CN103224461B - 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 PDFInfo
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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
Technical field
The present invention relates to a kind of preparation method and application thereof of macrobead crystal formation methionine metal chelate.
Background technology
Methionine(Met) series inner complex is compound trace element required for growth of animal and methionine(Met) effect being generated Chelating state, is a kind of trace element replenisher close to natural form in animal body.Compared with inorganic salt, having good chemical stability and biochemical stability, is a kind of desirable high-efficiency feed additive.
Methionine(Met) series inner complex product many employings of current commercial type for raw material, utilize acid-base neutralisation method synthetic methionine inner complex with methionine(Met) and inorganic salt.The method operational path is feasible, and operational condition is not severe
Carve, equipment is uncomplicated, and experimental product purity is high.But in actual production process, the methionine chelate thing product particle size of synthesis is little, and filter cake is sticky, dehydration is difficult, and drying time is long, and production process dust is large, to production operation and energy consumption causing inconvenience greatly and waste.Meanwhile, the zinc methionine product stickiness produced is large, and density is little, and fluency is poor.Be difficult to fully mix with feed, easily cause feed quality unstable, affect 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 metal chelate.
Another object of the present invention is to provide the above-mentioned macrobead crystal formation methionine metal chelate prepared preparing the application on fodder additives.
The technical solution used in the present invention is:
A preparation method for macrobead crystal formation methionine metal chelate, comprises the steps:
1) in reactor, methionine(Met), alkali salt, crystallizing agent and water is added, heating for dissolving;
2) pH adjusting agent regulator solution pH value to 6 ~ 8 are added under stirring;
3) metal-salt is added, 60 DEG C ~ 90 DEG C reactions;
4) crystallisation by cooling, obtains methionine metal chelate after drying.
Described crystallizing agent is any one in Trisodium Citrate, sodium bicarbonate, sodium formiate, sodium acetate.
The consumption of crystallizing agent is 10 ~ 20% of methionine(Met) quality.
Described metal-salt is any one in zinc sulfate, copper sulfate, chromium chloride, 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 adjusting agent is sodium hydroxide or ammoniacal liquor.
In step 1), the mass volume ratio of methionine(Met) and water is 1g:1 ~ 2ml.
The time of reacting described in step 3) is 10 ~ 20min.
The macrobead crystal formation methionine metal chelate that above method prepares is preparing the application on fodder additives.
Methionine chelate thing synthetic route of the present invention is shown in Fig. 1, its structural formula (M represents metallic element) as follows:
The invention has the beneficial effects as follows:
The invention provides a kind of technical intelligence of synthesizing macrobead crystal formation methionine(Met) series inner complex, can effectively solve in actual production process, filter cake be sticky, and hard-pumped is filtered, and after drying, 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 large, and in crystallinity gloss, the methionine(Met) series inner complex fluency simultaneously obtained is good, can effectively mix with feed,
simplify the operation flow process, can be used as animal feedstuff additive, supplements each dvielement in daily ration, improves growth performance and the immune performance of animal body.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart (for zinc methionine) of macrobead crystal formation methionine(Met) of the present invention series inner complex;
Fig. 2 be embodiment 1 zinc methionine inner complex before improvement with improve after crystalline structure comparison diagram;
Fig. 3 be embodiment 4 methionine copper chelate before improvement with improve after crystalline structure comparison diagram;
Fig. 4 be embodiment 6 manganese methionine inner complex before improvement with improve after crystalline structure comparison diagram;
Fig. 5 be embodiment 7 chromium methionine chelate before improvement with improve after crystalline structure comparison diagram.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but be not limited thereto.
embodiment 1
The preparation method of macrobead crystal formation zinc methionine, its concrete steps are as follows:
Take 30.1g(0.2mol) methionine(Met), add water 100mL, adds sodium hydroxide 8.0g, sodium laurylsulfonate 6.0g, and heated and stirred is dissolved; Add 29.8g(0.1mol again) Zinc Sulphate Heptahydrate, mixing solutions pH value is regulated to be about 7 with a small amount of sodium hydroxide again, control temperature was 60 DEG C of reactions 15 minutes, cooling suction filtration, solid is dried to constant weight at 105 DEG C, obtain zinc methionine 34.8g, detecting Zn 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 60.2g(0.4mol) methionine(Met), add water 200ml, adds sodium hydroxide 15.0g, anhydrous sodium acetate 6.0g, heated and stirred is dissolved, then adds 59.6g(0.2mol) Zinc Sulphate Heptahydrate, regulate mixing solutions pH value to be about 7 with ammoniacal liquor, control temperature was 70 DEG C of reactions 15 minutes, cooling suction filtration, solid is dried to constant weight at 105 DEG C, obtains zinc methionine 56.4g, detecting Zn 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 60.2g(0.4mol) methionine(Met), add water 200ml, adds sodium bicarbonate 6.0g, then add the sodium hydroxide of 15.0g, add 59.6g(0.2mol) Zinc Sulphate Heptahydrate, regulate mixing solutions pH to be about 7 with sodium hydroxide, control temperature, 80 DEG C of reactions 15 minutes, cools suction filtration, solid is dried to constant weight at 105 DEG C, obtain zinc methionine 68.3g, detecting Zn content is 17.86%, and methionine content is 80.99%.
The product that embodiment 1 ~ 3 obtains is washed with water repeatedly, dries, the zinc methionine inner complex that purity is higher can be obtained, in white crystalline powder gloss, be insoluble in water.Be placed in basis of microscopic observation, simultaneously with former technique (with reference to Chinese grain and oil journal 1997 02 interim " research of Synthetic Conditions for Methionine Chelated Zinc ", adopt 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 DEG C, and the reaction times is 15 minutes) products therefrom contrasts, and before and after zinc methionine, the contrast of technique crystal formation is as shown in Figure 2.
embodiment 4
The preparation method of macrobead crystal formation copper methionine, its concrete steps are as follows:
Take 30.1g(0.2mol) methionine(Met), add water 100ml, adds sodium hydroxide 8.0g, adds Trisodium Citrate 6.0g, add 25.5g(0.1mol again) cupric sulfate pentahydrate, regulate pH to be about 7 with sodium hydroxide, control temperature, 80 DEG C of reactions 15 minutes, cools suction filtration, solid is dried to constant weight at 105 DEG C, obtain 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 90.3g(0.6mol) methionine(Met), add water 250ml, adds sodium hydroxide 23.0g, sodium formiate 6.0g, add 76.5g(0.3mol again) cupric sulfate pentahydrate, regulate pH to be about 7.0 with sodium hydroxide, control temperature, 70 DEG C of reactions 15 minutes, cools suction filtration, solid is dried to constant weight at 105 DEG C, obtain copper methionine 103.0g, detecting copper content is 17.54%, and nitrogen content is 81.38%.
The product that embodiment 4 and 5 obtains is washed with water repeatedly, dries, the methionine copper chelate that purity is higher can be obtained, in blue crystalline powder gloss, be insoluble in water.Be placed in basis of microscopic observation, simultaneously with former technique (with reference to Chinese grain and oil journal 1997 02 interim " research of Synthetic Conditions for Methionine Chelated Zinc ", adopt 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 DEG C, and the reaction times is 15 minutes) products therefrom contrasts, and before and after copper methionine, the contrast of technique crystal formation is as shown in Figure 3.
embodiment 6
The preparation method of macrobead crystal formation manganese methionine, its concrete steps are as follows:
Take 60.2g(0.4mol) methionine(Met), add water 180ml, adds sodium formiate 8.0g, then add the sodium hydroxide of 15.0g, add 33.8g(0.2mol) manganese sulfate monohydrate, regulate mixing solutions pH to be about 7 with sodium hydroxide, control temperature reacts 15 minutes at 80 DEG C, crystallisation by cooling suction filtration, solid is dried to constant weight at 105 DEG C, obtain manganese methionine 67.9g, detecting Fe content is 15.49%, and methionine content is 82.83%.
Product washing with alcohol embodiment 6 obtained repeatedly, is dried, can be obtained the manganese methionine inner complex that purity is higher, in white crystalline particle, more soluble in water.Be placed in basis of microscopic observation, simultaneously with former technique (with reference to Chinese grain and oil journal 1997 02 interim " research of Synthetic Conditions for Methionine Chelated Zinc ", adopt 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 DEG C, and the reaction times is 15 minutes) products therefrom contrasts, and before and after manganese methionine, the contrast of technique crystal formation is as shown in Figure 4.
embodiment 7
The preparation method of macrobead crystal formation chromium methionine, its concrete steps are as follows:
Take 45.1g(0.3mol) methionine(Met), add water 100ml, adds sodium hydroxide 11.5g, adds Trisodium Citrate 9.0g, add 26.7g(0.1mol again) chromium chloride hexahydrate, regulate pH to be about 7 with sodium hydroxide, control temperature, 80 DEG C of reactions 15 minutes, cools suction filtration, solid is dried to constant weight at 105 DEG C, obtain chromium methionine 48.5g, detecting chromium content is 10.17%, and methionine content is 85.39%.
Product washing with alcohol embodiment 7 obtained repeatedly, is dried, can be obtained the chromium methionine chelate that purity is higher, in burgundy crystals particle, more soluble in water.Be placed in basis of microscopic observation, simultaneously with former technique (with reference to Chinese grain and oil journal 1997 02 interim " research of Synthetic Conditions for Methionine Chelated Zinc ", adopt 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 DEG C, and the reaction times is 15 minutes) products therefrom contrasts, and before and after chromium methionine, the contrast of technique crystal formation is as shown in Figure 4.
Analyze the methionine(Met) series inner complex product that two kinds of techniques obtain, analytical results is in table 1 simultaneously.
By contrast, we can find that the methionine(Met) serial inner complex product Crystal type after improving obviously increases, and unit weight improves, and granularity increases, and sticks greasy phenomenon for improving filter cake, and dehydration is difficult, drying time length has very great help.
experimentation on animals 1
The macrobead crystal formation zinc methionine prepared with embodiment 1 below carries out experimentation on animals.
Will be even with a collection of 200 sizes, athletic 160 age in days Luo Man hens raise one week in advance, therefrom select 180 healthy hens that Age at first laying is identical, body weight is close and be divided into 3 groups at random, 1 experimental group (basal diet per ton adds the zinc methionine 70 grams of embodiment 1), 1 negative control group (basal diet), 1 positive control group (basal diet per ton adds the zinc methionine 70 grams prepared by former technique), often organizes 60 chickens.
This experiment is carried out in semi open model hen house, and trial period is 6 weeks.Duration of test, feeds powder, and free choice feeding is drunk water; Keep 16 h light every day, temperature is at 20-28 DEG C, 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: the egg number of each experimental group of time recording every day and egg size; Measure weekly each repetition feed consumption rate and laying hen individual weight; Add up weekly egg size, laying rate, feed consumption rate and feedstuff-egg ratio.
Slaughter determining: randomly draw 9 hens and butcher, carotid artery gets the level of methionine(Met) and zinc element in hematometry blood.
Experimental result shows, the average growth rate of 3 groups of laying hens is followed successively by from high to low: positive control group ﹥ experimental group ﹥ bears control group, but there was no significant difference (P>0.05) between three groups.
Laying rate is followed successively by from high to low: experimental group ﹥ positive control group ﹥ bears control group.Experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
In blood, the level of methionine(Met) is followed successively by from high to low: experimental group ﹥ positive control group ﹥ bears control group.Equally, experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
In blood, the level of zinc element is followed successively by from high to low: experimental group ﹥ positive control group ﹥ bears control group.Equally, experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
Above description of test, the zinc methionine utilizing the inventive method to prepare can be used as the zinc source in feed, supplements the zinc element in daily ration and methionine(Met), improves growth performance and the immune performance of animal body.And increase due to its granularity, unit weight improves, and sticks greasy phenomenon for improving filter cake, and dehydration is difficult, drying time is long has very great help, and can effectively enhance productivity.
experimentation on animals 2
The macrobead crystal formation copper methionine prepared with embodiment 4 below carries out experimentation on animals.
1, Setup Experiments
By 30 close batch, body weight 35 age in days weanling pigs that are close, that be in a good state of health raise one week in advance, be divided into 3 groups at random, 1 experimental group (adding macrobead crystal formation copper methionine 100 grams in basal diet per ton), 1 negative control group (basal diet), 1 positive control group (basal diet per ton adds the copper methionine 100 grams prepared by former technique), often organizes 10 pigs.
This experiment is carried out in insulation pig house, and trial period is 8 weeks.Duration of test, free choice feeding is drunk water; Natural lighting, temperature is at 22-28 DEG C, 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 time recording every day every hurdle piglet; Measure weekly the individual weight of each piglet; Add up feedstuff-meat ratio weekly, calculate all food consumptions, day weight gain.
3, experimental result
Experimental result shows, daily ingestion amount is followed successively by from high to low: positive control group ﹥ experimental group ﹥ bears control group, but there was no significant difference (P>0.05) between three groups.
Feedstuff-meat ratio is followed successively by from low to high: experimental group ﹤ positive control group ﹤ bears control group.Experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
Average growth rate is followed successively by from high to low: experimental group ﹥ positive control group ﹥ bears control group.Equally, experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
Above description of test, the macrobead crystal formation copper methionine utilizing the inventive method to prepare can be used as the copper source in feed, supplements the copper in daily ration and methionine(Met), improves growth performance and the immune performance of animal body.And increase due to its granularity, unit weight improves, and sticks greasy phenomenon for improving filter cake, and dehydration is difficult, drying time is long has very great help, and can effectively enhance productivity.
experimentation on animals 3
The macrobead crystal formation manganese methionine prepared with embodiment 6 below carries out experimentation on animals.
Will be even with a collection of 200 sizes, athletic 160 age in days Luo Man hens raise one week in advance, therefrom select 180 healthy hens that Age at first laying is identical, body weight is close and be divided into 3 groups at random, 1 experimental group (basal diet per ton adds the manganese methionine 100 grams of embodiment 1), 1 negative control group (basal diet), 1 positive control group (basal diet per ton adds the manganese methionine 100 grams prepared by former technique), often organizes 60 chickens.
This experiment is carried out in semi open model hen house, and trial period is 6 weeks.Duration of test, feeds powder, and free choice feeding is drunk water; Keep 16 h light every day, temperature is at 20-28 DEG C, 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: the egg number of each experimental group of time recording every day and egg size; Measure weekly each repetition feed consumption rate and laying hen individual weight; Add up weekly egg size, laying rate, feed consumption rate and feedstuff-egg ratio.
Slaughter determining: randomly draw 9 hens and butcher, carotid artery gets the level of methionine(Met) and manganese element in hematometry blood.
Experimental result shows, the average growth rate of 3 groups of laying hens is followed successively by from high to low: experimental group ﹥ positive control group ﹥ bears control group, but there was no significant difference (P>0.05) between three groups.
Laying rate is followed successively by from high to low: positive control group ﹥ experimental group ﹥ bears control group.Experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
In blood, the level of methionine(Met) is followed successively by from high to low: experimental group ﹥ positive control group ﹥ bears control group.Equally, experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
In blood, the level of manganese element is followed successively by from high to low: experimental group ﹥ positive control group ﹥ bears control group.Equally, experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
Above description of test, the manganese methionine utilizing the inventive method to prepare can be used as the manganese source in feed, supplements the manganese element in daily ration and methionine(Met), improves animal tissues to the utilization of manganese element.And increase due to its granularity, unit weight improves, and sticks greasy phenomenon for improving filter cake, and dehydration is difficult, drying time is long has very great help, and can effectively enhance productivity.
experimentation on animals 4
The macrobead crystal formation chromium methionine prepared with embodiment 7 below carries out experimentation on animals.
Will be even with a collection of 200 sizes, athletic 160 age in days Luo Man hens raise one week in advance, therefrom select 180 healthy hens that Age at first laying is identical, body weight is close and be divided into 3 groups at random, 1 experimental group (basal diet per ton adds the chromium methionine 0.2 gram of embodiment 1), 1 negative control group (basal diet), 1 positive control group (basal diet per ton adds the chromium methionine 0.2 gram prepared by former technique), often organizes 60 chickens.
This experiment is carried out in semi open model hen house, and trial period is 6 weeks.Duration of test, feeds powder, and free choice feeding is drunk water; Keep 16 h light every day, temperature is at 20-28 DEG C, 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: the egg number of each experimental group of time recording every day and egg size; Measure weekly each repetition feed consumption rate and laying hen individual weight; Add up weekly egg size, laying rate, feed consumption rate and feedstuff-egg ratio.
Slaughter determining: randomly draw 9 hens and butcher, carotid artery gets the level of methionine(Met) and chromium element in hematometry blood.
Experimental result shows, the average growth rate of 3 groups of laying hens is followed successively by from high to low: positive control group ﹥ experimental group ﹥ bears control group, but there was no significant difference (P>0.05) between three groups.
Laying rate is followed successively by from high to low: positive control group ﹥ experimental group ﹥ bears control group, but there was no significant difference (P>0.05) between three groups.
Feedstuff-meat ratio is followed successively by from low to high: experimental group ﹤ positive control group ﹤ bears control group.Experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
In blood, the level of methionine(Met) is followed successively by from high to low: experimental group ﹥ positive control group ﹥ bears control group.Equally, experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
In blood, the level of chromium element is followed successively by from high to low: experimental group ﹥ positive control group ﹥ bears control group.Equally, experimental group and positive control group difference not significantly (P>0.05), but all with negative control group significant difference (P<0.05).
Above description of test, the chromium methionine utilizing the inventive method to prepare can be used as the chromium source in feed, supplements the chromium element in daily ration and methionine(Met), improves efficiency of feed utilization.And increase due to its granularity, unit weight improves, and sticks greasy phenomenon for improving filter cake, and dehydration is difficult, drying time is long has very great help, and can effectively enhance productivity.
Claims (4)
1. a preparation method for macrobead crystal formation methionine metal chelate, comprises the steps:
1) in reactor, methionine(Met), NaOH, crystallizing agent and water is added, heating for dissolving;
2) pH adjusting agent regulator solution pH value to 6 ~ 8 are added under stirring;
3) metal-salt is added, 60 DEG C ~ 90 DEG C reactions;
4) crystallisation by cooling, obtains methionine metal chelate after drying;
Described crystallizing agent is any one in Trisodium Citrate, sodium bicarbonate, sodium formiate, sodium acetate;
The consumption of crystallizing agent is 10 ~ 20% of methionine(Met) quality;
Described metal-salt is any one in zinc sulfate, copper sulfate, chromium chloride, manganous sulfate, and the mol ratio of methionine(Met) and metal-salt is 2 ~ 8:1 ~ 4;
The mol ratio of methionine(Met) and NaOH is 1:0.8 ~ 1.2;
In step 1), the mass volume ratio of methionine(Met) and water is 1g:1 ~ 2ml.
2. method according to claim 1, is characterized in that, the mol ratio of methionine(Met) and metal-salt is 2:1.
3. method according to claim 1, is characterized in that, described pH adjusting agent is sodium hydroxide or ammoniacal liquor.
4. method according to claim 1, is characterized in that, the time of reacting described in step 3) is 10 ~ 20min.
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| CN103497131B (en) * | 2013-10-08 | 2015-05-13 | 重庆紫光化工股份有限公司 | Preparation method of 2-hydroxy-4-methylthio butyric acid metal chelate |
| CN103467348B (en) * | 2013-10-08 | 2015-09-16 | 重庆紫光化工股份有限公司 | The preparation method of macrobead crystal formation high-bulk-density MHA calcium |
| CN103497135B (en) * | 2013-10-24 | 2016-06-08 | 重庆紫光化工股份有限公司 | One prepares N-methylol-D, the method for L-Methionine microelement chelate |
| CN103497133B (en) * | 2013-10-24 | 2015-05-13 | 重庆紫光化工股份有限公司 | Method for preparing N-methylol group-D,L-calcium methionine microelement chelates by means of saponification liquid produced through D,L- methionine |
| 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 |
| 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 |
| 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 |
| 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) |
| CN109678769B (en) * | 2019-02-14 | 2024-04-19 | 天宝动物营养科技股份有限公司 | Method for producing methionine metal chelate by comprehensively utilizing methionine crystallization mother liquor |
| CN109678768B (en) * | 2019-02-14 | 2020-12-22 | 天宝动物营养科技股份有限公司 | Method for producing methionine metal chelate by using methionine crystallization mother liquor |
| 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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Inventor after: Shu Xugang Inventor after: Duan Jingna Inventor after: Wu Chunli Inventor after: Fan Mingzhi Inventor after: Xu Xiang Inventor after: Gao Junyong Inventor before: Shu Xugang Inventor before: Duan Jingna Inventor before: Wu Chunli Inventor before: Fan Mingzhi Inventor before: Xu Xiang Inventor before: Gao Junyong |