CN105061244B - Preparation method of glycine iron zinc complex - Google Patents
Preparation method of glycine iron zinc complex Download PDFInfo
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- CN105061244B CN105061244B CN201510593208.3A CN201510593208A CN105061244B CN 105061244 B CN105061244 B CN 105061244B CN 201510593208 A CN201510593208 A CN 201510593208A CN 105061244 B CN105061244 B CN 105061244B
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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, more particularly to a kind of system of ferrous glycine Zn complex
Preparation Method.
Background technology
Iron, zinc are micro- necessary to be the animals such as poultry and livestock, and they exist in the form of protein and metalloenzyme
In humans and animals, with tachyauxesis development, promote blood-hemoglobin generation, improve the sense of taste, regulation immunity of organism, prevent sense
The function such as dye and promotion wound healing.Therefore, iron should be added in feed and zinc supplies animal normal growth.
For a long time, the trace element such as zinc, iron compound in various different formats is added by way of being simply mixed
Enter in mixed feed.The organic or inorganic trace element of so form easily causes problems with：1. ferrous sulfate and sulphur
Mineral sulfates present in the ferrous bisglycinate chelate announced in sour zinc and standard GB/T/T 21996-2008 is easily and feed
In ANFs combine cause organic trace element iron, zinc and inorganic microelement iron, zinc biology utilization rate decline.
Fe2+、Zn2+By competing absorption and transport, passage DMT-1Fe2+、Zn2+Ratio meet physiology optimal proportions can then realize collaboration
Absorb, otherwise cause Fe2+、Zn2+Transport vehicle Reverse transcriptase and antagonism.If simply by being simply mixed, Fe2+、Zn2+
Residing local environment is inconsistent in animal body, causes absorbable Fe2+、Zn2+Proportional imbalance influence animal body suction
Receive, so as to influence to be absorbed into the amount of internal iron and zinc, cause iron zinc metabolic imbalance, so as to influence the biology of iron and zinc to imitate
Valency.
Continued to develop with aquaculture with the improvement of people ' s living standards, glycine is used as food additives, medicine, change
Cosmetic additive and feed amino acid, are widely used in food, medicine, cosmetics and pig starter feed, boar food, broiler chicken feeding
Material, prawn feed and eel feed etc..Glycine has the characteristics that as animal feed additive：Can be used to produce albumen feeding
Material；Can be used as the phagostimulant (attractant) in feed addictive, improve animal feed intake；Hay bacillus and Escherichia coli can be suppressed
Breeding, play important antisepsis, reduce diarrhea rate of the piglet caused by daily ration goes mouldy.Therefore, add in animal diets
Plus glycine can to greatest extent improve efficiency of feed utilization.
Aminoacetic acid complex is an important class in food and feed additive, its be applied to food, medicine,
In the processing industries such as household chemicals, cosmetics, daily flavouring, feed, it is different from general industrial chemicals, not only special with it
Some physiological functions, but also there is purity very high and to human body, the absolute safety of animal.Recently as food and
The fast development of feed industry, the industry of the edible aminoacetic acid complex series of products of synthon also obtains considerable raising, so
And, at present also there are following problems in the aminoacetic acid complex feed addictive of synthesis：
1) aminoacetic acid complex product is mainly based on monomer, even if occurring ferrous glycine Zn complex product, its
Also it is only to be simply mixed two kinds of products of ferrous bisglycinate chelate and glycine zine, not only production cost is higher for this, composition is multiple
It is miscellaneous, and mixture homogeneity is poor；Additionally, existing part mixes product can also be influenceed by its mixed carrier, there are pit, Huang
Point, influences the market sale of product, and metal and Glycine Levels can only be often detected in these simple mixtures products, can not
Its structure and definite constituent content are determined, product quality is not easy to control；
2) in existing conventional synthetic reaction process, influenceed by raw material and accessory substance, ferrous glycine Zn complex is
Make to be purified by the way of crystallization, wash crystallization thing, insoluble impurities, larger molecular organicses and association are still suffered from product
The byproduct of reaction of crystallization, the purity aspect of product need to be improved；
3) in existing conventional copper, the preparation process of zinc aminoacetic acid complex, by its grinding operation, the work of washing operation
Skill step influences, and not only the yield of product is smaller, is unfavorable for there is likely to be part unreacted in industrialized production, and product
The raw material of completion, influences product quality and process costs；
4) ferrous bisglycinate chelate monomer is easy to by the dioxygen oxidation in air into ferrous glycine in production and process,
And then cause discoloration；And animal to ferrous glycine in ferric absorption rate it is extremely low；
5) there is bad dispersibility in glycine zine product, the problems such as the easy moisture absorption is lumpd.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to be mentioned and defect in background above technology, there is provided one
Kind of processing step is simple, low cost, environmental protection, product purity high, steady quality, not easy to change in production and process
The preparation method of ferrous glycine Zn complex.
In order to solve the above technical problems, technical scheme proposed by the present invention is a kind of preparation side of ferrous glycine Zn complex
Method, comprises the following steps：
To addition glycine, zinc raw material, ferrous salt and solvent, Zn-ef ficiency and ferrous salt in the zinc raw material in reaction unit
The mol ratio of middle ferro element is controlled to 1: 5~5: 1, the molal quantity of the glycine and foregoing Zn-ef ficiency, the total moles of ferro element
The ratio between number is 1: 1~2.2: 1；After stirring, after whole-process control reaction temperature and pH value, fully reaction completely, blowing cooling
Crystallization, separation, wash crystallization thing dry, pulverize sieving, obtains finished product ferrous glycine Zn complex.
In the technical scheme of the invention described above, our experiments by substantial amounts of theoretical research and repeatedly are groped, and are summed up
Ferrous bisglycinate chelate and glycine zine can obtain the product and steady quality of a kind of crystal formation by crystallization simultaneously under specific ratio, and and
Different contribution ratios of the animal to ferrous and zinc are turned round and look at, it is determined that the rate of charge of reaction raw materials in the present invention.By chemical means
Iron, zinc and glycine are combined together according to specific ratio and solve that residual inorganic salts, ligand be unstable, anti-nutrition because
The problems such as influence of son；We design the ferrous glycine Zn complex of optimal proportions according to the different physiological condition of animal, so that
Make that iron, zinc are stable in animal body to remain iron zinc optimal absorption ratio, suppress and animal body so as to avoid competition and absorb
The problem of metabolic imbalance caused by the interior imbalance due to ratio, is imitated with preferably playing iron zinc biology in animal body
Valency.
In above-mentioned preparation method, preferably：It is described to adding glycine, zinc raw material, ferrous salt and molten in reaction unit
During agent, first add glycine, zinc raw material, ferrous salt and be well mixed, then add solvent.Thrown again by being first well mixed raw material
Material, can better assure that the product of two kinds of reaction generations is generated according to certain ratio, be conducive to regulating and controlling the component in product
Content.
In above-mentioned preparation method, preferably：It is described to adding glycine, zinc raw material, ferrous salt and molten in reaction unit
During agent, first to solvent is added in reaction unit, stirring is opened, then putting into zinc raw material and ferrous salt, then put into glycine makes it
With foregoing zinc raw material and ferrous reactant salt.
In above-mentioned preparation method, it is contemplated that the ferrous glycine Zn complex product for preparing is mainly used in feed,
Therefore its product will not only meet general target level of product quality, also meet sanitary standard.We sieve to raw material first
Choosing, to determine not existing the pollution sources for endangering animal health in raw material, secondly we can avoid generation new in preparation process
Harmfulness impurity, can finally remove most impurity present in raw material in preparation and purge process.Based on such think of
Think, preferred glycine be glycine of the purity more than 98%, by we detection and analyze repeatedly, these purity are higher
Glycine not only tenor is all extremely low, and Polychlorinated biphenyls, bioxin etc. is larger to harm in product has containing benzene
Machine thing content very little.More preferably：The zinc raw material is zinc sulfate, basic zinc salt, zinc chloride or zinc oxide, the ferrous salt
It is ferrous sulfate or frerrous chloride.These raw materials can be anhydrous compound or the compound with the crystallization water.
In above-mentioned preparation method, preferably：The solvent is water or water-organic solvent mixed system, more preferably water-have
Machine solvent mixed system.Organic solvent in the water-organic solvent mixed system is methyl alcohol, ethanol, acetone, propyl alcohol, second two
At least one in alcohol, glycerine, ethyl acetate, butanone；The water-organic solvent mixed system reclaimed water and organic solvent volume
Than being 1: 5~5: 1.The solvent is usually disposably to be added in reaction system.Preferred water in reaction system of the present invention-have
Machine solvent mixed system has the advantage that：1. organic solvent dissolved oxygen is relatively low, can avoid ferrous oxidation；2. zinc raw material,
Solubility is lower than water in organic solvent for ferrous salt, by controlling the ratio of water-organic solvent mixed system, can indirect control it is anti-
Answer speed and crystalline rate and crystal formation；3. the boiling point of organic solvent is relatively low, volatile, contributes to material to accelerate rate of drying, and
Making the space of storeroom increases, and keeps the fluffy degree of material, prevents hardened and false conglomeration.
In above-mentioned preparation method, preferably：A closed reaction cavity volume, the reaction can be formed in the reaction unit
Cavity volume includes interior room and mistress, and interior room and mistress are separated by a pellicle, is respectively equipped with the interior room and mistress interior
Room dog-house and mistress's dog-house；Agitating device, attemperating unit and pH value self-con-tained unit are additionally provided with the reaction cavity volume, it is described
Alkali lye is previously added in pH value self-con-tained unit, alkali lye can be added dropwise by the pH value determined in reaction at any time, reach whole-process control pH
The purpose of value.Employ membrane separation technique in above-mentioned preferred reaction unit, the major advantage of nanofiltration UF membrane is except can
Isolated outside bigger molecule with from technological process, moreover it is possible to from solution extract solute and purified, so as to reach purification and
The purpose of product is reclaimed, the purity and quality of product is greatly improved, this is used as the safety wind of feed addictive for reducing product
Danger is also significant.
In above-mentioned preparation method, more preferably：The interior room is surrounded by the mistress, and the agitating device is arranged at
In interior room, the pH value self-con-tained unit is communicated in mistress.During the course of the reaction, agitating device can not only control local reaction
Temperature, the reaction uniformity and reaction speed, the sweet ammonia that will can also be constantly generated near pellicle by the effect of current
Sour ferrous and glycine zine molecule prevents ferrous bisglycinate chelate and glycine zine from being deposited on pellicle and blocks half away from pellicle
Permeable membrane space；In crystallization process, because agitating device is located at interior room, mistress has flow action but will not produce vortex etc. no
Beneficial to the factor of crystallization, the purpose of uniform settlement crystallization can be reached.
In above-mentioned preparation method, more preferably：The pellicle is removably fixed on the cylinder of reaction unit
On this body support frame；The pellicle is preferably cellulose acetate composite film, aromatic polyamide membrane, PPSU terephthalamide
One kind in film, polybenzimidazole membrane, sulfonated poly (phenylene oxide) film, sulfonated polysulfone membrane, polytetrafluoroethylene (PTFE) graft copolymer membrane.The pellicle
Aperture is preferably 100-200pm.
In above-mentioned preparation method, more preferably：The feed postition of the solvent be it is following two in any one, more
2. preferably following plant mode：
1. to solvent is added in the interior room dog-house or mistress's dog-house, stand to the osmotic balance of inside and outside room；
2. to solvent is separately added into the interior room dog-house and mistress's dog-house, the infiltration stood to inside and outside room is flattened
Weighing apparatus.
In above-mentioned preparation method, it is furthermore preferred that the glycine, zinc raw material, the feed way of ferrous salt are：Described
Interior room dog-house puts into zinc raw material and ferrous salt, and putting into glycine again in mistress's dog-house makes it with foregoing zinc raw material and Asia
Molysite reacts, and finally closes interior room dog-house and mistress's dog-house.The interior room dog-house and mistress's dog-house are formula able to turn on or off,
Closed environment can be formed by closing inside and outside room dog-house in course of reaction, reach the purpose of insulation, starvation；In reaction
After the completion of crystallisation by cooling during, closed environment can realize uniform decrease in temperature, and extraneous interference is preferably minimized, and it also avoid two
Valency iron problem of oxidation.
In above-mentioned preparation method, it is preferred that the attemperating unit includes temp probe and heating in interior room
Component, the heating component is mainly made up of the chuck layer for being coated on the mistress, and hot water or vapours are led in the chuck layer
Heated.It is furthermore preferred that the course of reaction and crystallisation by cooling process are in the closed reaction cavity volume of the reaction unit
Carry out, leading to hot water or vapours in chuck layer in the course of reaction is uniformly heated, during the crystallisation by cooling
Cooling water is passed through in chuck layer carries out uniform decrease in temperature.Sampling valve collection after crystallisation by cooling by opening reaction unit bottom has been tied
Ferrous glycine Zn complex product that is brilliant and being deposited in reaction unit bottom.Crystallized product is deposited in reactor bottom, can pass through
The crystal formation and crystallization situation of take-off valve sampling observation product, are discharged, it is to avoid the labour intensity of material is dug after crystallization by baiting valve.
In above-mentioned preparation method, it is preferred that the reaction whole-process control reaction temperature is 20 DEG C~65 DEG C, control reaction
The pH value of system is 3.0-7.0 (more preferably 5-7)；Feed intake and solid contain (more solid containing than for without the crystallization water than being about 10%~50%
Raw material accounts for the mass ratio of raw material and solvent sum)；It is 15min~5h to control the reaction time.Our experiments repeatedly show,
The foregoing preferable Parameter Conditions to generate ferrous glycine Zn complex, if pH value is too high or under alkaline environment, ferrous iron is very
Easily with the oxidation material reaction generation ferric iron in water, cause product to turn yellow, have a strong impact on product appearance and quality；While this
Also the pH value ferrous with preferred raw material sulphuric acid in our productions is adaptable.
Compared with prior art, the advantage of the invention is that：
(1) present invention is based on ferrous bisglycinate chelate is similar with the physicochemical property of glycine zine, can use same synthesis technique
On the premise of, by multiple repetition test, it is found that ferrous bisglycinate chelate and glycine zine can be with ferrous glycine zinc under special ratios
Out, glycine zine and the spatially interleaved arrangement of ferrous bisglycinate chelate, solve actual production to complex co-crystallization in crystal
Three big technical barriers in process：1. ferrous glycine Zn complex considerably reduces ferrous bisglycinate chelate exposure in atmosphere
Position, ferrous bisglycinate chelate is chronically exposed in air the ferrous ferric iron that is easily oxidized to causes discoloration and utilization rate low；2. solve
Determine glycine zine product bad dispersibility, viscosity higher, easy moisture absorption caking, the problem that is not easy to Product processing and storage；3. originally
Ferrous bisglycinate chelate and glycine zine are evenly distributed and constitute an entirety in the ferrous glycine Zn complex of invention, compared to tradition
Ferrous bisglycinate chelate and glycine zine mixture, its mixture homogeneity is high, and the step for reduce dispensing and mix, reduces
Production cost and labour intensity, while huge noise and dust in it also avoid mixed process, improve employee's production operation
Environment, it is also more environmentally-friendly.
(2) interior room and mistress are separated using pellicle creatively in reaction unit of the invention, with advantages below：
1. reaction speed is controlled：Zinc raw material, ferrous salt and glycine are separately fed intake, glycine cannot pass through because of the relation of steric hindrance
Pellicle enters interior room, and zinc raw material and ferrous salt can enter into mistress by pellicle in the form of an ion；Stirred by adjusting
The speed of device, control osmotic pressure and solution ion concentration in itself is reached inorganic zinc raw material and ferrous salt and is at the uniform velocity spread with close
Mode reacted with glycine through pellicle.2. pellicle has filtration, can suitably reduce starting material inorganic ferrous
The purity of salt and zinc raw material, expands buying scope, reduces raw material supply shortage risk and reduces cost of material；Inorganic zinc raw material and ferrous iron
Salt because the influence of different production technologies exist the heavy metals such as different impurity, such as insoluble matter, lead, bismuth, thallium and Polychlorinated biphenyls,
Poisonous and harmful larger molecular organicses such as bioxin etc., have a strong impact on purity, security and the crystal formation homogeneity of subsequent product.Will be
Inorganic zinc raw material and ferrous salt put into from interior room dog-house, and under agitation, inorganic zinc raw material and ferrous salt are with ionic condition
Mistress is reached by pellicle, plays a part of a membrane filtration removal of impurities purification.
(3) after well mixed zinc raw material and ferrous salt put into solvent, can simultaneously dissolve and discharge zinc ion and Asia
Iron ion, is reacted through pellicle together with the current produced by stirring with the glycine outside film, while generation is certain
The glycine zine and ferrous bisglycinate chelate of ratio, and form the crystallite with certain space structure.During crystallisation by cooling, glycine zine and
Ferrous bisglycinate chelate can according to a certain percentage form mixed crystal, mutually coating, it is to avoid ferrous bisglycinate chelate is aoxidized in being excessively exposed to air.
If local zinc raw material and ferrous salt ratio are inconsistent, the glycine zine and ferrous bisglycinate chelate of different proportion can be generated, crystallite
Space structure is different, and the mixed crystal of formation is also different, eventually influences the quality of product.
(4) after last consignment of ferrous glycine Zn complex blowing of the present invention is finished, appropriate solvent can be supplemented, is put into again former
Material reaction, can carry out serialization large-scale production, it is not necessary to rejoin solvent, simplify production stage, reduce labour intensity, drop
Low production cost, improves production environment, improve production efficiency.The purity regarding raw material is only needed, periodic replacement pellicle and cleaning are anti-
Answer kettle.
(5) ferrous glycine Zn complex obtained in the inventive method, be by chemical means by iron, zinc and glycine according to
Specific ratio is combined together, and solves the problems such as residual inorganic salts, unstable ligand, ANFs influence, this
Not only processing step is simple for the preparation method of invention, low cost, environmental protection, and product grain is uniform, good dispersion, easily
Dry, product purity is high, steady quality, not easy to change in production and process；Cooling obtains mixed crystal, appearance after the completion of reaction
It is good, it is more beneficial for promoting the market sale of product, and product structure composition is detectable, product quality is easily-controllable.
(6) present invention can according to animal it is different physiological condition design optimal proportions ferrous glycine Zn complex so that
Iron, zinc stably remain iron zinc optimal absorption ratio in animal body, are absorbed in suppression and animal body so as to avoid competition
Due to the problem of metabolic imbalance caused by ratio imbalance, so as to preferably play iron zinc biology effect in animal body
Valency.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the structural representation of reaction unit used in the embodiment of the present invention 5,6.
Fig. 2 is the XRD diffracting spectrums of preparation-obtained ferrous glycine Zn complex in the embodiment of the present invention 2.
Fig. 3 is the XRD diffracting spectrums of preparation-obtained ferrous glycine Zn complex in the embodiment of the present invention 4.
Fig. 4 is the XRD diffracting spectrums 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 --- agitating device；
4 --- interior room dog-house；
5 --- mistress's dog-house；
6 --- mistress；
7 --- pellicle；
8 --- interior room；
9 --- chuck layer；
10 --- baiting valve；
11 --- sampling valve.
Specific embodiment
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can be by city
Field is commercially available or can be prepared by existing method.The raw material being below related to is commercial diet level.
Embodiment 1：
A kind of preparation method that can be used for the ferrous glycine Zn complex of animal feed additive of the invention, including it is following
Step：
Weigh glycine, the ferrous sulfate heptahydrate that 143.5g purity is 97%, 29.6g purity that 50.5g purity is 98%
White vitriol for 97% puts into reactor, and Zn-ef ficiency rubs with ferro element in ferrous sulfate heptahydrate in white vitriol
You are for about 1: 5 than control, and the molal quantity of glycine and the ratio between foregoing Zn-ef ficiency, the total mole number of ferro element are about 1.1: 1, then
Stir, add 300mL water, regulation reaction temperature is 20 DEG C, and regulation pH value in reaction is 3.0, stirring reaction 15 minutes, cooling
Centrifugation after stirring and crystallizing, wash crystallization thing, vacuum drying pulverizes and sieves, and obtains ferrous glycine Zn complex 183.0g.
By Fe in the ferrous glycine Zn complex that detection and analysis, the present embodiment are obtained2+Content is 13.9%, Fe3+Content
It is 0.1%, Zn2+Content is 3.3%, SO4 2-Content is 28.5%, and total Glycine Levels are 22.1%, and product is at 280 DEG C
Percentage of water loss is 26.5%.That is Fe2+∶Zn2+=5: 1, NH2CH2COO-∶(Fe2++Zn2+)=1: 1, products molecule formula is：
ZnFe5(NH2CH2COO-)6(SO4)6·30H2O, yield is 91%, and purity is 97%.
The percentage of water loss at 280 DEG C in above-mentioned analysis method：By repetitious experimental verification, find product 280
Constant weight after 3h is dried in DEG C baking oven, finds that its volatile substances is the crystallization water contained in product after testing, and all wave
Hair (following examples are identical with this).
Embodiment 2：
A kind of preparation method that can be used for the ferrous glycine Zn complex of animal feed additive of the invention, including it is following
Step：
Weigh glycine, the ferrous sulfate monohydrate that 56.1kg purity is 91%, 38.1kg that 38.3kg purity is 98% pure
The monohydrate zinc sulphate spent for 94% is put into reactor, Zn-ef ficiency and ferro element in ferrous sulfate monohydrate in monohydrate zinc sulphate
Mol ratio control is for about 2: 3, and the molal quantity of glycine and the ratio between foregoing Zn-ef ficiency, the total mole number of ferro element are about 1: 1, then
Stir, add water-ethyl acetate mixed solvent (water: ethyl acetate volume ratio is 1: 2) 120kg, regulation reaction temperature is
45 DEG C, regulation pH value in reaction is 4.5, stirring reaction 45 minutes, centrifugation after cooling and stirring crystallization, wash crystallization thing, vacuum
Sieving is dry, pulverize, ferrous glycine Zn complex 153.7kg is obtained.
By Fe in the ferrous glycine Zn complex that detection and analysis, the present embodiment are obtained2+Content is 10.1%, Fe3+Content
It is 0.1%, Zn2+Content is 7.8%, SO4 2-Content is 29.1%, and total Glycine Levels are 22.7%, the XRD diffraction patterns of product
Spectrum is as shown in Fig. 2 percentage of water loss of the product at 280 DEG C is 27.2%.That is Fe2+∶Zn2+=3: 2, NH2CH2COO-∶(Fe2++Zn2+)
=1: 1, products molecule formula is：Zn2Fe3(NH2CH2COO-)5(SO4)5·25H2O, yield is 93%, and purity is 97%.
Embodiment 3：
A kind of preparation method that can be used for the ferrous glycine Zn complex of animal feed additive of the invention, including it is following
Step：
Weighing glycine, the frerrous chloride that 14.0kg purity is 91%, 70.1kg purity that 48.3kg purity is 98% is
97% zinc chloride is put into reactor, and Zn-ef ficiency and the mol ratio control of ferro element in frerrous chloride are for about 5 in zinc chloride:
1, the molal quantity of glycine and the ratio between foregoing Zn-ef ficiency, the total mole number of ferro element are about 1.05: 1, then stir, and add
Water-ethanol mixed solvent (water: ethanol volume ratio is 5: 1) 200Kg, regulation reaction temperature is 35 DEG C, and regulation pH value in reaction is
5.0, stirring reaction 50 minutes, centrifugation after cooling and stirring crystallization, wash crystallization thing, vacuum drying pulverizes and sieves, and obtains sweet
Propylhomoserin iron Zn complex 166.1kg.
By Fe in the ferrous glycine Zn complex that detection and analysis, the present embodiment are obtained2+Content is 2.9%, Fe3+Content
It is 0.1%, Zn2+Content is 17.4%, Cl-Content is 22.8%, and total Glycine Levels are 23.8%, and product is at 280 DEG C
Percentage of water loss is：29.5%.That is Fe2+∶Zn2+=1: 5, NH2CH2COO-∶(Fe2++Zn2+)=1: 1, products molecule formula is：
Zn5Fe(NH2CH2COO-)6Cl12·30H2O, yield is 89%, and purity is 96%.
Embodiment 4：
A kind of preparation method that can be used for the ferrous glycine Zn complex of animal feed additive of the invention, including it is following
Step：
Weigh glycine, the ferrous sulfate monohydrate that 37.4kg purity is 91%, 55.0kg that 38.6kg purity is 98% pure
The monohydrate zinc sulphate spent for 98% is put into reactor, Zn-ef ficiency and ferro element in ferrous sulfate monohydrate in monohydrate zinc sulphate
Mol ratio control is for about 3: 2, and the molal quantity of glycine and the ratio between foregoing Zn-ef ficiency, the total mole number of ferro element are about 1: 1, then
Stir, add boiling mixed solvent (water: methyl alcohol volume ratio is 4: 1) 485Kg, regulation reaction temperature is 40 DEG C, regulation
PH value in reaction is 7.0, stirring reaction 1h, centrifugation after cooling and stirring crystallization, wash crystallization thing, vacuum drying, is pulverized and sieved,
Obtain ferrous glycine Zn complex 152.5kg.
By Fe in the ferrous glycine Zn complex that detection and analysis, the present embodiment are obtained2+Content is 6.6%, Fe3+Content
It is 0.2%, Zn2+Content is 11.7%, SO4 2-Content is 28.9%, and total Glycine Levels are 22.5%, the XRD diffraction patterns of product
Spectrum is as shown in figure 3, percentage of water loss of the product at 280 DEG C is 27.5%.That is Fe2+∶Zn2+=2: 3, NH2CH2COO-∶(Fe2++Zn2+)
=1: 1, products molecule formula is：Zn3Fe2(NH2CH2COO-)5(SO4)5·25H2O, yield is 92%, and purity is 97%.
Embodiment 5：
A kind of reaction unit as shown in Figure 1, can form a closed reaction cavity volume (about 1m in reaction unit3Left and right),
Reaction cavity volume includes interior room 8 and mistress 6, and interior room 8 and mistress 6 are separated by a pellicle 7, in interior room 8 and mistress 6 respectively
It is provided with interior room dog-house 4 and mistress's dog-house 5；Agitating device 3, attemperating unit and pH value self-con-tained unit are additionally provided with reaction cavity volume
1, alkali lye is previously added in pH value self-con-tained unit 1, alkali lye can be added dropwise by the pH value determined in reaction at any time, reach whole-process control
The purpose of pH value.
In the reaction unit of the present embodiment, interior room 8 is surrounded by mistress 6, and agitating device 3 is arranged in interior room 8, and pH value is certainly
Control device 1 is communicated in mistress 6.During the course of the reaction, agitating device 3 can not only control local reaction temperature, reaction uniform
Degree and reaction speed, the ferrous bisglycinate chelate and sweet ammonia that will can also be constantly generated near pellicle 7 by the effect of current
Sour zinc molecule prevents ferrous bisglycinate chelate and glycine zine from being deposited on pellicle 7 and blocking pellicle space away from pellicle；
In crystallization process, because agitating device 3 is located at interior room 8, mistress 6 has flow action but vortex etc. will not be produced to be unfavorable for crystallization
Factor, can reach uniform settlement crystallization purpose.The pellicle 7 of the present embodiment is removably fixed on reaction unit
On cylindrical body support；Pellicle 7 is polytetrafluoroethylene (PTFE) graft copolymer membrane, and the aperture of pellicle is 100-200pm.
Interior room dog-house 4 and mistress's dog-house 5 in the present embodiment are formula able to turn on or off, can be by closing in course of reaction
Inside and outside room dog-house forms closed environment, reaches the purpose of insulation, starvation；Crystallisation by cooling process after completion of the reaction
In, closed environment can realize uniform decrease in temperature, and extraneous interference is preferably minimized, and it also avoid ferrous oxidising problem.
The attemperating unit of the present embodiment includes temp probe 2 and heating component in interior room 8, and heating component is main
It is made up of the chuck layer 9 for being coated on mistress 6, leads to hot water in chuck layer 9 or vapours is heated.
Prepared using the reaction unit of above-mentioned the present embodiment and can be used for the ferrous glycine Zn complex of animal feed additive,
Specifically include following steps：
Added water simultaneously in mistress's dog-house 5 and interior room dog-house 4 of reaction unit, 0.4 ton altogether, stand 15min, opened
Agitating device 3 is opened, the monohydrate zinc sulphate 18.3kg that purity is 98% and the seven water sulphur that purity is 98% are put into interior room dog-house 4
Sour ferrous iron 28.4kg, the glycine 15.4kg of 98% purity, Zn-ef ficiency and seven water in monohydrate zinc sulphate are put into mistress's dog-house 5
The mol ratio control for about 1: 1 of ferro element, the molal quantity of glycine and foregoing Zn-ef ficiency, the total moles of ferro element in ferrous sulfate
The ratio between number about 1: 1, is then shut off interior room dog-house 4 and mistress's dog-house 5, opens pH value self-con-tained unit 1, whole-process control reaction
Temperature is 65 DEG C, and pH value is 7.0, and after reaction 3h, cooling and stirring to the uniform crystallization of room temperature, crystallized product is deposited in reaction unit bottom
Portion, every 20min from the sampling of sampling valve 11 observation crystal formation and crystallization situation to there is no the generation of new crystal, by the row of baiting valve 10
Go out, collect crystal and wash 3 times, expansion drying crushed 40 mesh sieves and obtains finished product ferrous glycine Zn complex 59.5kg.This
The course of reaction and crystallisation by cooling process of embodiment are carried out in the closed reaction cavity volume of reaction unit, in folder in course of reaction
Lead to vapours in jacket layer 9 uniformly to be heated, being passed through cooling water in chuck layer 9 during crystallisation by cooling carries out uniform decrease in temperature.
After crystallisation by cooling the sweet ammonia for having crystallized and being deposited in reaction unit bottom is collected by opening the sampling valve 11 of reaction unit bottom
Sour iron Zn complex product.
By Fe in detection and analysis ferrous glycine Zn complex2+Content is 8.6%, Fe3+Content ＜ 0.05%, Zn2+Content
It is 10.0%, SO4 2-Content is 29.5%, and total Glycine Levels are 22.9%, and the XRD diffracting spectrums of product are as shown in figure 4, produce
Percentage of water loss of the product at 280 DEG C be：27.6%.That is Fe2+∶Zn2+=1: 1, NH2CH2COO-∶(Fe2++Zn2+)=1: 1, product point
Minor is：ZnFe(NH2CH2COO-)2(SO4)2·10H2O, yield is 92%, and purity is 99%.
Embodiment 6：
The present embodiment equally using reaction unit as shown in Figure 1 in embodiment 5, is prepared using the reaction unit and can be used for
The ferrous glycine Zn complex of animal feed additive, specifically includes following steps：
To in mistress's dog-house 5 and interior room dog-house 4 of reaction unit simultaneously plus water-ethylene glycol mixed solvent (volume ratio 1
: 5), 0.3 ton altogether, 15min is stood, open agitating device 3, in the zinc oxide that the input purity of interior room dog-house 4 is 91%
8.9kg and purity are 88% frerrous chloride 72.2kg, and the glycine 101.1kg of 98% purity, oxygen are put into mistress's dog-house 5
The mol ratio control for changing ferro element in Zn-ef ficiency and frerrous chloride in zinc is for about 1: 5, the molal quantity of glycine and foregoing Zn-ef ficiency,
The ratio between total mole number of ferro element about 2.2: 1, is then shut off interior room dog-house 4 and mistress's dog-house 5, opens pH value automatic control dress
1 is put, whole-process control reaction temperature is 65 DEG C, and pH value is 5.0, after reaction 5h, cooling and stirring to the uniform crystallization of room temperature, crystallized product
Reaction unit bottom is deposited in, every 20min from the sampling of sampling valve 11 observation crystal formation and crystallization situation to there is no the life of new crystal
Into, discharged by baiting valve 10, to collect crystal and simultaneously wash 3 times, expansion drying, excessively 40 mesh sieves obtain finished product ferrous glycine zinc and match somebody with somebody
Compound 130.3kg.The course of reaction and crystallisation by cooling process of the present embodiment are carried out in the closed reaction cavity volume of reaction unit,
Lead to vapours in chuck layer 9 in course of reaction uniformly to be heated, cooling water is passed through in chuck layer 9 during crystallisation by cooling
Carry out uniform decrease in temperature.After crystallisation by cooling by open the sampling valve 11 of reaction unit bottom collect crystallized and be deposited in reaction dress
The ferrous glycine Zn complex product in bottom set portion.
By Fe in detection and analysis ferrous glycine Zn complex2+Content is 19.1%, Fe3+Content ＜ 0.05%, Zn2+Contain
It is 4.5% to measure, and total Glycine Levels are 60.6%, and percentage of water loss of the product at 280 DEG C is：14.6%.That is Fe2+∶Zn2+=5:
1, NH2CH2COO-∶(Fe2++Zn2+)=2: 1, products molecule formula is：ZnFe5(NH2CH2COO-)12·12H2O, yield is 89%,
Purity is 99%.
Claims (8)
1. a kind of preparation method that can be used for the ferrous glycine Zn complex of animal feed additive, comprises the following steps：
To addition glycine, zinc raw material, ferrous salt and solvent in reaction unit, Zn-ef ficiency and iron in ferrous salt in the zinc raw material
The mol ratio of element is controlled to 1: 5~5: 1, the molal quantity of the glycine and foregoing Zn-ef ficiency, ferro element total mole number it
Than being 1: 1~2.2: 1；After stirring, after whole-process control reaction temperature and pH value, fully reaction completely, blowing crystallisation by cooling,
Separate, wash crystallization thing dry, pulverize sieving, obtain finished product ferrous glycine Zn complex；
A closed reaction cavity volume can be formed in the reaction unit, the reaction cavity volume includes interior room（8）And mistress（6）, and
Interior room（8）And mistress（6）By a pellicle（7）Separate, the interior room（8）And mistress（6）On be respectively equipped with interior room and feed intake
Mouthful（4）With mistress's dog-house（5）；Agitating device is additionally provided with the reaction cavity volume（3）, attemperating unit and pH value self-con-tained unit
（1）；
The feed postition of the solvent be it is following two in any one：
1. to the interior room dog-house（4）Or mistress's dog-house（5）Middle addition solvent, stands to the osmotic balance of inside and outside room；
2. to the interior room dog-house（4）With mistress's dog-house（5）In be separately added into solvent, stand to the osmotic pressure of inside and outside room
Balance；
The glycine, zinc raw material, the feed way of ferrous salt are：In the interior room dog-house（4）Input zinc raw material and ferrous iron
Salt, in mistress's dog-house（5）Putting into glycine again makes it with foregoing zinc raw material and ferrous reactant salt；The interior room dog-house
（4）With mistress's dog-house（5）It is formula able to turn on or off.
2. preparation method according to claim 1, it is characterised in that：It is described former to addition glycine, zinc in reaction unit
When material, ferrous salt and solvent, first add glycine, zinc raw material, ferrous salt and be well mixed, then add solvent.
3. preparation method according to claim 1, it is characterised in that：It is described former to addition glycine, zinc in reaction unit
When material, ferrous salt and solvent, first to solvent is added in reaction unit, stirring is opened, then put into zinc raw material and ferrous salt, then throw
Entering glycine makes it with foregoing zinc raw material and ferrous reactant salt.
4. the preparation method according to claim 1,2 or 3, it is characterised in that：The zinc raw material is zinc sulfate, basic zinc
Class, zinc chloride or zinc oxide, the ferrous salt are ferrous sulfate or frerrous chloride；The solvent is that water or water-organic solvent are mixed
Zoarium system；Organic solvent in the water-organic solvent mixed system is methyl alcohol, ethanol, acetone, propyl alcohol, ethylene glycol, the third three
At least one in alcohol, ethyl acetate, butanone；The water-organic solvent mixed system reclaimed water is 1: 5 with organic solvent volume ratio
~5: 1.
5. the preparation method according to claim 1,2 or 3, it is characterised in that：The interior room（8）By the mistress（6）Bag
Enclose, and the agitating device（3）It is arranged at interior room（8）In, the pH value self-con-tained unit（1）It is communicated in mistress（6）In；Described half
Permeable membrane（7）Removably it is fixed on this body support frame of reaction unit；The pellicle（7）For cellulose acetate composite film,
Aromatic polyamide membrane, PPSU terephthalamide film, polybenzimidazole membrane, sulfonated poly (phenylene oxide) film, sulfonated polysulfone membrane, polytetrafluoro
One kind in Vinyl Graft film.
6. the preparation method according to claim 1,2 or 3, it is characterised in that：The attemperating unit includes being located at interior room（8）
In temp probe（2）And heating component, the heating component is mainly by being coated on the mistress（6）Chuck layer（9）Structure
Into the chuck layer（9）In lead to hot water or vapours and heated.
7. preparation method according to claim 6, it is characterised in that：The course of reaction and crystallisation by cooling process are in institute
State and carry out in the closed reaction cavity volume of reaction unit, in chuck layer in the course of reaction（9）In lead to hot water or vapours and carry out
Uniform heating, in chuck layer during the crystallisation by cooling（9）In be passed through cooling water and carry out uniform decrease in temperature.
8. the preparation method according to claim 1,2 or 3, it is characterised in that：It is described reaction whole-process control reaction temperature be
20 DEG C~65 DEG C, the pH value for controlling reaction system is 3.0-7.0；It is 15min~5h to control the reaction time.
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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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