CN103224461A - Preparation method of large granule crystal form methionine metal chelate and application thereof - Google Patents

Preparation method of large granule crystal form methionine metal chelate and application thereof Download PDF

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CN103224461A
CN103224461A CN2013101413914A CN201310141391A CN103224461A CN 103224461 A CN103224461 A CN 103224461A CN 2013101413914 A CN2013101413914 A CN 2013101413914A CN 201310141391 A CN201310141391 A CN 201310141391A CN 103224461 A CN103224461 A CN 103224461A
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methionine
met
control group
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salt
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CN103224461B (en
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舒绪刚
段晶娜
吴春丽
樊明智
许祥
高均勇
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GUANGZHOU TIANKE BIOLOGICAL SCIENCE AND TECHNOLOGY Co Ltd
Zhongkai University of Agriculture and Engineering
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GUANGZHOU TIANKE BIOLOGICAL SCIENCE AND TECHNOLOGY Co Ltd
Zhongkai University of Agriculture and Engineering
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Abstract

The invention discloses a preparation method of large granule crystal form methionine metal chelate and an application thereof. An effective crystallizing agent is added into the production technology for promoting crystallization of methionine series chelate. The preparation method has the advantages of simple technology operation, high purity of produced materials, easy dehydration, fast drying, good fluency of dried product, few dust, crystallinity luster, well mixing in forage and effectively improved production efficiency.

Description

The preparation method and the application thereof of macrobead crystal formation methionine(Met) metallo-chelate
Technical field
The present invention relates to a kind of preparation method and application thereof of macrobead crystal formation methionine(Met) metallo-chelate.
Background technology
Methionine(Met) series inner complex is the trace element that growth of animal is essential and the compound of methionine(Met) effect generation chelating attitude, is a kind of trace element replenisher that approaches natural form in the animal body.Comparing with inorganic salt, have good chemical stability and biochemical stability, is a kind of ideal high-efficiency feed additive.
It is raw material that the methionine(Met) series inner complex product of selling on the market at present adopts with methionine(Met) and inorganic salt more, utilizes acid-base neutralisation method synthetic methionine inner complex.This method operational path is feasible, and operational condition is not severe
Carve, equipment is uncomplicated, and experimental product purity height.But in actual production process, synthetic methionine chelate produce thing granularity is little, and filter cake is sticky, and dehydration is difficult, and drying time is long, and the production process dust is big, gives on production operation and the energy consumption and causes great inconvenience and waste.Simultaneously, the zinc methionine product stickiness of producing is big, and density is little, and fluency is poor.Be difficult to and the abundant mixing of feed, cause the feed quality instability easily, influence feeding effect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of macrobead crystal formation methionine(Met) metallo-chelate.
Another object of the present invention is to provide the application of the above-mentioned macrobead crystal formation methionine(Met) metallo-chelate for preparing on the preparation fodder additives.
The technical solution used in the present invention is:
A kind of preparation method of macrobead crystal formation methionine(Met) metallo-chelate comprises the steps:
1) in reactor, adds methionine(Met), alkali salt, crystallizing agent and water, heating for dissolving;
2) stir adding pH regulator agent regulator solution pH value to 6~8 down;
3) add metal-salt, 60 ℃~90 ℃ reactions;
4) crystallisation by cooling gets the methionine(Met) metallo-chelate after the drying.
Described crystallizing agent is any in Trisodium Citrate, sodium bicarbonate, sodium formiate, the sodium acetate.
The consumption of crystallizing agent is 10~20% of a methionine(Met) quality.
Described metal-salt is any in zinc sulfate, copper sulfate, chromium chloride, the manganous sulfate, and the mol ratio of methionine(Met) and metal-salt is 2~8:1~4.
Preferably, the mol ratio of methionine(Met) and metal-salt is 2:1.
Described alkali salt is NaOH, and the mol ratio of methionine(Met) and alkali salt is 1:0.8~1.2.
Described pH regulator agent is sodium hydroxide or ammoniacal liquor.
The mass volume ratio of methionine(Met) and water is 1g:1~2ml in the step 1).
The time of the described reaction of step 3) is 10~20min.
The application of the macrobead crystal formation methionine(Met) metallo-chelate that above method prepares on the preparation fodder additives.
Methionine chelate thing synthetic route of the present invention is seen Fig. 1, its structural formula (M represents metallic element) as follows:
Figure 374351DEST_PATH_IMAGE001
The invention has the beneficial effects as follows:
The invention provides a kind of technical intelligence of synthetic macrobead crystal formation methionine(Met) series inner complex, can effectively solve in the actual production process, filter cake is sticky, the hard-pumped filter, and oven dry back finished product is loose, and density is little, the problem of fluency difference.This synthesis technique is simple, and raw material is easy to get, and product density is big, is crystallinity gloss, and simultaneously resulting methionine(Met) series inner complex fluency is good, can effectively mix with feed,
Figure 341039DEST_PATH_IMAGE002
The flow process that simplifies the operation can be used as animal feedstuff additive, replenishes each dvielement in the daily ration, improves the growth performance and the immune performance of animal body.
Description of drawings
Fig. 1 is the synthetic route chart (is example with the zinc methionine) of macrobead crystal formation methionine(Met) series inner complex of the present invention;
Fig. 2 be embodiment 1 zinc methionine inner complex before improvement with improve after the crystalline structure comparison diagram;
Fig. 3 be embodiment 4 methionine copper chelates before improvement with improve after the crystalline structure comparison diagram;
Fig. 4 be embodiment 6 manganese methionine inner complexs before improvement with improve after the crystalline structure comparison diagram;
Fig. 5 be embodiment 7 chromium methionine inner complexs before improvement with improve after the crystalline structure comparison diagram.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but be not limited thereto.
Embodiment 1
The preparation method of macrobead crystal formation zinc methionine, its concrete steps are as follows:
Take by weighing 30.1g(0.2mol) methionine(Met), add water 100mL, add sodium hydroxide 8.0g, sodium laurylsulfonate 6.0g, heated and stirred dissolving; Add 29.8g(0.1mol again) Zinc Sulphate Heptahydrate, regulate mixing solutions pH value with small amounts of sodium hydroxide again and be about 7, controlled temperature was 60 ℃ of reactions 15 minutes, the cooling suction filtration, solid is dried to constant weight under 105 ℃, get zinc methionine 34.8g, detecting zinc content is 17.97%, and methionine content is 80.86%.
Embodiment 2
The preparation method of macrobead crystal formation zinc methionine, its concrete steps are as follows:
Take by weighing 60.2g(0.4mol) methionine(Met), add water 200ml, add sodium hydroxide 15.0g, anhydrous sodium acetate 6.0g, the heated and stirred dissolving adds 59.6g(0.2mol again) Zinc Sulphate Heptahydrate, regulate mixing solutions pH value with ammoniacal liquor and be about 7, controlled temperature was 70 ℃ of reactions 15 minutes, the cooling suction filtration, solid is dried to constant weight under 105 ℃, get zinc methionine 56.4g, detecting zinc content is 18.02%, and methionine content is 81.38%.
Embodiment 3
The preparation method of macrobead crystal formation zinc methionine, its concrete steps are as follows:
Take by weighing 60.2g(0.4mol) methionine(Met), add water 200ml, add sodium bicarbonate 6.0g, add the sodium hydroxide of 15.0g again, add 59.6g(0.2mol) Zinc Sulphate Heptahydrate, regulate mixing solutions pH with sodium hydroxide and be about 7, controlled temperature cools off suction filtration 80 ℃ of reactions 15 minutes, solid is dried to constant weight under 105 ℃, get zinc methionine 68.3g, detecting zinc content is 17.86%, and methionine content is 80.99%.
Embodiment 1~3 resulting product is washed with water repeatedly, and oven dry can obtain the higher zinc methionine inner complex of purity, and the crystalline powder gloss that is white in color is insoluble in water.Place microscopically to observe, simultaneously with former technology (reference Chinese grain and oil journal 1997 02 interim " research of zinc methionine complex compound synthesis technique ", adopt the organic solvent facture, the coordination ratio of methionine(Met) and metal ion is 2:1, pH value in reaction is 7, temperature of reaction is 60 ℃, and the reaction times is 15 minutes) products therefrom compares, and the contrast of technology crystal formation is as shown in Figure 2 before and after the zinc methionine.
Embodiment 4
The preparation method of macrobead crystal formation copper methionine, its concrete steps are as follows:
Take by weighing 30.1g(0.2mol) methionine(Met), add water 100ml, add sodium hydroxide 8.0g, add Trisodium Citrate 6.0g, add 25.5g(0.1mol again) cupric sulfate pentahydrate, regulate pH with sodium hydroxide and be about 7, controlled temperature cools off suction filtration 80 ℃ of reactions 15 minutes, solid is dried to constant weight under 105 ℃, get copper methionine 34.0g, detecting copper content is 17.58%, and methionine content is 81.96%.
Embodiment 5
The preparation method of macrobead crystal formation copper methionine, its concrete steps are as follows:
Take by weighing 90.3g(0.6mol) methionine(Met), add water 250ml, add sodium hydroxide 23.0g, sodium formiate 6.0g, add 76.5g(0.3mol again) cupric sulfate pentahydrate, regulate pH with sodium hydroxide and be about 7.0, controlled temperature cools off suction filtration 70 ℃ of reactions 15 minutes, solid is dried to constant weight under 105 ℃, get copper methionine 103.0g, detecting copper content is 17.54%, and nitrogen content is 81.38%.
The product that embodiment 4 and 5 is obtained washes with water repeatedly, and oven dry can get the higher methionine copper chelate of purity, is blue crystalline powder gloss, is insoluble in water.Place microscopically to observe, simultaneously with former technology (reference Chinese grain and oil journal 1997 02 interim " research of zinc methionine complex compound synthesis technique ", adopt the organic solvent facture, the coordination ratio of methionine(Met) and metal ion is 2:1, pH value in reaction is 7, temperature of reaction is 80 ℃, and the reaction times is 15 minutes) products therefrom compares, and the contrast of technology crystal formation is as shown in Figure 3 before and after the copper methionine.
Embodiment 6
The preparation method of macrobead crystal formation manganese methionine, its concrete steps are as follows:
Take by weighing 60.2g(0.4mol) methionine(Met), add water 180ml, add sodium formiate 8.0g, add the sodium hydroxide of 15.0g again, add 33.8g(0.2mol) manganese sulfate monohydrate, regulate mixing solutions pH with sodium hydroxide and be about 7, controlled temperature is at 80 ℃ of reactions 15 minutes, crystallisation by cooling suction filtration, solid is dried to constant weight under 105 ℃, get manganese methionine 67.9g, detecting manganese content is 15.49%, and methionine content is 82.83%.
With embodiment 6 resulting products with washing with alcohol repeatedly, oven dry can obtain the higher manganese methionine inner complex of purity, and the crystallinity that is white in color particle is more soluble in water.Place microscopically to observe, simultaneously with former technology (reference Chinese grain and oil journal 1997 02 interim " research of zinc methionine complex compound synthesis technique ", adopt the organic solvent facture, the coordination ratio of methionine(Met) and metal ion is 2:1, pH value in reaction is 7, temperature of reaction is 60 ℃, and the reaction times is 15 minutes) products therefrom compares, and the contrast of technology crystal formation is as shown in Figure 4 before and after the manganese methionine.
Embodiment 7
The preparation method of macrobead crystal formation chromium methionine, its concrete steps are as follows:
Take by weighing 45.1g(0.3mol) methionine(Met), add water 100ml, add sodium hydroxide 11.5g, add Trisodium Citrate 9.0g, add 26.7g(0.1mol again) chromium chloride hexahydrate, regulate pH with sodium hydroxide and be about 7, controlled temperature cools off suction filtration 80 ℃ of reactions 15 minutes, solid is dried to constant weight under 105 ℃, get chromium methionine 48.5g, detecting chromium content is 10.17%, and methionine content is 85.39%.
With embodiment 7 resulting products with washing with alcohol repeatedly, oven dry can obtain the higher chromium methionine inner complex of purity, is red-purple crystallinity particle, and is more soluble in water.Place microscopically to observe, simultaneously with former technology (reference Chinese grain and oil journal 1997 02 interim " research of zinc methionine complex compound synthesis technique ", adopt the organic solvent facture, the coordination ratio of methionine(Met) and metal ion is 3:1, pH value in reaction is 7, temperature of reaction is 80 ℃, and the reaction times is 15 minutes) products therefrom compares, and the contrast of technology crystal formation is as shown in Figure 4 before and after the chromium methionine.
The methionine(Met) series inner complex product that two kinds of technologies are obtained is analyzed simultaneously, and analytical results sees Table 1.
By contrast, the methionine(Met) series inner complex product crystallization crystal formation after we can find to improve obviously increases, and unit weight improves, and granularity increases, and stick greasy phenomenon for improving filter cake, and dehydration is difficult, drying time length has very great help.
Figure 736248DEST_PATH_IMAGE003
Experimentation on animals 1
The macrobead crystal formation zinc methionine for preparing with embodiment 1 carries out experimentation on animals below.
Will be even with a collection of 200 sizes, athletic 160 age in days Luo Man hens are raised a week in advance, therefrom select out product age in days 180 healthy hens identical, that body weight is close and be divided into 3 groups at random, 1 experimental group (basal diet per ton adds zinc methionine 70 grams of embodiment 1), 1 negative control group (basal diet), 1 positive control group (basal diet per ton adds zinc methionine 70 grams with former prepared), every group of 60 chickens.
This experiment is carried out in the semi open model hen house, and trial period was 6 weeks.Duration of test is fed powder, free choice feeding drinking-water; Keep illumination in 16 hours every day, temperature is at 20-28 ℃, and humidity is at 60-70%.The crude protein content of basal diet is 16.5%, and metabolizable energy is 2750 Kcal/kg, and calcium contents is 3.5%, and phosphorus content is 0.62%.
Performance test: every day each experimental group of time recording egg number and egg size; Measure each weekly and repeat feed consumption rate and laying hen individual weight; Add up egg size, laying rate, feed consumption rate and feedstuff-egg ratio weekly.
Slaughter determining: randomly draw 9 hens and butcher, carotid artery is got the level of methionine(Met) and zinc element in the hematometry blood.
Experimental result shows that the average growth rate of 3 groups of laying hens is followed successively by from high to low: the negative control group of positive control group ﹥ experimental group ﹥, but there was no significant difference between three groups (P〉0.05).
Laying rate is followed successively by from high to low: the positive control group ﹥ of experimental group ﹥ bears control group.Experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
The level of methionine(Met) is followed successively by from high to low in the blood: the positive control group ﹥ of experimental group ﹥ bears control group.Equally, experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
The level of zinc element is followed successively by from high to low in the blood: the positive control group ﹥ of experimental group ﹥ bears control group.Equally, experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
Above description of test, the zinc methionine that utilizes the inventive method to prepare can be used as the zinc source in the feed, replenish zinc element and methionine(Met) in the daily ration, improve the growth performance and the immune performance of animal body.And, stick greasy phenomenon for improving filter cake, and dehydration is difficult, drying time length has very great help, and can effectively enhance productivity because its granularity increases, and unit weight improves.
Experimentation on animals 2
The macrobead crystal formation copper methionine for preparing with embodiment 4 carries out experimentation on animals below.
1, experiment is provided with
30 close batch, body weight 35 age in days weanling pigs close, that be in a good state of health are raised a week in advance, be divided into 3 groups at random, 1 experimental group (adding macrobead crystal formation copper methionine 100 grams in the basal diet per ton), 1 negative control group (basal diet), 1 positive control group (basal diet per ton adds copper methionine 100 grams with former prepared), every group of 10 pigs.
This experiment is carried out in the insulation pig house, and trial period was 8 weeks.Duration of test, free choice feeding drinking-water; Natural lighting, temperature is at 22-28 ℃, and humidity is at 60-70%.The crude protein content of basal diet is 18.0%, and metabolizable energy is 3400 Kcal/kg, and calcium contents is 0.8%, and available phosphorus content is 0.35%.
2, production performance test
The food consumption of the every hurdle of time recording every day piglet; Measure the individual weight of each piglet weekly; Add up feedstuff-meat ratio weekly, calculate all food consumptions, day weight gain.
3, experimental result
Experimental result shows that daily ingestion amount is followed successively by from high to low: the negative control group of positive control group ﹥ experimental group ﹥, but there was no significant difference between three groups (P〉0.05).
Feedstuff-meat ratio is followed successively by from low to high: the positive control group ﹤ of experimental group ﹤ bears control group.Experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
Average growth rate is followed successively by from high to low: the positive control group ﹥ of experimental group ﹥ bears control group.Equally, experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
Above description of test, the macrobead crystal formation copper methionine that utilizes the inventive method to prepare can be used as the copper source in the feed, replenishes copper and methionine(Met) in the daily ration, improves the growth performance and the immune performance of animal body.And, stick greasy phenomenon for improving filter cake, and dehydration is difficult, drying time length has very great help, and can effectively enhance productivity because its granularity increases, and unit weight improves.
Experimentation on animals 3
The macrobead crystal formation manganese methionine for preparing with embodiment 6 carries out experimentation on animals below.
Will be even with a collection of 200 sizes, athletic 160 age in days Luo Man hens are raised a week in advance, therefrom select out product age in days 180 healthy hens identical, that body weight is close and be divided into 3 groups at random, 1 experimental group (basal diet per ton adds manganese methionine 100 grams of embodiment 1), 1 negative control group (basal diet), 1 positive control group (basal diet per ton adds manganese methionine 100 grams with former prepared), every group of 60 chickens.
This experiment is carried out in the semi open model hen house, and trial period was 6 weeks.Duration of test is fed powder, free choice feeding drinking-water; Keep illumination in 16 hours every day, temperature is at 20-28 ℃, and humidity is at 60-70%.The crude protein content of basal diet is 16.5%, and metabolizable energy is 2750 Kcal/kg, and calcium contents is 3.5%, and phosphorus content is 0.62%.
Performance test: every day each experimental group of time recording egg number and egg size; Measure each weekly and repeat feed consumption rate and laying hen individual weight; Add up egg size, laying rate, feed consumption rate and feedstuff-egg ratio weekly.
Slaughter determining: randomly draw 9 hens and butcher, carotid artery is got the level of methionine(Met) and manganese element in the hematometry blood.
Experimental result shows that the average growth rate of 3 groups of laying hens is followed successively by from high to low: the positive control group ﹥ of experimental group ﹥ bears control group, but there was no significant difference between three groups (P〉0.05).
Laying rate is followed successively by from high to low: the negative control group of positive control group ﹥ experimental group ﹥.Experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
The level of methionine(Met) is followed successively by from high to low in the blood: the positive control group ﹥ of experimental group ﹥ bears control group.Equally, experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
The level of manganese element is followed successively by from high to low in the blood: the positive control group ﹥ of experimental group ﹥ bears control group.Equally, experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
Above description of test, the manganese methionine that utilizes the inventive method to prepare can be used as the manganese source in the feed, replenish manganese element and methionine(Met) in the daily ration, improve the utilization of animal tissues to manganese element.And, stick greasy phenomenon for improving filter cake, and dehydration is difficult, drying time length has very great help, and can effectively enhance productivity because its granularity increases, and unit weight improves.
Experimentation on animals 4
The macrobead crystal formation chromium methionine for preparing with embodiment 7 carries out experimentation on animals below.
Will be even with a collection of 200 sizes, athletic 160 age in days Luo Man hens are raised a week in advance, therefrom select out product age in days 180 healthy hens identical, that body weight is close and be divided into 3 groups at random, 1 experimental group (basal diet per ton adds chromium methionine 0.2 gram of embodiment 1), 1 negative control group (basal diet), 1 positive control group (basal diet per ton adds chromium methionine 0.2 gram with former prepared), every group of 60 chickens.
This experiment is carried out in the semi open model hen house, and trial period was 6 weeks.Duration of test is fed powder, free choice feeding drinking-water; Keep illumination in 16 hours every day, temperature is at 20-28 ℃, and humidity is at 60-70%.The crude protein content of basal diet is 16.5%, and metabolizable energy is 2750 Kcal/kg, and calcium contents is 3.5%, and phosphorus content is 0.62%.
Performance test: every day each experimental group of time recording egg number and egg size; Measure each weekly and repeat feed consumption rate and laying hen individual weight; Add up egg size, laying rate, feed consumption rate and feedstuff-egg ratio weekly.
Slaughter determining: randomly draw 9 hens and butcher, carotid artery is got the level of methionine(Met) and chromium element in the hematometry blood.
Experimental result shows that the average growth rate of 3 groups of laying hens is followed successively by from high to low: the negative control group of positive control group ﹥ experimental group ﹥, but there was no significant difference between three groups (P〉0.05).
Laying rate is followed successively by from high to low: the negative control group of positive control group ﹥ experimental group ﹥, but there was no significant difference between three groups (P〉0.05).
Feedstuff-meat ratio is followed successively by from low to high: the positive control group ﹤ of experimental group ﹤ bears control group.Experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
The level of methionine(Met) is followed successively by from high to low in the blood: the positive control group ﹥ of experimental group ﹥ bears control group.Equally, experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
The level of chromium element is followed successively by from high to low in the blood: the positive control group ﹥ of experimental group ﹥ bears control group.Equally, experimental group and positive control group difference is (P〉0.05) not significantly, but all with negative control group significant difference (P<0.05).
Above description of test, the chromium methionine that utilizes the inventive method to prepare can be used as the chromium source in the feed, replenish chromium element and methionine(Met) in the daily ration, improve efficiency of feed utilization.And, stick greasy phenomenon for improving filter cake, and dehydration is difficult, drying time length has very great help, and can effectively enhance productivity because its granularity increases, and unit weight improves.

Claims (10)

1. the preparation method of a macrobead crystal formation methionine(Met) metallo-chelate comprises the steps:
1) in reactor, adds methionine(Met), alkali salt, crystallizing agent and water, heating for dissolving;
2) stir adding pH regulator agent regulator solution pH value to 6~8 down;
3) add metal-salt, 60 ℃~90 ℃ reactions;
4) crystallisation by cooling gets the methionine(Met) metallo-chelate after the drying.
2. method according to claim 1 is characterized in that, described crystallizing agent is any in Trisodium Citrate, sodium bicarbonate, sodium formiate, the sodium acetate.
3. method according to claim 1 and 2 is characterized in that, the consumption of crystallizing agent is 10~20% of a methionine(Met) quality.
4. method according to claim 1 is characterized in that, described metal-salt is any in zinc sulfate, copper sulfate, chromium chloride, the manganous sulfate, and the mol ratio of methionine(Met) and metal-salt is 2~8:1~4.
5. method according to claim 4 is characterized in that, the mol ratio of methionine(Met) and metal-salt is 2:1.
6. method according to claim 1 is characterized in that, described alkali salt is NaOH, and the mol ratio of methionine(Met) and alkali salt is 1:0.8~1.2.
7. method according to claim 1 is characterized in that, described pH regulator agent is sodium hydroxide or ammoniacal liquor.
8. method according to claim 1 is characterized in that, the mass volume ratio of methionine(Met) and water is 1g:1~2ml in the step 1).
9. method according to claim 1 is characterized in that, the time of the described reaction of step 3) is 10~20min.
10. the application of macrobead crystal formation methionine(Met) metallo-chelate on the preparation fodder additives that prepare of each method of claim 1-9.
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CN109456239A (en) * 2018-11-09 2019-03-12 禄丰天宝磷化工有限公司 A kind of production technology of a-amino acid chelated chromium (III)
CN109678769A (en) * 2019-02-14 2019-04-26 禄丰天宝磷化工有限公司 A method of comprehensive utilization methionine crystalline mother solution produces methionine metal chelate
CN109678768A (en) * 2019-02-14 2019-04-26 禄丰天宝磷化工有限公司 A method of methionine metal chelate is produced using methionine crystalline mother solution
CN110663823A (en) * 2019-11-05 2020-01-10 化学工业(全国)饲料添加剂工程技术中心山东科技公司 Preparation method of feed additive copper methionine

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CN103497132B (en) * 2013-10-24 2016-01-13 重庆紫光化工股份有限公司 Utilize D, the saponification liquor that L-Methionine is produced prepares N-methylol-D, the method for L-Methionine calcium
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CN103641755A (en) * 2013-11-19 2014-03-19 重庆紫光化工股份有限公司 Preparation method of D,L-2-hydroxy-4-methylthiobutyric acid-trace element chelate
CN103641754A (en) * 2013-11-19 2014-03-19 重庆紫光化工股份有限公司 Preparation method of medicinal D,L-2-hydroxy-4-methylthiobutyric acid metal chelate
CN103641755B (en) * 2013-11-19 2016-03-30 重庆紫光化工股份有限公司 The preparation method of D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate
CN103641754B (en) * 2013-11-19 2016-08-24 宁夏紫光天化蛋氨酸有限责任公司 The preparation method of medicinal D, L-2-hydroxy-4-methylthiobutyric acid metallo-chelate
CN104041675A (en) * 2014-06-25 2014-09-17 福建深纳生物工程有限公司 Simple preparation method for amino acid microelement chelate
CN104592303A (en) * 2015-01-06 2015-05-06 广州天科生物科技有限公司 Di(mu-) hydroxyl. tetramethionine-chelated dichromium (III) as well as preparation method and application thereof
CN109456239A (en) * 2018-11-09 2019-03-12 禄丰天宝磷化工有限公司 A kind of production technology of a-amino acid chelated chromium (III)
CN109678769A (en) * 2019-02-14 2019-04-26 禄丰天宝磷化工有限公司 A method of comprehensive utilization methionine crystalline mother solution produces methionine metal chelate
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