reaction is regulated to be 7.0, stirring reaction 1h, centrifugation after cooling and stirring crystallization, wash crystallization thing, vacuum-drying, pulverize and sieve, obtain ferrous glycine Zn complex 152.5kg.
Analyze through detecting, Fe in the ferrous glycine Zn complex that the present embodiment obtains
2+content is 6.6%, Fe
3+content is 0.2%, Zn
2+content is 11.7%, SO
4 2-content is 28.9%, and total Glycine Levels is 22.5%, and as shown in Figure 3, the percentage of water loss of product at 280 DEG C is 27.5% to the XRD diffracting spectrum of product.I.e. Fe
2+: Zn
2+=2: 3, NH
2cH
2cOO
-: (Fe
2++ Zn
2+)=1: 1, products molecule formula is: Zn
3fe
2(NH
2cH
2cOO
-)
5(SO
4)
525H
2o, yield is 92%, and purity is 97%.
Embodiment 5:
A reaction unit as shown in Figure 1, can form an airtight reaction cavity volume (about 1m in reaction unit
3left and right), reaction cavity volume comprises interior room 8 and mistress 6, and interior room 8 and mistress 6 are separated by a semi-permeable membranes 7, and interior room 8 and mistress 6 are respectively equipped with interior room dog-house 4 and mistress's dog-house 5; Also be provided with whipping appts 3, temperature control unit and pH value self-con-tained unit 1 in reaction cavity volume, in pH value self-con-tained unit 1, add alkali lye in advance, alkali lye can be dripped by the pH value in assaying reaction at any time, reach the object of whole-process control pH value.
In the reaction unit of the present embodiment, interior room 8 is surrounded by mistress 6, and whipping appts 3 is arranged in interior room 8, and pH value self-con-tained unit 1 is communicated in mistress 6.In reaction process, whipping appts 3 not only can controls local temperature of reaction, reaction uniformity coefficient and speed of response, can also by the effect of current constantly by the glycine ferrous of generation semi-permeable membranes 7 near and zinc glycinate molecule away from semi-permeable membranes, prevent glycine ferrous and zinc glycinate from depositing on semi-permeable membranes 7 and blocking semi-permeable membranes space; In crystallisation process, because whipping appts 3 is located at interior room 8, mistress 6 has flow action but can not produce the factor that eddy current etc. is unfavorable for crystallization, can reach the object of uniform settling crystallization.The semi-permeable membranes 7 of the present embodiment is fixed on the cylindrical body support of reaction unit removably; Semi-permeable membranes 7 is tetrafluoroethylene graft copolymer membrane, and the aperture of semi-permeable membranes is 100-200pm.
Interior room dog-house 4 in the present embodiment and mistress's dog-house 5 are formula able to turn on or off, forming closed environment, reaching the object of insulation, starvation in reaction process by closing inside and outside room dog-house; In crystallisation by cooling process after completion of the reaction, closed environment can realize uniform decrease in temperature, drops to minimum by the interference in the external world, it also avoid ferrous oxidising problem.
The temperature control unit of the present embodiment comprises is located at temp probe 2 in interior room 8 and heating component, and heating component is formed primarily of the chuck layer 9 being coated on mistress 6, and in chuck layer 9, logical hot water or hot steam heat.
Adopt the reaction unit of above-mentioned the present embodiment to prepare the ferrous glycine Zn complex that can be used for animal feedstuff additive, specifically comprise the following steps:
Add water in mistress's dog-house 5 and interior room dog-house 4 of reaction unit simultaneously, amount to 0.4 ton, leave standstill 15min, open whipping appts 3, interior room dog-house 4 drop into purity be 98% Zinc Sulphate Monohydrate 18.3kg and purity be 98% iron vitriol 28.4kg, the glycine 15.4kg of 98% purity is dropped at mistress's dog-house 5, in Zinc Sulphate Monohydrate, in zinc element and iron vitriol, the mol ratio of ferro element controls as about 1: 1, the mole number of glycine and aforementioned zinc element, the ratio of the total mole number of ferro element is about 1: 1, then room dog-house 4 and mistress's dog-house 5 in closing, open pH value self-con-tained unit 1, whole-process control temperature of reaction is 65 DEG C, pH value is 7.0, after reaction 3h, cooling and stirring is to the even crystallization of room temperature, crystallized product is deposited in bottom reaction unit, generate to no longer including new crystal from sampling valve 11 sampling observation crystal formation and crystallization situation every 20min, discharged by baiting valve 10, collect crystallisate and wash 3 times, expansion drying, pulverize 40 mesh sieves and obtain finished product ferrous glycine Zn complex 59.5kg.The reaction process of the present embodiment and crystallisation by cooling process are all carried out in the airtight reaction cavity volume of reaction unit, and in reaction process, in chuck layer 9, logical hot steam carries out homogeneous heating, passes into water coolant and carry out uniform decrease in temperature in crystallisation by cooling process in chuck layer 9.Collect crystallization by the sampling valve 11 opened bottom reaction unit after crystallisation by cooling and be deposited in the ferrous glycine Zn complex product bottom reaction unit.
Fe in ferrous glycine Zn complex is analyzed through detecting
2+content is 8.6%, Fe
3+content < 0.05%, Zn
2+content is 10.0%, SO
4 2-content is 29.5%, and total Glycine Levels is 22.9%, and as shown in Figure 4, the percentage of water loss of product at 280 DEG C is the XRD diffracting spectrum of product: 27.6%.I.e. Fe
2+: Zn
2+=1: 1, NH
2cH
2cOO
-: (Fe
2++ Zn
2+)=1: 1, products molecule formula is: ZnFe (NH
2cH
2cOO
-)
2(SO
4)
210H
2o, yield is 92%, and purity is 99%.
Embodiment 6:
The present embodiment to adopt in embodiment 5 reaction unit as shown in Figure 1 equally, adopts this reaction unit to prepare the ferrous glycine Zn complex that can be used for animal feedstuff additive, specifically comprises the following steps:
Add water-ethylene glycol mixed solvent (volume ratio 1: 5) in mistress's dog-house 5 and interior room dog-house 4 of reaction unit simultaneously, amount to 0.3 ton, leave standstill 15min, open whipping appts 3, interior room dog-house 4 drop into purity be 91% zinc oxide 8.9kg and purity be 88% iron protochloride 72.2kg, the glycine 101.1kg of 98% purity is dropped at mistress's dog-house 5, in zinc in zinc oxide element and iron protochloride, the mol ratio of ferro element controls as about 1: 5, the mole number of glycine and aforementioned zinc element, the ratio of the total mole number of ferro element is about 2.2: 1, then room dog-house 4 and mistress's dog-house 5 in closing, open pH value self-con-tained unit 1, whole-process control temperature of reaction is 65 DEG C, pH value is 5.0, after reaction 5h, cooling and stirring is to the even crystallization of room temperature, crystallized product is deposited in bottom reaction unit, generate to no longer including new crystal from sampling valve 11 sampling observation crystal formation and crystallization situation every 20min, discharged by baiting valve 10, collect crystallisate and wash 3 times, expansion drying, cross 40 mesh sieves and obtain finished product ferrous glycine Zn complex 130.3kg.The reaction process of the present embodiment and crystallisation by cooling process are all carried out in the airtight reaction cavity volume of reaction unit, and in reaction process, in chuck layer 9, logical hot steam carries out homogeneous heating, passes into water coolant and carry out uniform decrease in temperature in crystallisation by cooling process in chuck layer 9.Collect crystallization by the sampling valve 11 opened bottom reaction unit after crystallisation by cooling and be deposited in the ferrous glycine Zn complex product bottom reaction unit.
Fe in ferrous glycine Zn complex is analyzed through detecting
2+content is 19.1%, Fe
3+content < 0.05%, Zn
2+content is 4.5%, and total Glycine Levels is 60.6%, and the percentage of water loss of product at 280 DEG C is: 14.6%.I.e. Fe
2+: Zn
2+=5: 1, NH
2cH
2cOO
-: (Fe
2++ Zn
2+)=2: 1, products molecule formula is: ZnFe
5(NH
2cH
2cOO
-)
1212H
2o, yield is 89%, and purity is 99%.
Claims (10)
1. can be used for a preparation method for the ferrous glycine Zn complex of animal feedstuff additive, comprise the following steps:
Glycine, zinc raw material, ferrous salt and solvent is added in reaction unit, in described zinc raw material, in zinc element and ferrous salt, the mol ratio of ferro element controls to be 1: 5 ~ 5: 1, and the mole number of described glycine is 1: 1 ~ 2.2: 1 with the ratio of the total mole number of aforementioned zinc element, ferro element; After stirring, whole-process control temperature of reaction and pH value, after fully reacting completely, blowing crystallisation by cooling, separation, wash crystallization thing, dry, pulverize and sieve, and obtains finished product ferrous glycine Zn complex.
2. preparation method according to claim 1, is characterized in that: described when adding glycine, zinc raw material, ferrous salt and solvent in reaction unit, first adds glycine, zinc raw material, ferrous salt mixing, then adds solvent.
3. preparation method according to claim 1, it is characterized in that: described when adding glycine, zinc raw material, ferrous salt and solvent in reaction unit, first in reaction unit, add solvent, open and stir, then drop into zinc raw material and ferrous salt, then drop into glycine itself and aforementioned zinc raw material and ferrous salt are reacted.
4. the preparation method according to claim 1,2 or 3, is characterized in that: described zinc raw material is zinc sulfate, basic zinc class, zinc chloride or zinc oxide, and described ferrous salt is ferrous sulfate or iron protochloride; Described solvent is water or water-organic solvent mixed system; Organic solvent in described water-organic solvent mixed system is at least one in methyl alcohol, ethanol, acetone, propyl alcohol, ethylene glycol, glycerol, ethyl acetate, butanone; In described water-organic solvent mixed system, water is 1: 5 ~ 5: 1 with organic solvent volume ratio.
5. the preparation method according to claim 1,2 or 3, it is characterized in that: an airtight reaction cavity volume in described reaction unit, can be formed, described reaction cavity volume comprises interior room (8) and mistress (6), and interior room (8) and mistress (6) are separated by a semi-permeable membranes (7), described interior room (8) and mistress (6) are respectively equipped with interior room dog-house (4) and mistress's dog-house (5); Whipping appts (3), temperature control unit and pH value self-con-tained unit (1) is also provided with in described reaction cavity volume.
6. preparation method according to claim 5, it is characterized in that: described interior room (8) is surrounded by described mistress (6), and described whipping appts (3) is arranged in interior room (8), described pH value self-con-tained unit (1) is communicated in mistress (6); Described semi-permeable membranes (7) is fixed on this body support frame of reaction unit removably; Described semi-permeable membranes (7) is cellulose acetate composite film, one in aromatic polyamide membrane, Polyphenylene Sulfone terephthalamide film, polybenzimidazole membrane, sulfonated poly (phenylene oxide) film, sulfonated polysulfone membrane, tetrafluoroethylene graft copolymer membrane.
7. preparation method according to claim 5, is characterized in that, the feed postition of described solvent is any one in following two kinds:
1. in described interior room dog-house (4) or mistress's dog-house (5), add solvent, leave standstill the osmotic balance to inside and outside room;
2. in described interior room dog-house (4) and mistress's dog-house (5), add solvent respectively, leave standstill the osmotic balance to inside and outside room;
The feed way of described glycine, zinc raw material, ferrous salt is: drop into zinc raw material and ferrous salt described interior room dog-house (4), drop into glycine again itself and aforementioned zinc raw material and ferrous salt are reacted described mistress's dog-house (5); Described interior room dog-house (4) and mistress's dog-house (5) are formula able to turn on or off.
8. preparation method according to claim 5, it is characterized in that: described temperature control unit comprises is located at temp probe (2) in interior room (8) and heating component, described heating component is formed primarily of the chuck layer (9) being coated on described mistress (6), and in described chuck layer (9), logical hot water or hot steam heat.
9. preparation method according to claim 8, it is characterized in that: described reaction process and crystallisation by cooling process are all carried out in the airtight reaction cavity volume of described reaction unit, in described reaction process, in chuck layer (9), logical hot water or hot steam carry out homogeneous heating, pass into water coolant and carry out uniform decrease in temperature in described crystallisation by cooling process in chuck layer (9).
10. the preparation method according to claim 1,2 or 3, is characterized in that: described reaction whole-process control temperature of reaction is 20 DEG C ~ 65 DEG C, and the pH value controlling reaction system is 3.0-7.0; Controlling the described reaction times is 15min ~ 5h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108125193A (en) * | 2017-12-29 | 2018-06-08 | 南通市飞宇精细化学品有限公司 | A kind of preparation method of food additive citric acid iron |
| 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 |
| CN113666836A (en) * | 2021-08-03 | 2021-11-19 | 四川吉隆达生物科技集团有限公司 | Production process of feed-grade zinc glutamate |
| CN113666836B (en) * | 2021-08-03 | 2024-06-11 | 四川吉隆达生物科技集团有限公司 | Production process of feed-grade zinc glutamate |
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| WO2002030947A2 (en) * | 2000-10-11 | 2002-04-18 | Albion International, Inc. | Compositions and methods of preparing amino acid chelates and complexes |
| US20150093469A1 (en) * | 2012-05-02 | 2015-04-02 | Pancosma Sa | Organometallic complex, powder intended for animal feed and preparation methods thereof |
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| CN1178786A (en) * | 1996-10-04 | 1998-04-15 | 上海福赐德营养保健品有限责任公司 | Method for preparing amino-acid metal chelate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108125193A (en) * | 2017-12-29 | 2018-06-08 | 南通市飞宇精细化学品有限公司 | A kind of preparation method of food additive citric acid iron |
| 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 |
| CN113666836A (en) * | 2021-08-03 | 2021-11-19 | 四川吉隆达生物科技集团有限公司 | Production process of feed-grade zinc glutamate |
| CN113666836B (en) * | 2021-08-03 | 2024-06-11 | 四川吉隆达生物科技集团有限公司 | Production process of feed-grade zinc glutamate |
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Denomination of invention: Preparation method for iron and zinc glycine complex Effective date of registration: 20200630 Granted publication date: 20170531 Pledgee: Bank of Changsha Limited by Share Ltd. HSBC branch Pledgor: CHANGSHA XINGJIA BIO-ENGINEERING Co.,Ltd. Registration number: Y2020980003606 |
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