CN101139300A - Method for preparing copper zinc aminoacetic acid complex by grinding solid phase - Google Patents
Method for preparing copper zinc aminoacetic acid complex by grinding solid phase Download PDFInfo
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- CN101139300A CN101139300A CNA2007100301225A CN200710030122A CN101139300A CN 101139300 A CN101139300 A CN 101139300A CN A2007100301225 A CNA2007100301225 A CN A2007100301225A CN 200710030122 A CN200710030122 A CN 200710030122A CN 101139300 A CN101139300 A CN 101139300A
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Abstract
The present invention is a method of preparing the copper, zinc glycine complex with the milling solid phase. The steps of the preparation are as follows: the glycine and the copper, zinc metal compound are mixed in the mortar at the room temperature; the mixture is milled for 15 to 30 minutes; the glycine and the copper, zinc metal compound do the chemical reaction; the mixture is continually milled for 40 to 80 minutes until the reaction is complete; the ethanol of 75 percent is used for washing the product twice; the product is then dried first at the room temperature and then fully dried at the temperature of 80 DEG C. The present invention has the simple process, the short reaction time, the high production and the low energy consumption; the method can not only effectively avoid the hard agglomeration of the products, but also have no use of the solvent the small environmental pollution. Besides, the content of copper and zinc is relatively high; the results are safe and reliable. The invention realizes the production of the copper and zinc glycine complex of the low cost and is the real green chemical reaction.
Description
Technical field
The present invention relates to the synthetic making field of amino acids metal title complex, be specially a kind of method of grinding solid phase preparation copper, zinc aminoacetic acid complex.
Background technology
Copper, zinc are the essential trace elements of animal such as human body and poultry and livestock, and they are present in humans and animals with the form of protein and metalloenzyme, have accelerating growth and grow, and improve the sense of taste, adjusting body, immunity, protect from infection and promote functions such as wound healing.Therefore should add copper and zinc in the feed for the animal normal growth.For a long time, trace element such as zinc, copper all makes an addition in the mixed feed with the form of vitriol, the existence of sulfate radical not only easily causes burn into to influence vitamins stability to feed-processing equipment, and even more serious is the health that can influence animal intestinal after a large amount of sulfate radicals is absorbed by animal.
In order to overcome the deficiency that inorganic microelement exists in the fodder additives, organising of trace element is the trend of mineral additive development, and the use of humatite matter trace element in recent years constantly increases.Humatite matter trace element also can improve the immunizing power of animal except biological value is higher, organism can significantly improve vitamins stability than common inorganic microelement in Preblend.
The chemical stability of trace element aminoacetic acid complex is moderate; glycine shields to metal ion; can prevent that trace element from forming insoluble compound or be attracted on the insoluble colloid that hinders element absorption in enteron aisle; be both bivalent ions trace element and calcium the competition sorption is arranged; the external micro-aminoacetic acid complex of complexing in advance then can be warded off the approach of digesting and assimilating in addition, and efficient is heightened.Simultaneously, also prevent the bad interference of antinutritional factor such as phytic acid contained in the natural feed, oxalic acid, tannic acid to a considerable extent, therefore helped the absorption of body.
Glycine can convert multiple important active substance and other humans and animals essential amino acid in vivo to simultaneously, also has effects such as buffering, relieving haperacidity, is used for the treatment of hyperchlorhydria etc.Because the peculiar physiological function of amino acid, the title complex of it and copper, zinc, along with animal to amino acid whose absorption, copper, zinc also are absorbed, and can produce the synergy that helps animal, both have good coordination, and zinc glycinate helps the active absorption of small intestine, external glycine and copper, zinc is combined into stable glycocoll-copper, zinc glycinate, can not be subjected to the influence of things other factors, overall absorption has certain germicidal action and suitable trophism.Can be used as ideal nutrition-fortifying agent and fodder additives.
The trace element amino acid coordination compound has been obtained effect preferably as fodder additives.It is reported that the micro-aminoacetic acid complex of feeding is to the weightening finish of chicken, laying rate and improving food conversion ratio etc. has effect preferably.Generally speaking micro-amino acid coordination compound major function and purposes are as follows: (1) is satisfied the animal needs and is promoted growth of animal, improves amino acid balance, improves efficiency of feed utilization, saves protein resource; (2) nutritive value of raising plant protein and feed thereof helps developing protein feed resource; (3) improve the quality of meat: add Methionin in the feed and can improve the corpse quality, improve lean ratio, and improve chick and the proteinic deposition of broiler, reduce fatty deposits; (4) absorption of promotion calcium; (5) can resist stress disease; (6) disease resistance enhancemen; (7) prevent animal diarrhoea; (8) can lure the shoal of fish and as seasonings.In a word, a certain amount of micro-amino acid coordination compound fodder additives can stimulate certain biological procedures, more is of value to body growth.
Therefore, the synthetic of glycocoll-copper, zinc will have great importance to China's feed advance, and the present situation that changes present animal-feed and the economic growth of China are played a driving role.At present no matter the synthetic method of glycocoll-copper, zinc is in China, and still in the world, electrolytic process, liquid phase synthesize, the balance each other method, scorification of mainly using waits synthetic.These traditional chemical synthesis process carry out in solution or in the gas phase often, and are long and environmental pollution is serious, complex process, the high restriction of production cost are repelled more and more because of its energy consumption height, time.And meet energy-conservation, the solid-phase synthesis that requires of green production did not all disclose in patent documentation and relevant technical journal efficiently.
Summary of the invention
The objective of the invention is deficiency at the above copper, zinc aminoacetic acid complex making method, provide that a kind of technology is simple, the reaction times is short, the productive rate height, energy consumption is low, not only effectively avoided the hard aggregation phenomenon of product, and do not used solvent, environmental pollution is little, and copper, zinc content are higher relatively, and safe and reliable feed grade is ground the method for solid phase preparation copper, zinc aminoacetic acid complex.
The present invention is achieved in that the method for grinding solid phase preparation copper, zinc aminoacetic acid complex, preparation process is as follows: glycine and copper, zinc metallic compound are at room temperature mixed placing mortar, ground 15～30 minutes, glycine and copper, zinc metallic compound generation chemical reaction, continue to grind 40～80 minutes, until reacting completely; The washing reaction thing, final drying.
Described washing can be with 75% washing with alcohol product 2 times.
Described drying mode is prior to drying at room temperature, again in 80 ℃ of thorough dryings.
The mol ratio of described glycine and copper, zinc reaction is 2: 1.
It is as follows that described glycine and ventilation breather prepare the glycocoll-copper step: accurately take by weighing glycine and basic carbonate copper crystal, making its mol ratio is 2: 1, at room temperature mixes placing mortar to grind; Grind 20min, mix and grind the thing color and shoal, be light blue; Continue to be ground to 40min, the mixture color deepens gradually, is blue; When being ground to 60min, the blue pasty state of one-tenth uniformly afterreaction is complete; With 75% washing with alcohol product 2 times; Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
The step that described glycine and venus crystals prepare glycocoll-copper is as follows: accurately take by weighing glycine and venus crystals crystal, making its mol ratio is 2: 1, mixes placing agate mortar to grind under the room temperature; Grind 20min, mix and grind the thing color and shoal, be blue, and have pungency acetic acid smell to emit; Continue to be ground to 40min, the mixture color is a bluish voilet, and irritating smell is thin out; When being ground to 60min, it is complete can not heard acetic acid smell afterreaction; With 75% washing with alcohol product 2 times; Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
The step that described glycine and cupric chloride prepare glycocoll-copper is as follows: accurately take by weighing glycine and cupric chloride crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature; After grinding 20min, the mixture color is by the light blue green that becomes; Continue to be ground to 40min, have a large amount of moisture content to generate, it is complete that product is the grume afterreaction; With 75% washing with alcohol product 2 times; Dry: elder generation and drying at room temperature are 80 ℃ of thorough dryings.
The step that described glycine and zinc acetate prepare zinc glycinate is as follows: accurately take by weighing glycine and zinc acetate crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature; After grinding 20min, wherein there is pungency acetic acid smell to emit; Continue to be ground to 40min, irritating smell is thin out, and when being ground to 60min, it is complete can not heard acetic acid smell afterreaction; With 75% absolute ethanol washing product 2 times; Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
The step that described glycine and zinc sulfate prepare zinc glycinate is as follows: accurately take by weighing glycine and zinc sulfate crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature; After grinding 20min, become grume, have small amount of moisture to generate, be white in color; Continue to be ground to 40min, it is mixed; React completely when being ground to about 60min; With 75% washing with alcohol product 2 times; Dry: as, to fill a part drying in 80 ℃ again prior to drying at room temperature.
The method that the present invention grinds solid phase preparation copper, zinc aminoacetic acid complex is a raw material with copper, zn cpdss such as glycine and ventilation breather, venus crystals, zinc acetate, cupric chloride, zinc carbonates, adopts the synthetic glycocoll-copper of the solid phase method that grinds, Zn complex.Technology of the present invention is simple, and the reaction times is short, the productive rate height, and energy consumption is low, has not only effectively avoided the hard aggregation phenomenon of product, and has not used solvent, and environmental pollution is little, and copper, zinc content are higher relatively, and its result is safe and reliable.Realizing copper with low cost, the production of zinc aminoacetic acid complex fodder additives, is real Green Chemistry reaction.
Description of drawings
Fig. 1 grinds the infrared spectrogram of the glycocoll-copper (ventilation breather+glycine) of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Fig. 2 grinds the infrared spectrogram of the glycocoll-copper (venus crystals+glycine) of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Fig. 3 grinds the infrared spectrogram of the glycocoll-copper (cupric chloride+glycine) of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Fig. 4 grinds the infrared spectrogram of the zinc glycinate (zinc acetate+glycine) of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Fig. 5 grinds the infrared spectrogram of the zinc glycinate (zinc sulfate+glycine) of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Fig. 6 grinds the ownership table of each bands of a spectrum of aminoacetic acid complex of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Fig. 7 grinds the DTA and the GT graphic representation of the glycocoll-copper (ventilation breather+glycine) of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Fig. 8 grinds the DTA and the GT graphic representation of the glycocoll-copper (venus crystals+glycine) of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Fig. 9 grinds the DTA and the GT graphic representation of the glycocoll-copper (zinc acetate+glycine) of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Figure 10 grinds the DTA and the GT graphic representation of the glycocoll-copper (zinc sulfate+glycine) of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention;
Figure 11 grinds the aminoacetic acid complex thermogravimetric analysis table of the method for solid phase preparation copper, zinc aminoacetic acid complex for the present invention.
Figure 12 is that method Figure 12 of ball milling solid phase preparation copper of the present invention, zinc aminoacetic acid complex is that the daily ration of chicken test of the method for ball milling solid phase preparation copper of the present invention, zinc aminoacetic acid complex is formed and the nutritive index table;
Figure 13 is the chicken test-results table of the method for ball milling solid phase preparation copper of the present invention, zinc aminoacetic acid complex;
Figure 14 is the pig test-results table of the method for ball milling solid phase preparation copper of the present invention, zinc aminoacetic acid complex.
Embodiment
The present invention will be described in detail below in conjunction with the drawings and specific embodiments.
Reaction mechanism: room temperature is solid-the abundant contact that originates in two reactant molecules of solid state reaction.Chemical reaction then takes place, generate the product molecule, the product molecular dispersion after running up to a certain size, the nucleus of product occurs in parent, along with growing up of nucleus, reaches the independent crystal that occurs product after a certain size.Under the room temperature, grinding fully not only makes the solid particulate of reaction diminish with abundant contact, and provides the trace that promotes reaction to carry out to cause energy.Be that solid state reaction is divided four-stage: diffusion-reaction-nucleation-growth, per step all might be the deciding step of speed of reaction.
Reaction principle is:
4NH
2CH
2COOH+CuCO
3·Cu(OH)
2·H
2O→[Cu(NH
2CH
2COO)
2·H
2O]+3H
2O+CO
2↑
Preparation process is as follows: accurately take by weighing glycine and basic carbonate copper crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature.After grinding 20min, mix and grind the thing color and shoal, be light blue.Continue to be ground to 40min, the mixture color deepens gradually, is blue.When being ground to about 60min, evenly blue.Adhere on a small quantity on the wall, become pasty state.With 75% washing with alcohol product 2 times.Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
Products therefrom is carried out Infrared spectroscopy.Measure glycocoll-copper at 400～4000cm with the KBr pressed disc method
-1Infrared spectra.As shown in Figure 1, after glycine and cupric ion formed title complex, the main absorption peak of it some was compared with part obvious displacement has been taken place, and relative intensity also changes to some extent, thereby confirmed that coordination has taken place for bivalent cupric ion and glycine.Hydroxyl association peak dwindles, and this is because strengthened by the influence of other groups after the coordination, at 3100cm
-1About the peak move; 1432cm
-1Absorption peak belong to-CH
2-group.Glycine is at 2250cm
-1-NE
3+Characteristic peak completely dissolve in the IR of title complex spectrogram.3333cm
-1And 3264cm
-1The antisymmetric stretching vibration v that the N-H key occurred
As(N-H) and symmetrical stretching vibration v
s(N-H) charateristic avsorption band, coincidence formula vs=345.5+0.876vas between their frequency.At 1605cm
-1And 1389cm
-1The absorption peak that occurs is respectively the antisymmetric vibration v of carboxylic acid ion
As(COO-) and symmetrical stretching vibration v
s(COO-), move to lower wave number and high wave number respectively than part, its difference is the flexible v=216cm of Δ
-1, show that carboxylic acid ion participates in coordination with monodentate, exist in the molecule and join ring.1120cm
-1The 1127cm of v (C-N) peak and glycine has appearred in the place
-1Compare, wave number is low.At 558cm
- 1And 456cm
-1Have the stretching vibration peak of Cu-N and the stretching vibration peak of Cu-O respectively, this further specifies the formation that Diglycocol closes copper complex.
Products therefrom is carried out thermogravimetric-differential thermal analysis.In nitrogen protection, heat-up rate is 10 ℃ of .min
-1Measure the thermogravimetric-differential thermal spectrum of title complex by room temperature-900 ℃.The differential thermal of title complex-thermogravimetric analysis curve is seen Fig. 7.Cu (gly) H
2The thermolysis of O is divided into two stages: at first have an endotherm(ic)peak to lose a part water at 138 ℃, generate Cu (gly)., the TG curve table reveals 7.72% weightlessness, and is approaching with calculated value (7.84%), and an endotherm(ic)peak is arranged in the time of 255 ℃, for Cu (gly) decomposes, shows as 55.1% on the TG curve, approaching with calculated value (57.52%).Last residual volume is 37.1%, and its calculated value is (34.64%), and is identical substantially with measured value.We draw thus, and after ventilation breather and glycine solid phase synthesis glycine closed copper (II), heat decomposition temperature had risen to 255 ℃, the stability increase from 237 ℃.
Reaction principle is:
2NH
2CH
2COOH+Cu(Ac)
2·H
2O→[Cu(NH
2CH
2COO)
2·H
2O]+2HAc↑
Preparation process is as follows: accurately take by weighing glycine and venus crystals crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature.After grinding 20min, mix and grind the thing color and shoal, be blue.And there is pungency acetic acid smell to emit.Continue to be ground to 40min, the mixture color is a bluish voilet, and irritating smell is thin out.When being ground to about 60min, can not hear the acetic acid smell, reacted completely.With 75% washing with alcohol product 2 times.Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
Products therefrom is carried out Infrared spectroscopy.Measure glycocoll-copper at 400～4000cm with the KBr pressed disc method
-1Infrared spectra.As shown in Figure 2, after glycine and cupric ion formed title complex, the main absorption peak of it some was compared with part obvious displacement has been taken place, and relative intensity also changes to some extent, thereby confirmed that coordination has taken place for bivalent cupric ion and glycine.Hydroxyl association peak dwindles, and this is because strengthened by the influence of other groups after the coordination, at 3100cm
-1About the peak be subjected to displacement; 1408cm
-1Absorption peak belong to-CH
2One group.Glycine is at 2250cm
-1-NH
3+Characteristic peak completely dissolve in the IR of title complex spectrogram.3333cm
-1And 3264cm
-1The antisymmetric stretching vibration v that the N-H key occurred
As(N-H) and symmetrical stretching vibration v
s(N-H) charateristic avsorption band, coincidence formula v between their frequency
s=345.5+0.876v
AsAt 1605cm
-1And 1389cm
-1The absorption peak that occurs is respectively the antisymmetric vibration v of carboxylic acid ion
As(COO-) and symmetrical stretching vibration v
s(COO-), move to lower wave number and high wave number respectively than part, its difference is the flexible v=216cm of Δ
-1, show that carboxylic acid ion participates in coordination with monodentate, exist in the molecule and join ring.1120cm
-1The 1127cm of v (C-N) peak and glycine has appearred in the place
-1Compare, wave number is low.At 558cm
-1And 456cm
-1Have the stretching vibration peak of Cu-N and the stretching vibration peak of Cu-O respectively, this further specifies the formation that Diglycocol closes copper complex.
Products therefrom is carried out differential thermal-difference weight analysis.In nitrogen protection, heat-up rate is 10 ℃ of min
-1Measure the thermogravimetric-differential thermal spectrum of title complex, as shown in Figure 8 by room temperature-900 ℃.Cu (gly) H
2The thermolysis of O is divided into two stages: at first have an endotherm(ic)peak to lose a part water at 132 ℃, generate Cu (gly).The TG curve table reveals 7.57% weightlessness, and is approaching with calculated value (7.84%), and an endotherm(ic)peak is arranged in the time of 255 ℃, for Cu (gly) decomposes, shows as 51.34% on the TG curve, approaching with calculated value (57.52%).Last residual volume is 41.09%, and its calculated value is (34.64%), with measured value a difference is arranged.May be because product purity is not good, contain impurity and cause.We draw thus, and after neutralized verdigris and glycine solid phase synthesis glycine closed copper (II), heat decomposition temperature had risen to 255 ℃, the stability increase from 237 ℃.
Reaction principle is:
2NH
2CH
2COOH+CuCl
2·H
2O→[Cu(NH
2CH
2COO)
2·H
2O]+2HCl↑
Preparation process is as follows: accurately take by weighing glycine and cupric chloride crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature.After grinding 20min, the mixture color is by the light blue green that becomes.Continue to be ground to 40min, have a large amount of moisture content to generate, product is grume.Seasoning 12 hours, product are deep green.Water-soluble back is a dark blue solution.With 75% washing with alcohol product 2 times.Dry: elder generation and drying at room temperature are 80 ℃ of thorough dryings.
Products therefrom is carried out Infrared spectroscopy.Measure glycocoll-copper at 400～4000cm with the KBr pressed disc method
-1Infrared spectra.As among Fig. 3 as can be seen: the infrared spectra of glycine is at 3100cm
-1About strong broad band is arranged, this is NH
3 +Charateristic avsorption band, and do not have this absorption peak in the infrared spectra of glycocoll-copper, illustrating does not have free NH in the glycocoll-copper
3 +, simultaneously, glycine is at 2100cm
-1There is a stronger absorption peak at the place, and this is the charateristic avsorption band of a-amino acid, and does not have this absorption peak in the glycocoll-copper.Therefore can determine not have in the glycocoll-copper free glycine to exist.Glycine is at 3100cm
-1The N at place
2Tangible displacement after forming title complex, has taken place in the charateristic avsorption band of H key, appears at 3230cm
-1The place is simultaneously at 553cm
-1The stretching vibration peak of Cu-N has appearred in the place, illustrates that the N atom has participated in coordination.In addition, v in the glycine
sCOO-and v
AsThe red shift that the absorption peak of COO-has also taken place after forming title complex has neither part nor lot in coordinate C-C and C-H and has all kept, and is respectively 1448cm
-1And 1130cm
-1The above fact all illustrates to exist in the glycocoll-copper molecule joins ring, and the glycocoll-copper title complex forms.But absorb the too mixed and disorderly complexity of honeybee among the figure, as seen this title complex purity is not good, reacts complete inadequately.
Reaction principle is:
2NH
2CH
2COOH+Zn(Ac)
2·H
2O→[Zn(NH
2CH
2COO)
2·H
2O]+2HAc↑
Preparation process is as follows: accurately take by weighing glycine and zinc acetate crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature.After grinding 20min, wherein there is pungency acetic acid smell to emit.Continue to be ground to 40min, irritating smell is thin out.When being ground to about 60min, can not hear the acetic acid smell, reacted completely.Seasoning 12 hours.With 75% washing with alcohol product 2 times.Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
Products therefrom is carried out Infrared spectroscopy.Measure zinc glycinate at 400～4000cm with the KBr pressed disc method
-1Infrared spectra, as shown in Figure 4.After glycine and zine ion formed title complex, the main absorption peak of it some was compared with part obvious displacement has been taken place, and relative intensity also changes to some extent, thereby confirmed that coordination has taken place for divalent zinc ion and glycine.Hydroxyl association peak dwindles, and this is because strengthened by the influence of other groups after the coordination, at 3100cm
-1About peak generation red shift; 1439cm
-1Absorption peak belong to-CH
2-group.Glycine is at 2250cm
-1-NH
3+Characteristic peak completely dissolve in the IR of title complex spectrogram.3261cm
-1And 3058cm
-1Antisymmetric stretching vibration vas (N-H) and symmetrical stretching vibration vs (N-H) charateristic avsorption band that the N-H key occurred, coincidence formula v between their frequency
s=345.5+0.876vas.At 1653cm
-1And 1398cm
-1The absorption peak that occurs is respectively the antisymmetric vibration vas (COO-) and the symmetrical stretching vibration v of carboxylic acid ion
s(COO-), move to lower wave number and high wave number respectively than part, its difference is the flexible v=220cm of Δ
-1, show that carboxylic acid ion participates in coordination with monodentate, exist in the molecule and join ring.1122cm
-1The 1127cm of v (C-N) peak and glycine has appearred in the place
-1Compare, wave number is low.At 680cm
-1And 574cm
-1Have the stretching vibration peak of Cu-N and the stretching vibration peak of Cu-O respectively, this advances-goes on foot the formation that the explanation glycine closes copper complex.
Thermogravimetric-differential thermal carries out Infrared spectroscopy to products therefrom.In nitrogen protection, heat-up rate is 10 ℃ of min
-1Measure the thermogravimetric-differential thermal spectrum of title complex, as shown in Figure 9 by room temperature-900 ℃.On the TG curve weightlessness being arranged, is 0.92%, and analysis may be a planar water.On the TG curve weightlessness being arranged, promptly is the dehydration process of zinc glycinate title complex, and fluid loss is 9.64%, is equivalent to 1 molecular water weightlessness, with Theoretical Calculation result 7.78% basically identical, illustrates that the water in the title complex is crystal water.Weightless constant, residual volume 32.27% coincide with w in the title complex (ZnO)=35.15%, illustrates that final degradation production is ZnO.
Reaction principle is:
2NH
2CH
2COOH+ZnSO
4·5H
2O→[Zn(NH
2CH
2COO)
2·H
2O]+H
2SO
4
Preparation process is as follows: accurately take by weighing glycine and neutralized verdigris crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature.After grinding 20min, become grume, have small amount of moisture to generate, be white in color.Continue to be ground to 40min, it is mixed.React completely when being ground to about 60min.With 75% washing with alcohol product 2 times.Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
Products therefrom is carried out Infrared spectroscopy.Measure zinc glycinate at 400～4000cm with the KBr pressed disc method
-1Infrared spectra, as shown in Figure 5.After glycine and zine ion formed title complex, the main absorption peak of it some was compared with part obvious displacement has been taken place, and relative intensity also changes to some extent, thereby confirmed that coordination has taken place for divalent zinc ion and glycine.Hydroxyl association peak dwindles, and this is because strengthened by the influence of other groups after the coordination, at 3100cm
-1About peak generation red shift; 1437cm
-1Absorption peak belong to-CH
2-group.Glycine is at 2250cm
-1-NH
3 +Characteristic peak completely dissolve in the IR of title complex spectrogram.3521cm
-1And 3168cm
-1The antisymmetric stretching vibration v that the N-H key occurred
As(N-H) and symmetrical stretching vibration v
s(N-H) charateristic avsorption band, coincidence formula v between their frequency
s=345.5+0.876v
AsAt 1646cm
-1And 1411cm
-1The absorption peak that occurs is respectively the antisymmetric vibration v of carboxylic acid ion
As(COO-) and symmetrical stretching vibration v
s(COO-), move to lower wave number and high wave number respectively than part, its difference is the flexible v=220cm of Δ
-1, show that carboxylic acid ion participates in coordination with monodentate, exist in the molecule and join ring.1113cm
-1The 1127cm of v (C-N) peak and glycine has appearred in the place
-1Compare, wave number is low.At 617cm
-1And 506cm
-1Have the stretching vibration peak of Cu-N and the stretching vibration peak of Cu-O respectively, this further specifies the formation that glycine closes copper complex.The infrared spectra of relatively above each product, as shown in Figure 6:
Products therefrom is carried out differential thermal-thermogravimetric analysis.In nitrogen protection, heat-up rate is 10 ℃ of min
-1Measure the thermogravimetric-differential thermal spectrum of title complex, as shown in figure 10 by room temperature-900 ℃.On the TG curve weightlessness being arranged, promptly is the dehydration process of zinc glycinate title complex, and fluid loss is 7.74%, is equivalent to 1 molecular water weightlessness, with Theoretical Calculation result 7.78% basically identical, illustrates that the water in the title complex is crystal water.Residual volume 41.1%, identical substantially with w in the title complex (ZnO)=35.15%, illustrate that final degradation production is ZnO.
Above-described room temperature is to be 18～37 ℃, and temperature range is quite extensive, need not the refrigeration or the heating installation of being correlated with in the preparation process.The aminoacetic acid complex of preparation is random crystal after grinding oven dry, and soluble in water, is insoluble to organic solvents such as alcohol, ether.Glycocoll-copper odorless, tasteless, the glycocoll-copper of ventilation breather and glycine preparation is a blue powder, and venus crystals and glycine are glycocoll-copper bluish voilet powder, and water-soluble back is a blue solution; Zinc glycinate odorless, tasteless white needle-like crystals, water-soluble back is a colourless transparent liquid.
As shown in Figure 6, the absorption peak of each product moves basic identical, illustrates that the solid state reaction result of glycocoll-copper, zinc is basic identical.But,, has a little difference in its coordination for complex system because solid state reaction raw material difference adds the difference of grinding.
The relatively heat analysis of aminoacetic acid complex, as shown in figure 11:
Thermogravimetric one differential thermal analysis relatively, can release its weightless process and be:
[Cu(NH
2CH
2COO)
2·H
2O]→Cu(NH
2CH
2COO)
2
Cu(NH
2CH
2COO)
2→CuO
[Zn(NH
2CH
2COO)
2·H
2O]→Zn(NH
2CH
2COO)
2
Zn(NH
2CH
2COO)
2→ZnO
Preliminary definite product is copper, zinc aminoacetic acid complex (coordination ratio is 2: 1).On this basis, infer it
Molecular formula is: C
4H
10N
2O
5Cu, C
4H
10N
2O
5Zn;
Structural formula is: [Cu (NH
2CH
2COO)
2H
2O], [Zn (NH
2CH
2COO)
2H
2O];
Relative molecular mass is: 230,231.5.
It is basic identical to illustrate that glycine closes the solid state reaction result of copper (II), zinc (II), but because solid state reaction raw material difference, the difference of grinding there are differences on its purity.
Technology of the present invention is simple, and the reaction times is short, the productive rate height, and energy consumption is low, has not only effectively avoided the hard aggregation phenomenon of product, and has not used solvent, and environmental pollution is little, and copper, zinc content are higher relatively, and its result is safe and reliable.Realizing copper with low cost, the production of zinc aminoacetic acid complex fodder additives, is real Green Chemistry reaction.
The animal clinical trial
The laying hen test
With the inorganic copper of the glycocoll-copper of above method gained and zinc glycinate and equivalent and each self-configuring addition of zinc element 0.4% Preblend.The prescription of daily ration as shown in figure 12.Experimental animal is the extra large blue w-36 laying hen in 440 42 ages in week, is divided into contrast at random and tests two groups.Lay eggs before each group examination, feed consumption difference not significantly (P＞0105).
Test method: test chicken is raised in cages, two groups of chicken position symmetrical distributions, and test group is fed the dry mash that contains glycocoll-copper and zinc glycinate Preblend, and control group is fed the dry mash that contains common inorganic copper, zinc element Preblend, free choice feeding; Tank is for cleaning drinking-water; Two groups of other management conditions are in full accord.The official test phase is 45 days.Food consumption, egg number and the egg productivity of chicken respectively organized in record.
Test-results: as shown in figure 13, two groups of red plumages of cockscomb are bright, in good health in trial period, and honey stomach is anosis, dead, superseded.Test group is than the voluminous 320 pieces of eggs of control group, 1.45 pieces of average every chicken fecund.Compare with control group, the average food consumption of test group chicken has raising slightly, and egg productivity has increased nearly 20kg, thereby feed efficiency improves.Overall economic efficiency improves 2.2%.
As seen, laying hen is under the daily ration condition of nutrition equivalence, and the control group laying rate, egg productivity, feed efficiency and the overall economic efficiency that provide the test group of trace element to add inorganic salt than equivalent with complex form improve 4.2%, 4.37%, 2.2% and 2.2% respectively.
The pork pig test
The test group daily ration: soya-bean oil 1.5%, dregs of beans 18%, wheat bran 8%, with the Preblend 3% that glycocoll-copper and zinc glycinate are joined, the 0.2%-0.6% that the test additive is pressed labeling requirement adds, and corn is assorted to 100%.
The control group daily ration: soya-bean oil 1.5%, dregs of beans 18%, wheat bran 8% is joined Preblend 3% with the inorganic copper of equivalent, zinc element, and other adds 0.1% Qi Libao, and corn is assorted to 100%.
Test pig: select 100 of 70 kilograms of left and right sides pork pigs of DLY three way cross kind, to being divided into 4 groups, 25 every group, every component is 5 repetitions by body weight, sex and blood lineage.
Test method: three groups is test group, feeding study group daily ration, and one group is control group, feeds the control group daily ration; Other management condition is identical.
Test-results: as shown in figure 14, added glycocoll-copper, the live pig day weight gain of zinc glycinate title complex is greater than the weightening finish of inorganic salt, and weightening finish reaches 74 grams, and yellowish pink red degree well.
Claims (9)
1. method of grinding solid phase preparation copper, zinc aminoacetic acid complex, it is characterized in that: preparation process is as follows: glycine and copper, zinc metallic compound are at room temperature mixed placing mortar to grind 15～30 minutes, glycine and copper, zinc metallic compound generation chemical reaction, continue to grind 40～80 minutes, until reacting completely; The washing reaction thing, final drying.
2. the method for grinding solid phase preparation copper as claimed in claim 1, zinc aminoacetic acid complex is characterized in that: described washing is with 75% washing with alcohol product 2 times.
3. the method for grinding solid phase preparation copper as claimed in claim 1, zinc aminoacetic acid complex is characterized in that: described drying mode is prior to drying at room temperature, again in 80 ℃ of thorough dryings.
4. the method for grinding solid phase preparation copper as claimed in claim 1, zinc aminoacetic acid complex is characterized in that: the mol ratio of described glycine and copper, zinc reaction is 2: 1.
5. the method for grinding solid phase preparation copper as claimed in claim 1, zinc aminoacetic acid complex, it is characterized in that: it is as follows that described glycine and ventilation breather prepare the glycocoll-copper step: accurately take by weighing glycine and basic carbonate copper crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature; Grind 20min, mix and grind the thing color and shoal, be light blue; Continue to be ground to 40min, the mixture color deepens gradually, is blue; When being ground to 60min, the blue pasty state of one-tenth uniformly afterreaction is complete; With 75% washing with alcohol product 2 times, drying: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
6. the method for grinding solid phase preparation copper as claimed in claim 1, zinc aminoacetic acid complex, it is characterized in that: the step that described glycine and venus crystals prepare glycocoll-copper is as follows: accurately take by weighing glycine and venus crystals crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature; Grind 20min, mix and grind the thing color and shoal, be blue; And there is pungency acetic acid smell to emit; Continue to be ground to 40min, the mixture color is a bluish voilet, and irritating smell is thin out; When being ground to 60min, it is complete can not heard acetic acid smell afterreaction; With 75% washing with alcohol product 2 times; Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
7. the method for grinding solid phase preparation copper as claimed in claim 1, zinc aminoacetic acid complex, it is characterized in that: the step that described glycine and cupric chloride prepare glycocoll-copper is as follows: accurately take by weighing glycine and cupric chloride crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature; After grinding 20min, the mixture color is by the light blue green that becomes; Continue to be ground to 40min, have a large amount of moisture content to generate, it is complete that product is the grume afterreaction; With 75% washing with alcohol product 2 times; Dry: elder generation and drying at room temperature are 80 ℃ of thorough dryings.
8. the method for grinding solid phase preparation copper as claimed in claim 1, zinc aminoacetic acid complex, it is characterized in that: the step that described glycine and zinc acetate prepare zinc glycinate is as follows: accurately take by weighing glycine and zinc acetate crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature; After grinding 20min, wherein there is pungency acetic acid smell to emit; Continue to be ground to 40min, irritating smell is thin out, and when being ground to 60min, it is complete can not heard acetic acid smell afterreaction; With 75% washing with alcohol product 2 times; Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
9. the method for grinding solid phase preparation copper as claimed in claim 1, zinc aminoacetic acid complex, it is characterized in that: the step that described glycine and zinc sulfate prepare zinc glycinate is as follows: accurately take by weighing glycine and zinc sulfate crystal, making its mol ratio is 2: 1, mixes placing mortar to grind under the room temperature; After grinding 20min, become grume, have small amount of moisture to generate, be white in color; Continue to be ground to 40min, it is mixed; React completely when being ground to 60min; With 75% washing with alcohol product 2 times; Dry: prior to drying at room temperature, again in 80 ℃ of thorough dryings.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278916A (en) * | 2016-09-05 | 2017-01-04 | 河北东华冀衡化工有限公司 | A kind of preparation method of cupric glycinate |
| CN110859675A (en) * | 2019-10-21 | 2020-03-06 | 昆山洁宏无纺布制品有限公司 | Broad-spectrum long-acting antibacterial medical operation bag |
| CN115975209A (en) * | 2022-12-29 | 2023-04-18 | 武汉理工大学 | Method for synthesizing MOFs material in all solid phases |
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2007
- 2007-09-06 CN CNA2007100301225A patent/CN101139300A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278916A (en) * | 2016-09-05 | 2017-01-04 | 河北东华冀衡化工有限公司 | A kind of preparation method of cupric glycinate |
| CN110859675A (en) * | 2019-10-21 | 2020-03-06 | 昆山洁宏无纺布制品有限公司 | Broad-spectrum long-acting antibacterial medical operation bag |
| CN110859675B (en) * | 2019-10-21 | 2021-07-09 | 昆山洁宏无纺布制品有限公司 | Broad-spectrum long-acting antibacterial medical operation bag |
| CN115975209A (en) * | 2022-12-29 | 2023-04-18 | 武汉理工大学 | Method for synthesizing MOFs material in all solid phases |
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