CN104341329A - Production method of calcium 2-hydroxy-4-(methylthio)butyrate - Google Patents

Production method of calcium 2-hydroxy-4-(methylthio)butyrate Download PDF

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Publication number
CN104341329A
CN104341329A CN201410556877.9A CN201410556877A CN104341329A CN 104341329 A CN104341329 A CN 104341329A CN 201410556877 A CN201410556877 A CN 201410556877A CN 104341329 A CN104341329 A CN 104341329A
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China
Prior art keywords
methionine
calcium
hydroxy
production method
stirring
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CN201410556877.9A
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Chinese (zh)
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高纪峰
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Individual
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Individual
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Priority to CN201410556877.9A priority Critical patent/CN104341329A/en
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Abstract

The invention discloses a production method of calcium 2-hydroxy-4-(methylthio)butyrate. The method comprises the following steps: warming and keeping liquid methionine at about 80 DEG C for later use; firstly feeding calcium hydroxide powder to a reaction tank with a warming and stirring device; stirring and slowly adding liquid methionine at about 80 DEG C within 60 minutes; further stirring for 10 minutes; stopping and discharging, wherein no water is added to the materials in the formula, and according to the formula, washing or drying is not needed, and post processing is not needed; and cooling, packaging and warehousing the product.

Description

A kind of methionine hydroxy calcium production method
Technical field
The present invention relates to a kind of method for producing feed additive, particularly relate to a kind of preparation method of methionine hydroxy calcium.
Background technology
Methionine(Met) as amino acids fodder additives, is a kind of animal growth promoter in feed, for the synthesis of protein, can improve feed conversion rate, growth of animal rate and laying rate of poultry.But methionine(Met) production cost is higher, domestic production is less, almost do not have, source of goods shortage, in order to the development of satisfied Chinese aquaculture and fodder industry, scientific and technical personnel develop methionine(Met) similar compound as 2-hydroxy-4-methyl sulphur-butyric acid, " have the preparation method of the 2-hydroxy-4-methyl-thiobutanoic acid of stability in storage " in China Patent No. CN97125703.5.It is short that it has technical process, the low advantage of cost, and this compound can be converted into methionine(Met) in vivo equally, the solid amino acid that commercially fictitious hosts is more expensive gradually, but because be liquid, and there is stronger corrodibility and irritating smell, therefore store, transport, use inconvenience, expensive dedicated liquid charging system must be installed, cause the rising of use cost.And the said products compound is only to provide a kind of growth of animal promoter action, and action function is single.
In view of the variety of problems that existing document exists, the present invention, according to the character of reaction raw materials and reaction mechanism, after the relative merits in conjunction with relevant different document, has invented a kind of method preparing hydroxyl egg acid calcium newly.
Summary of the invention
The invention provides with the method for feed grade liquid methionine for Material synthesis hydroxyl Methionine calcium salt, shortcoming and the deficiency of prior art existence can be solved.
For realizing object of the present invention, this methionine hydroxy calcium production method, is characterized in that, it comprises the following steps: main is raw material with liquid methionine, in container airtight especially, and same calcium hydroxide reaction, generate methionine hydroxy calcium, specifically comprise the following steps:
(1) liquid methionine temperature rising reflux is heated be retained to about 80 DEG C, insulation 7-10 hour;
(2) calcium hydroxide powder first drops into be with and adds in the retort of gentle whipping appts, and keep temperature 120 DEG C in tank, start is stirred;
(3) slowly add the liquid methionine of temperature about 80 DEG C while stirring, after adding, continue stirring 10 minutes again, shut down discharging;
(4) reactant slow cooling is to room temperature, sieves, packaging, warehouse-in.
The weight ratio of described calcium hydroxide and hydroxy methionine is 4:11.Described step (2) retort inwall and agitating vane are stainless steels, antivacuum.
Adopt methionine hydroxy calcium (CH3SCH2C (NH2) CHCOO) 2Ca that present method is produced, solid granular product, containing 100% monomer, as a kind of methionine(Met) source in feed, be directly used in feed premix, concentrated fodder etc., operation simplifies, and efficiency improves, when changing that liquid methionine is for feed in the past, not easily dry, stink Strong is strong, the shortcoming that the production cycle is long.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment
Heat is retained to about 80 DEG C to raw material liq methionine(Met) of purchasing (2-amino-4-methylmercapto butyric acid), for subsequent use.The feed hydrogen calcium oxide CaHO3 that purchases, Powdered, normal temperature, for subsequent use.400 kilograms of calcium hydroxide powder first drop into band and add in the retort of gentle whipping appts.(retort inwall and agitating vane are stainless steels, antivacuum, keep temperature 120 DEG C in tank), start is stirred.Slowly add the liquid methionine 1100 kilograms of temperature about 80 DEG C while stirring, within 60 minutes, add, then continue stirring 10 minutes, shut down discharging.Now reactant is fine particle shape, is finished product.Formula does not add water, and does not wash and does not dry, do not need post-treatment.Finished product cooling packing is put in storage.
test example
Two groups of milk cow research methionine hydroxy calciums are selected to test as the feeding effect of ruminant feed supplement.
1. test materials
1.1 1 groups with the addition of methionine hydroxy calcium; One group is not added methionine hydroxy calcium; Material is all provided by honest source feed group.
1.2 test milk cows are selected and grouping:
1.2.1 the selection of kind
Purebred Holstein cow.The unique dairy breed ox of China that selection cross offspring formed jointly is carried out, 305 days average milk production 6359 kilograms, milk fat content 3.56% abroad by the Holstein cow pure breeding offspring introduced and with Chinese Cattle level.
1.2.2 the selection of production performance
The average milk production of parity more than 6359 kilograms, A.milkfat percentage more than 3.5%, adult weight more than 550 kilograms.
1.2.3 the selection of appearance
Hair color: chequered with black and white, flower sheet is clearly demarcated, and forehead has day shift, and belly, lower extremities and tail end are in white, and angle is yellow, the top of the horn black.
Build: figure is delicate and pretty, corner angle are clearly demarcated, and obviously, muscle development appropriateness, subcutaneous lipids is few for joint, muscle tendon.The thin bone of skin is thin, and exposed vessel, capillary is short and glossy.Neck is thin and grow, and there is stringer wrinkle neck side.Back of the body waist is straight, and four limbs are well-balanced, and tail is elongated.The comparatively front body of rear quarters is flourishing, sees from the side, above, above all in wedge type.
2. test method
The milk cow selecting diary farm to raise in test milk cow of first 8 weeks within third trimester of pregnancy in last week and lactation period, 21 g/d N mono-methylol one DL mono-Methionine calcium salts are added in identical dairy cow diet, accomplish that in test environment is consistent, unified raising, free choice feeding and management as far as possible.
3. trial period test:
In dairy cow diet, N mono-methylol one DL mono-Methionine calcium salt is added in table 1, the food ration of per day dry-matter can be improved, mineral substance has similar trend with the consumption of other nutritive substances to the consumption of dry-matter, in interpolation group blood plasma, average urea level is 28.88mg/kg, and do not add group for 30.57mg/kg, but the two difference is not too remarkable;
Sequence number Add title Food consumption Urea level in blood plasma Improve milk yield ; Milk fat content
1 Add methionine hydroxy calcium 10Kg 28.88mg/kg 4.79% 4.50%;
2 Do not add methionine hydroxy calcium 7.0Kg 30.57mg/kg 3.80% 3.12%
4. conclusion:
In the test milk cow of choosing, be divided into two groups, one group is added methionine hydroxy calcium, and one group is not added, and makes them grow up in identical environment, raising, free choice feeding and management.Test result shows that methionine hydroxy calcium adds the increase that can reduce ketone body levels in blood in dairy cow diet to, and the reduction of sugared concentration in limit blood, this effect especially shows in energy limited daily ration, in the daily ration of energy abundance, milk yield is not by the impact of N mono-methylol one DL mono-Methionine calcium salt, and in energy limited daily ration, N mono-methylol one DL mono-Methionine calcium salt can improve milk yield.In daily ration, add the dairy fat content that N mono-methylol one DL mono-Methionine calcium salt can reduce earlier lactating period, and increase the dairy fat content of late lactation.

Claims (3)

1. a methionine hydroxy calcium production method, is characterized in that: main is raw material with liquid methionine, and in container airtight especially, same to calcium hydroxide reaction, generates methionine hydroxy calcium, specifically comprise the following steps:
(1) liquid methionine temperature rising reflux is heated be retained to about 80 DEG C, insulation 7-10 hour;
(2) calcium hydroxide powder first drops into be with and adds in the retort of gentle whipping appts, and keep temperature 120 DEG C in tank, start is stirred;
(3) slowly add the liquid methionine of temperature about 80 DEG C while stirring, after adding, continue stirring 10 minutes again, shut down discharging;
(4) reactant slow cooling is to room temperature, sieves, packaging, warehouse-in.
2. methionine hydroxy calcium production method according to claim 1, is characterized in that: the weight ratio of calcium hydroxide and hydroxy methionine is 4:11.
3. methionine hydroxy calcium production method according to claim 1, is characterized in that: described step (2) retort inwall and agitating vane are stainless steels, antivacuum.
CN201410556877.9A 2014-10-20 2014-10-20 Production method of calcium 2-hydroxy-4-(methylthio)butyrate Pending CN104341329A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577479A (en) * 2019-09-25 2019-12-17 福安药业集团重庆博圣制药有限公司 Novel crystal form A of racemic hydroxy methionine calcium and preparation method and application thereof
CN114436920A (en) * 2022-01-21 2022-05-06 湖南德邦生物科技有限公司 Preparation method of feed-grade copper hydroxymethionine

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2044755A (en) * 1979-03-06 1980-10-22 Degussa Derivatives of D-2-hydroxy-4- methylmercaptobutyric acid, a Process for their Production and their Use
CN1493560A (en) * 2002-10-30 2004-05-05 周建康 Compond for implementing methionine and calcium and its production method
US20060287543A1 (en) * 2005-04-29 2006-12-21 Novus International, Inc. Process for purification and decolorization of 2-hydroxy-4-(methylthio)butanoic acid (HMTBA)-containing complexes
CN101348451A (en) * 2008-09-05 2009-01-21 南京生命能科技开发有限公司 Preparation of medicinal D,L-2-hydroxy-4-methylthio calcium butyrate
CN103153937A (en) * 2010-09-22 2013-06-12 安迪苏爱尔兰有限公司 Method for preparing a complex of an acid and a metal
CN103420881A (en) * 2013-09-02 2013-12-04 绍兴民生医药有限公司 Novel method for preparing medicinal despun hydroxyl methionine calcium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2044755A (en) * 1979-03-06 1980-10-22 Degussa Derivatives of D-2-hydroxy-4- methylmercaptobutyric acid, a Process for their Production and their Use
CN1493560A (en) * 2002-10-30 2004-05-05 周建康 Compond for implementing methionine and calcium and its production method
US20060287543A1 (en) * 2005-04-29 2006-12-21 Novus International, Inc. Process for purification and decolorization of 2-hydroxy-4-(methylthio)butanoic acid (HMTBA)-containing complexes
CN101348451A (en) * 2008-09-05 2009-01-21 南京生命能科技开发有限公司 Preparation of medicinal D,L-2-hydroxy-4-methylthio calcium butyrate
CN103153937A (en) * 2010-09-22 2013-06-12 安迪苏爱尔兰有限公司 Method for preparing a complex of an acid and a metal
CN103420881A (en) * 2013-09-02 2013-12-04 绍兴民生医药有限公司 Novel method for preparing medicinal despun hydroxyl methionine calcium

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577479A (en) * 2019-09-25 2019-12-17 福安药业集团重庆博圣制药有限公司 Novel crystal form A of racemic hydroxy methionine calcium and preparation method and application thereof
CN114436920A (en) * 2022-01-21 2022-05-06 湖南德邦生物科技有限公司 Preparation method of feed-grade copper hydroxymethionine

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Application publication date: 20150211