CN103497133B - Method for preparing N-methylol group-D,L-calcium methionine microelement chelates by means of saponification liquid produced through D,L- methionine - Google Patents
Method for preparing N-methylol group-D,L-calcium methionine microelement chelates by means of saponification liquid produced through D,L- methionine Download PDFInfo
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Abstract
The invention relates to the field of the chemical industry, in particular to a method for preparing N-methylol group-D,L-calcium methionine microelement chelates. The method is environmentally friendly and low in cost. According to the method, saponification liquid produced in the production process of D,L-methionine serves as production raw materials and reacts with trace metal element calcium salt to obtain D,L-methionine microelement chelates, the obtained D,L-methionine microelement chelates react with formaldehyde in a water medium, filtering, washing in cold water, drying and crushing are carried out after the reaction, and the powdered N-methylol group-D,L-calcium methionine microelement chelates are obtained. According to the method, high-purity D,L-methionine is needless, the N-methylol group-D,L-calcium methionine microelement chelates are directly prepared through the saponification liquid, and production cost is reduced. According to the method, the high-purity N-methylol group-D,L-calcium methionine microelement chelates are prepared, stability is high, animals can easily digest and absorb the N-methylol group-D,L-calcium methionine microelement chelates, the N-methylol group-D,L-calcium methionine microelement chelates can serve as feed additions, obtained filter liquor can be recycled, and the method is environmentally friendly.
Description
Technical field
The present invention is directed to chemical field, relate to a kind of N-methylol-D, the preparation method of L-Methionine microelement chelate, is specifically related to utilize D, and the saponification liquor that L-Methionine is produced prepares N-methylol-D, the method for L-Methionine microelement chelate.
Background technology
Metal trace element uses as fodder additives and experienced by three developmental stage: the first stage, the inorganic salt of the trace element used, mainly vitriol and its oxide compound etc., but find many shortcomings in the application, such as with the antagonistic action of other nutritive substances, to the destruction of the nutrition such as VITAMIN, the low and mixture homogeneity of biological value is low; Subordinate phase: in order to overcome the shortcoming of the inorganic salt using trace element, people bring into use trace mineral supplement-organic acid salt.But organo-metallic trace element salt also exists the weak points such as biology utilization ratio is low, biochemical function is unstable equally; Phase III: micro-metals amino-acid chelate is the new and effective fodder additives of a class that first 20 century 70s are succeeded in developing the earliest by U.S.'s ALBICN biology laboratory, have good stability, anti-interference, easily by animal absorb, biological value advantages of higher, be described as the third generation of micro-metals additive.
The eighties in 20th century, China starts to be studied microelements aminophenol chelated and to apply, and achieves good effect on pig, fowl, ruminating animal, rabbit and fish thereof.Product main at present has ferrous methionine, copper methionine, cobalt methionine, Methionin ferrous iron, Copper lysinate, glycine ferrous etc., and some composite trace element amino-acid chelate additives.Because amino acid is easily by ruminant tumor gastric microbiological deterioration, do not utilized by organism by cud, utilization ratio is lower, limits the application of above-mentioned microelements aminophenol chelated.
How to meet the demand of high yield ruminating animal to gal4 amino acid and trace element thereof to have become domestic and international dietician and paid close attention to.Much research shows: in its feed, add rumen-bypass amino acid microelement chelate is the advanced means that ruminating animal provides desirable Small intestine amino acid, not only be conducive to amino acid whose absorption, and the daily required trace element of supplementary animal, effect can not be damaged to other nutritive elements, to improve feed utilization ratio, reduce gal4 amino acid waste, reduce production cost, to improve the throughput of ruminating animal all very favourable.
Methionine(Met) is the first limiting amino acids of poultry, methionine additive conventional in feed mainly contains powdery D, L-Methionine (DLM) and methionine hydroxy analog (HMB), at present, methionine trace element chelate (application number be 201110342880.7 patent of invention disclose a kind of method preparing methionine trace element chelate) and microelement methionine hydroxy analogue chelate (application number be 201310199220.7 patent of invention disclose a kind of preparation method of microelement methionine hydroxy analogue chelate additive) developed the application that comes into the market.But, existingly prepare in the method for methionine(Met) secondary element inner complex, all also exist that the synthesis technique cycle is long, yield is low, production cost is high, the purity of product is low, the phenomenon of poor stability.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of N-methylol-D of environmental friendliness low cost, the preparation method of L-Methionine microelement chelate, with D, the saponification liquor produced in L-Methionine production process is raw material, production cost is reduced, and synthesis technique shortens, and improves synthetic ratio.
For achieving the above object, technical scheme of the present invention is:
Utilize D, L-Methionine is produced saponification liquor and is prepared N-methylol-D, the method for L-Methionine microelement chelate, comprises the step of carrying out as follows:
(1) with D, it is raw material that L-Methionine produces saponification liquor, and with solubility micro-metals reactant salt, reaction terminates rear filtration, and gained filtrate crystallisation obtains D, L-Methionine microelement chelate; Described D, it is by D that L-Methionine produces saponification liquor, and L-Methionine is produced intermediate material 5-(2-methylthio ethyl)-glycolylurea and produced through basic hydrolysis; In the method for the invention, after saponification liquor and micro-metals reactant salt, filter the filtrate continuation obtained and utilize, the solid matter obtained is mainly carbonic acid micro-metals insolubles, discharges reaction system, free from environmental pollution;
(2) by the D of step (1) gained, L-Methionine microelement chelate carries out hydroxymethylation with formaldehyde in water medium, filters to obtain N-methylol-D, L-Methionine microelement chelate after reaction terminates.
In the method for the invention, in step (1), take saponification liquor as raw material, with micro-metals reactant salt, reaction terminates rear filtration, and filtrate also without crystallization treatment, can be cooled to 20 DEG C ~ 30 DEG C by gained filtrate, obtain containing D, the mixed serum of L-Methionine microelement chelate is directly used in next step and formaldehyde to carry out hydroxymethylation and carries out methylolation.Gained filtrate crystallisation is preferably obtained D by the present invention, L-Methionine microelement chelate solid, and then carries out hydroxymethylation for next step and formaldehyde.
Above-mentioned preparation N-methylol-D, the method reaction formula of L-Methionine microelement chelate is as follows:
Wherein: M is micro-metals, as the one in iron, copper, zinc, manganese, cobalt, nickel and chromium.
Further, described preparation N-methylol-D, the method of L-Methionine microelement chelate, described D, the saponification liquor that L-Methionine is produced is after adding sodium hydroxide by described intermediate product 5-(2-methylthio ethyl)-glycolylurea, is heated to 130 DEG C ~ 165 DEG C hydrolysis gained, described D, it is composed of the following components that L-Methionine produces saponification liquor: mass percent is the Sodium L-methioninate of 15% ~ 19%, and mass percent is the sodium carbonate of 9% ~ 13%, and the water medium of surplus.
In the present invention, the preparation of 5-(2-methylthio ethyl)-glycolylurea is by 3-methylthiopropionaldehyde and sodium cyanide, bicarbonate of ammonia reacts and obtains, 5-(2-methylthio ethyl)-glycolylurea, have another name called glycolylurea, it obtains described saponification liquor through basic hydrolysis, saponification liquor is D, intermediate in L-Methionine production process, main containing Sodium L-methioninate, saponification liquor is utilized to produce N-methylol-D, L-Methionine microelement chelate, comparatively D, L-Methionine is raw material, save sodium hydroxide, and save D, the purge process that L-Methionine is produced, therefore, saponification liquor is utilized to produce N-methylol-D, L-Methionine microelement chelate, comparatively use D, L-Methionine produces N-methylol-D, L-Methionine microelement chelate has larger cost advantage, and shorten the production cycle.As 5-(2-methylthio ethyl)-glycolylurea, after adding sodium hydroxide, be heated to 130 DEG C ~ 165 DEG C to hydrolysising reacting system, the saponification liquor (comprising Sodium L-methioninate and sodium carbonate) described in reaction generates, reaction formula is as follows:
In the present invention, described saponification liquor is that Chongqing purple light chemical company produces D, and produce in L-Methionine process, the saponification liquor of generation is without the need to purifying, without the need to adding alkali adjust ph, reaction can be participated in directly for the preparation of N-methylol-D, L-Methionine microelement chelate.Preferred saponification liquor is composed of the following components: mass percent is the Sodium L-methioninate (D, L-Methionine sodium) of 15% ~ 19%, and mass percent is 9% ~ 13% sodium carbonate, and the water medium of surplus;
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, in step (1), described solubility micro-metals salt is the trace metal salts of the solubility of iron, copper, zinc, manganese, cobalt, nickel and chromium.Described micro-metals salt is one or more in iron protochloride, ferrous sulfate, cupric chloride, copper sulfate, zinc chloride, zinc sulfate, Manganous chloride tetrahydrate, manganous sulfate, cobalt chloride, rose vitriol, nickelous chloride, single nickel salt, chromium chloride, chromium sulphate.
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, in step (1), saponification liquor is raw material, and with micro-metals reactant salt, described micro-metals salt is excessive.Preferably, in reaction system, trace metal atom and D, the mol ratio of L-Methionine is 1.35 ~ 1.8:1.
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, the temperature of reaction of described saponification liquor and described micro-metals salt is 60 DEG C ~ 90 DEG C, and the reaction times is 1 ~ 3 hour.
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, crystallization described in step (1) is that filtrate is cooled to 0 DEG C ~ 10 DEG C crystallizations.
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, in step (2), described D, the mol ratio that L-Methionine microelement chelate and formaldehyde carry out hydroxymethylation is 1.0 ~ 1.2:1.
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, in step (2), described D, L-Methionine microelement chelate and formaldehyde carry out hydroxymethylation temperature and control at 20 DEG C ~ 30 DEG C, and the reaction times is 0.5 ~ 2 hour.
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, the D described in step (2), L-Methionine microelement chelate and formaldehyde carry out after hydroxymethylation terminates, filter, gained N-methylol-D, L-Methionine microelement chelate cold water washing, then dry, pulverize, obtain Powdered N-methylol-D, L-Methionine microelement chelate.
Another object of the present invention is to provide several N-methylol-D, the preparation method of L-Methionine microelement chelate, this several method is all be raw material based on described saponification liquor, and preparation is produced; Its wastage rate are low, and yield is high;
Utilize D, L-Methionine produces saponification liquor cyclic production N-methylol-D, the production method of L-Methionine microelement chelate, described D, it is by D that L-Methionine produces saponification liquor, L-Methionine is produced intermediate material 5-(2-methylthio ethyl)-glycolylurea and produced through basic hydrolysis, comprised the following steps:
A is with D, and it is raw material that L-Methionine produces saponification liquor, and with solubility micro-metals reactant salt, reaction terminates rear filtration, gained filtrate crystallisation, obtains D after filtration, L-Methionine microelement chelate and filtrate 1; Described filtrate 1 takes turns N-methylol-D at another, and with D in the preparation process of L-Methionine microelement chelate, L-Methionine is produced saponification liquor mixing and continued to participate in reaction;
B is by the D of gained in steps A, and L-Methionine microelement chelate carries out hydroxymethylation with formaldehyde in water medium, filters to obtain N-methylol-D, L-Methionine microelement chelate and filtrate 2 after reaction terminates; Gained filtrate 2 takes turns N-methylol-D at another, continues to carry out hydroxymethylation with formaldehyde in the preparation process of L-Methionine microelement chelate.
Utilize N-methylol-D, N-methylol-D prepared by L-Methionine microelement chelate production equipment, the production method of L-Methionine microelement chelate, it is characterized in that: described N-methylol-D, L-Methionine microelement chelate production equipment, comprise D, L-Methionine produces the retort of saponification liquor and solubility micro-metals reactant salt, tripping device, hydroxymethylation tank, liquid storage tank, washing device, drying installation and shredding unit, described retort is communicated with tripping device respectively by being with the reflux line of valve with hydroxymethylation tank, described liquid storage tank respectively with retort, tripping device is connected with hydroxymethylation tank, described washing device is connected with described tripping device, described drying installation is connected with described washing device, described shredding unit is connected with described drying installation,
A adds D in retort, L-Methionine produces saponification liquor raw material, then solubility micro-metals salt is added, after question response terminates, send into tripping device and be separated removing solid matter, gained filtrate crystallisation, then D is separated through tripping device, L-Methionine microelement chelate and filtrate 1, described filtrate 1 is sent in liquid storage tank and is stored, another takes turns N-methylol-D, when the preparation of L-Methionine microelement chelate starts, described filtrate 1 takes turns N-methylol-D at another, with D in the preparation process of L-Methionine microelement chelate, L-Methionine is produced saponification liquor mixing and is continued to participate in reaction, described saponification liquor is through basic hydrolysis gained by 5-(2-methylthio ethyl)-glycolylurea,
B is by the D of gained in step a, L-Methionine microelement chelate sends into hydroxymethylation tank, in water medium, carry out hydroxymethylation with formaldehyde, reaction terminates to be separated to obtain N-methylol-D in rear feeding tripping device, L-Methionine microelement chelate and filtrate 2; Gained N-methylol-D, L-Methionine microelement chelate is sent in drying installation dry after sending into washing device cold water washing, send in shredding unit to pulverize to obtain Powdered N-methylol-D, L-Methionine microelement chelate after dry; Gained filtrate 2 is sent in liquid storage tank and is stored, and takes turns N-methylol-D at another, continues to carry out hydroxymethylation with formaldehyde in the preparation process of L-Methionine microelement chelate, for the preparation of N-methylol-D, and L-Methionine microelement chelate.
Beneficial effect of the present invention: the N-methylol-D that 1) the invention provides a kind of environmental friendliness low cost, the preparation method of L-Methionine microelement chelate, can effectively solve in actual production process, N-methylol-D, the yield of L-Methionine microelement chelate is low, production cost is high, and product purity is not high, the problem of poor stability; 2) preparation method's synthesis technique of the present invention is simple, and saponification liquor raw material is easy to get, and saponification liquor raw material does not need purifying, do not need adjust ph, can be directly used in reaction, overcomes D in the past, and L-Methionine raw material needs the problem of purifying; 3) the N-methylol-D that obtains of preparation method of the present invention, L-Methionine microelement chelate product purity is high, can as animal feedstuff additive, not only supplement the calcium constituent in daily ration, improve the production performance in animal body and immune performance, and the utilization ratio improving feed, the throughput that reduces the decomposition of methionine(Met) in cud, be beneficial to the absorption of methionine(Met), reduce production cost, improve ruminating animal.
Accompanying drawing explanation
Fig. 1 is N-methylol-D, L-Methionine microelement chelate production equipment structural representation.
Embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.The experimental technique of unreceipted actual conditions in preferred embodiment, usually conveniently condition.
Embodiment 1 D, L-Methionine produces saponification liquor
The 3-methylthiopropionaldehyde of 99.5% is mixed with the sodium cyanide solution of 30%, add ammonium bicarbonate aqueous solution again, airtightly be heated to 120 DEG C, react 20 minutes, obtain 5-(2-methylthio ethyl)-glycolylurea, described 5-(2-methylthio ethyl)-glycolylurea, through with after activated carbon decolorizing, is added sodium hydroxide hydrolysis, 130 DEG C ~ 165 DEG C is heated to hydrolysising reacting system and namely obtains saponification liquor to abundant hydrolysis.Be hydrolyzed the saponification liquor that obtains after activated carbon decolorizing can directly with below embodiment produce N-methylol-D, L-Methionine microelement chelate.Analyze the composition of saponification liquor, composed of the following components: D, the mass percentage of L-Methionine sodium is for being 17% ± 2%, and sodium carbonate mass percentage is 11% ± 2%, and surplus is water.
5-(2-methylthio ethyl)-glycolylurea also can directly be bought, and by purple light Tian Hua methionine(Met), company limited provides.
Embodiment 2 N-methylol-D, the preparation of L-Methionine zinc
D after the decolouring that Example 1 is mentioned, L-Methionine produces saponification liquor 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
Zinc Chloride Anhydrous 253.1 grams (1.87mol) is added in batches in above-mentioned saponification liquor after decolouring, be heated to 90 DEG C, temperature of reaction is kept to be 90 DEG C, react 1 hour, filter insolubles zinc carbonate, filtrate is cooled to 0 DEG C, obtain white precipitate, filter, obtain white D, L-Methionine zinc solid.
By D obtained above, L-Methionine zinc solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine zinc slurries, keeps temperature to be 23 DEG C, reacts 1 hour.After reaction terminates, suction filtration, cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 193 grams, L-Methionine zinc, yield 91%, purity is 99%, and wherein methionine content is 77.5%, and Zn content is 8.9%, and formaldehyde content is 12.6%.
Embodiment 3 N-methylol-D, the preparation of L-Methionine ferrous iron
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
Four water iron protochloride 352.8 grams (1.80mol) is added in above-mentioned saponification liquor after decolouring; be heated to 90 DEG C; nitrogen protection, keeps temperature of reaction to be 90 DEG C, reacts 1 hour; filter insolubles; filtrate is cooled to 0 DEG C, obtains tan precipitate, filters; obtain brown D, the ferrous solid of L-Methionine.
By D obtained above, the ferrous solid of L-Methionine adds the water of 1 times of quality, stirs, and to D, adds the formaldehyde solution 100 grams (1.0mol) of 30%, keep temperature to be 20 DEG C, react 1 hour in the ferrous slurries of L-Methionine.After reaction terminates, suction filtration, cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of brown powder shape, ferrous 187.3 grams of L-Methionine, yield 90%, purity is 99%, and wherein methionine content is 77.5%, and ferrous content is 8.8%, and formaldehyde content is 12.7%.
Embodiment 4 N-methylol-D, the preparation of L-Methionine copper
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
In above-mentioned saponification liquor after decolouring, add copper chloride dihydrate 302.9 grams (1.80mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains blue precipitate, filter, obtain blue D, L-Methionine copper solid.
By D obtained above, L-Methionine copper solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine copper slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration, cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of blue powder shape, L-Methionine copper 190.5 grams, yield 90%, purity is 99%, and wherein methionine content is 77.5%, and copper content is 9.0%, and formaldehyde content is 12.5%.
Embodiment 5 N-methylol-D, the preparation of L-Methionine manganese
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
In above-mentioned saponification liquor after decolouring, add tetrahydrate manganese chloride 352.8 grams (1.8mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains lightpink precipitation, filter, obtain D, L-Methionine manganese solid.
By D obtained above, L-Methionine manganese solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 90 grams (0.9mol) of 30% in L-Methionine manganese slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration, cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 187.7 grams, L-Methionine manganese, yield 90%, purity is 99%, and wherein methionine content is 77.8%, and Fe content is 8.5%, and formaldehyde content is 12.7%.
Embodiment 6 N-methylol-D, the preparation of L-Methionine cobalt
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
In above-mentioned saponification liquor after decolouring, add CoCL2 6H2O 408.7 grams (1.7mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains white precipitate, filter, obtain white D, L-Methionine cobalt solid.
By D obtained above, L-Methionine cobalt solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine cobalt slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration, cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, L-Methionine cobalt 188.6 grams, yield 90%, purity is 99%, and wherein methionine content is 77.5%, and cobalt contents is 8.9%, and formaldehyde content is 12.6%.
Embodiment 6 N-methylol-D, the preparation of L-Methionine chromium
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
In above-mentioned saponification liquor after decolouring, add chromium chloride hexahydrate 377 grams (1.4mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains red-purple precipitation, filter, obtain red-purple D, L-Methionine chromium solid.
By D obtained above, L-Methionine chromium solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine chromium slurries, and keep temperature to be 20 DEG C, nitrogen protection, reacts 1 hour.After reaction terminates, suction filtration, cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the pulverous N-methylol of red-purple-D, L-Methionine chromium 187.5 grams, yield 91%, purity is 99%, and wherein methionine content is 77.9%, and trivalent chromium content is 8.5%, and formaldehyde content is 12.6%.
Embodiment 7 N-methylol-D, the preparation of L-Methionine nickel
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
In above-mentioned saponification liquor after decolouring, add Dehydrated nickel chloride 222.5 grams (1.7mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains green precipitate, filter, obtain green D, L-Methionine nickel solid.
By D obtained above, L-Methionine nickel solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine nickel slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration, cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of green powder, 192.4 grams, L-Methionine nickel, yield 92%, purity is 99%, and wherein methionine content is 77.5%, and nickel content is 9.0%, and formaldehyde content is 12.5%.
Embodiment 8 utilizes D, the saponification liquor cyclic production N-methylol-D that L-Methionine is produced, L-Methionine zinc
The first round:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
Zinc Chloride Anhydrous 253.1 grams (1.87mol) is added in batches in above-mentioned saponification liquor after decolouring, be heated to 90 DEG C, temperature of reaction is kept to be 90 DEG C, react 1 hour, filter insolubles zinc carbonate, filtrate is cooled to 0 DEG C, obtain white precipitate, filter, obtain white D, L-Methionine zinc solid and filtrate 1.Gained filtrate 1 is circulated to second and takes turns reaction.
By D obtained above, L-Methionine zinc solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine zinc slurries, keeps temperature to be 23 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine zinc solid and filtrate 2, gained N-methylol-D, L-Methionine zinc solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 193 grams, L-Methionine zinc, yield 91%, purity is 99%, wherein methionine content is 77.5%, and Zn content is 8.9%, and formaldehyde content is 12.6%.Gained filtrate 2 is circulated to second and takes turns reaction.
Second takes turns:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
After above-mentioned saponification liquor after decolouring mixes with the filtrate 1 of first round gained, add Zinc Chloride Anhydrous 253.1 grams (1.87mol) in batches, be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles zinc carbonate, filtrate is cooled to 0 DEG C, obtains white precipitate, filters, obtain white D, L-Methionine zinc solid and filtrate 1.Gained filtrate 1 is recycled to next round reaction.
By D obtained above, L-Methionine zinc solid adds the filtrate 2 of gained in first round reaction, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine zinc slurries, keeps temperature to be 23 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine zinc solid and filtrate 2, gained N-methylol-D, L-Methionine zinc solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 195.2 grams, L-Methionine zinc, yield 92%, purity is 99%, wherein methionine content is 77.3%, and Zn content is 9.0%, and formaldehyde content is 12.7%.Gained filtrate 2 is recycled to next round reaction.
Special instruction, in the above-mentioned methods, is no less than the production of two-wheeled, can significantly improves productive rate, reduces production cost; In case of no particular description, the present embodiment can technical at foregoing, continues to use the first round and/or the second mode of taking turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, second takes turns, third round and fourth round, and often wheel feeds intake the saponification liquor 1140 grams after decolouring), and N-methylol-D, the ultimate production of L-Methionine zinc is 783.7g, and productive rate is 94%.
Embodiment 9 utilizes D, the saponification liquor cyclic production N-methylol-D that L-Methionine is produced, and L-Methionine is ferrous
The first round:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
Four water iron protochloride 352.8 grams (1.80mol) is added in above-mentioned saponification liquor after decolouring, be heated to 90 DEG C, temperature of reaction is kept to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtain tan precipitate, filter, obtain brown D, the ferrous solid of L-Methionine and filtrate 1.Gained filtrate 1 is circulated to second and takes turns reaction.
By D obtained above, the ferrous solid of L-Methionine adds the water of 1 times of quality, stirs, and to D, adds the formaldehyde solution 100 grams (1.0mol) of 30%, keep temperature to be 20 DEG C, react 1 hour in the ferrous slurries of L-Methionine.After reaction terminates, suction filtration obtains N-methylol-D, the ferrous solid of L-Methionine and filtrate 2, gained N-methylol-D, the ferrous solid cold water washing of L-Methionine, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of brown powder shape, ferrous 187.3 grams of L-Methionine, yield 90%, purity is 99%, wherein methionine content is 77.5%, and ferrous content is 8.8%, and formaldehyde content is 12.7%.Gained filtrate 2 is circulated to second and takes turns reaction.
Second takes turns:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
After above-mentioned saponification liquor after decolouring mixes with the filtrate 1 of first round gained, add four water iron protochloride 352.8 grams (1.80mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains tan precipitate, filters, obtain brown D, the ferrous solid of L-Methionine and filtrate 1.Gained filtrate 1 is recycled to next round reaction.
By D obtained above, the ferrous solid of L-Methionine adds the filtrate 2 of gained in first round reaction, stirs, and to D, adds the formaldehyde solution 100 grams (1.0mol) of 30%, keep temperature to be 20 DEG C, react 1 hour in the ferrous slurries of L-Methionine.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine ferrous iron and filtrate 2, gained N-methylol-D, the ferrous solid cold water washing of L-Methionine, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of brown powder shape, ferrous 191.4 grams of L-Methionine, yield 92%, purity is 99%, wherein methionine content is 77.5%, and ferrous content is 8.8%, and formaldehyde content is 12.7%.Gained filtrate 2 is recycled to next round reaction.
Special instruction, in the above-mentioned methods, is no less than the production of two-wheeled, can significantly improves productive rate, reduces production cost; In case of no particular description, the present embodiment can technical at foregoing, continues to use the first round and/or the second mode of taking turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, second takes turns, third round and fourth round, and often wheel feeds intake the saponification liquor 1140 grams after decolouring), and N-methylol-D, the ultimate production of L-Methionine ferrous iron is 765.9g, and productive rate is 94.4%.
Embodiment 10 utilizes D, the saponification liquor cyclic production N-methylol-D that L-Methionine is produced, L-Methionine copper
The first round:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
Copper chloride dihydrate 302.9 grams (1.80mol) is added in above-mentioned saponification liquor after decolouring, be heated to 90 DEG C, temperature of reaction is kept to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtain blue precipitate, filter, obtain blue D, L-Methionine copper solid and filtrate 1.Gained filtrate 1 is circulated to second and takes turns reaction.
By D obtained above, L-Methionine copper solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine copper slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine copper solid and filtrate 2, gained N-methylol-D, L-Methionine copper solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of blue powder shape, L-Methionine copper 190.5 grams, yield 90%, purity is 99%, wherein methionine content is 77.5%, and copper content is 9.0%, and formaldehyde content is 12.5%.Gained filtrate 2 is circulated to second and takes turns reaction.
Second takes turns:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
After above-mentioned saponification liquor after decolouring mixes with the filtrate 1 of first round gained, add copper chloride dihydrate 302.9 grams (1.80mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains blue precipitate, filters, obtain blue D, L-Methionine copper solid and filtrate 1.Gained filtrate 1 is recycled to next round reaction.
By D obtained above, L-Methionine copper solid adds the filtrate 2 of gained in first round reaction, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine copper slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine copper solid and filtrate 2, gained N-methylol-D, L-Methionine copper solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of blue powder shape, L-Methionine copper 192.6 grams, yield 91%, purity is 99%, wherein methionine content is 77.5%, and copper content is 9.0%, and formaldehyde content is 12.5%.Gained filtrate 2 is recycled to next round reaction.
Special instruction, in the above-mentioned methods, is no less than the production of two-wheeled, can significantly improves productive rate, reduces production cost; In case of no particular description, the present embodiment can technical at foregoing, continues to use the first round and/or the second mode of taking turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, second takes turns, third round and fourth round, and often wheel feeds intake the saponification liquor 1140 grams after decolouring), and N-methylol-D, the ultimate production of L-Methionine copper is 771.8g, and productive rate is 93%.
Embodiment 11 utilizes D, the saponification liquor cyclic production N-methylol-D that L-Methionine is produced, L-Methionine manganese
The first round:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
In above-mentioned saponification liquor after decolouring, add tetrahydrate manganese chloride 352.8 grams (1.8mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains lightpink precipitation, filter, obtain D, L-Methionine manganese solid and filtrate 1.Gained filtrate 1 is circulated to second and takes turns reaction.
By D obtained above, L-Methionine manganese solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 90 grams (0.9mol) of 30% in L-Methionine manganese slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine manganese solid and filtrate 2, gained N-methylol-D, L-Methionine manganese solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 187.7 grams, L-Methionine manganese, yield 90%, purity is 99%, wherein methionine content is 77.8%, and Fe content is 8.5%, and formaldehyde content is 12.7%.Gained filtrate 2 is circulated to second and takes turns reaction.
Second takes turns:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
After above-mentioned saponification liquor after decolouring mixes with the filtrate 1 of first round gained, add tetrahydrate manganese chloride 352.8 grams (1.8mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains lightpink precipitation, filters, obtain D, L-Methionine manganese solid and filtrate 1.Gained filtrate 1 is recycled to next round reaction.
By D obtained above, L-Methionine manganese solid adds the filtrate 2 of gained in first round reaction, stirs, to D, adds the formaldehyde solution 90 grams (0.9mol) of 30% in L-Methionine manganese slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine manganese solid and filtrate 2, gained N-methylol-D, L-Methionine manganese solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 188.9 grams, L-Methionine manganese, yield 91%, purity is 99%, wherein methionine content is 77.8%, and Fe content is 8.5%, and formaldehyde content is 12.7%.Gained filtrate 2 is recycled to next round reaction.
Special instruction, in the above-mentioned methods, is no less than the production of two-wheeled, can significantly improves productive rate, reduces production cost; In case of no particular description, the present embodiment can technical at foregoing, continues to use the first round and/or the second mode of taking turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, second takes turns, third round and fourth round, and often wheel feeds intake the saponification liquor 1140 grams after decolouring), and N-methylol-D, the ultimate production of L-Methionine manganese is 757.3g, and productive rate is 93%.
Embodiment 12 utilizes D, the saponification liquor cyclic production N-methylol-D that L-Methionine is produced, L-Methionine cobalt
The first round:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
CoCL2 6H2O 408.7 grams (1.7mol) is added in above-mentioned saponification liquor after decolouring, be heated to 90 DEG C, temperature of reaction is kept to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtain white precipitate, filter, obtain white D, L-Methionine cobalt solid and filtrate 1.Gained filtrate 1 is circulated to second and takes turns reaction.
By D obtained above, L-Methionine cobalt solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine cobalt slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine cobalt solid and filtrate 2, gained N-methylol-D, L-Methionine cobalt solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, L-Methionine cobalt 188.6 grams, yield 90%, purity is 99%, wherein methionine content is 77.5%, and cobalt contents is 8.9%, and formaldehyde content is 12.6%.Gained filtrate 2 is circulated to second and takes turns reaction.
Second takes turns:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
After above-mentioned saponification liquor after decolouring mixes with the filtrate 1 of first round gained, add CoCL2 6H2O 408.7 grams (1.7mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains white precipitate, filters, obtain white D, L-Methionine cobalt solid and filtrate 1.Gained filtrate 1 is recycled to next round reaction.
By D obtained above, L-Methionine cobalt solid adds the filtrate 2 of gained in first round reaction, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine cobalt slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine cobalt solid and filtrate 2, gained N-methylol-D, L-Methionine cobalt solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, L-Methionine cobalt 192.8 grams, yield 92%, purity is 99%, wherein methionine content is 77.3%, and cobalt contents is 8.9%, and formaldehyde content is 12.8%.Gained filtrate 2 is recycled to next round reaction.
Special instruction, in the above-mentioned methods, is no less than the production of two-wheeled, can significantly improves productive rate, reduces production cost; In case of no particular description, the present embodiment can technical at foregoing, continues to use the first round and/or the second mode of taking turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, second takes turns, third round and fourth round, and often wheel feeds intake the saponification liquor 1140 grams after decolouring), and N-methylol-D, the ultimate production of L-Methionine cobalt is 771.9g, and productive rate is 94%.
Embodiment 13 utilizes D, the saponification liquor cyclic production N-methylol-D that L-Methionine is produced, L-Methionine chromium
The first round:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
Chromium chloride hexahydrate 377 grams (1.4mol) is added in above-mentioned saponification liquor after decolouring, be heated to 90 DEG C, temperature of reaction is kept to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtain red-purple precipitation, filter, obtain red-purple D, L-Methionine chromium solid and filtrate 1.Gained filtrate 1 is circulated to second and takes turns reaction.
By D obtained above, L-Methionine chromium solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine chromium slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine chromium solid and filtrate 2, gained N-methylol-D, L-Methionine chromium solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the pulverous N-methylol of red-purple-D, L-Methionine chromium 183.5 grams, yield 91%, purity is 99%, wherein methionine content is 77.9%, and trivalent chromium content is 8.5%, and formaldehyde content is 12.6%.Gained filtrate 2 is circulated to second and takes turns reaction.
Second takes turns:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
After above-mentioned saponification liquor after decolouring mixes with the filtrate 1 of first round gained, add chromium chloride hexahydrate 377 grams (1.4mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains red-purple precipitation, filters, obtain red-purple D, L-Methionine chromium solid and filtrate 1.Gained filtrate 1 is recycled to next round reaction.
By D obtained above, L-Methionine chromium solid adds the filtrate 2 of gained in first round reaction, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine chromium slurries, and keep temperature to be 20 DEG C, nitrogen protection, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine chromium solid and filtrate 2, gained N-methylol-D, L-Methionine chromium solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the pulverous N-methylol of red-purple-D, L-Methionine chromium 187.5 grams, yield 93%, purity is 99%, wherein methionine content is 78.3%, and trivalent chromium content is 7.9%, and formaldehyde content is 12.8%.Gained filtrate 2 is recycled to next round reaction.
Special instruction, in the above-mentioned methods, is no less than the production of two-wheeled, can significantly improves productive rate, reduces production cost; In case of no particular description, the present embodiment can technical at foregoing, continues to use the first round and/or the second mode of taking turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, second takes turns, third round and fourth round, and often wheel feeds intake the saponification liquor 1140 grams after decolouring), and N-methylol-D, the ultimate production of L-Methionine chromium is 751.1g, and productive rate is 94%.
Embodiment 14 utilizes D, the saponification liquor cyclic production N-methylol-D that L-Methionine is produced, L-Methionine nickel
The first round:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
Dehydrated nickel chloride 222.5 grams (1.7mol) is added in above-mentioned saponification liquor after decolouring, be heated to 90 DEG C, temperature of reaction is kept to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtain green precipitate, filter, obtain green D, L-Methionine nickel solid and filtrate 1.Gained filtrate 1 is circulated to second and takes turns reaction.
By D obtained above, L-Methionine nickel solid adds the water of 1 times of quality, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine nickel slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine nickel solid and filtrate 2, gained N-methylol-D, L-Methionine nickel solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of green powder, 192.4 grams, L-Methionine nickel, yield 92%, purity is 99%, wherein methionine content is 77.5%, and nickel content is 9.0%, and formaldehyde content is 12.5%.Gained filtrate 2 is circulated to second and takes turns reaction.
Second takes turns:
Saponification liquor after the decolouring that Example 1 is mentioned 1140 grams, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
After above-mentioned saponification liquor after decolouring mixes with the filtrate 1 of first round gained, add Dehydrated nickel chloride 222.5 grams (1.7mol), be heated to 90 DEG C, keep temperature of reaction to be 90 DEG C, react 1 hour, filter insolubles, filtrate is cooled to 0 DEG C, obtains green precipitate, filters, obtain green D, L-Methionine nickel solid and filtrate 1.Gained filtrate 1 is recycled to next round reaction.
By D obtained above, L-Methionine nickel solid adds the filtrate 2 of gained in first round reaction, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine nickel slurries, keeps temperature to be 20 DEG C, reacts 1 hour.After reaction terminates, suction filtration obtains N-methylol-D, L-Methionine nickel solid and filtrate 2, gained N-methylol-D, L-Methionine nickel solid cold water washing, then 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of green powder, 194.5 grams, L-Methionine nickel, yield 93%, purity is 99%, wherein methionine content is 77.6%, and nickel content is 8.9%, and formaldehyde content is 12.5%.Gained filtrate 2 is recycled to next round reaction.
Special instruction, in the above-mentioned methods, is no less than the production of two-wheeled, can significantly improves productive rate, reduces production cost; In case of no particular description, the present embodiment can technical at foregoing, continues to use the first round and/or the second mode of taking turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, second takes turns, third round and fourth round, and often wheel feeds intake the saponification liquor 1140 grams after decolouring), and N-methylol-D, the ultimate production of L-Methionine nickel is 783.9g, and productive rate is 95%.
Embodiment 15 utilizes N-methylol-D, and L-Methionine microelement chelate production equipment associating D, the saponification liquor that L-Methionine is produced produces N-methylol-D, L-Methionine zinc
Utilize N-methylol-D, N-methylol-D prepared by L-Methionine microelement chelate production equipment, the production method of L-Methionine microelement chelate, described N-methylol-D, L-Methionine microelement chelate production equipment, comprise the retort 1 of saponification liquor and micro-metals reactant salt, tripping device 2, D, the hydroxymethylation tank 3 of L-Methionine microelement chelate and formaldehyde reaction, liquid storage tank 4, washing device 5, drying installation 6 and shredding unit 7, described retort 1 is communicated with tripping device 2 respectively by being with the reflux line of valve with hydroxymethylation tank 3, described liquid storage tank 4 respectively with retort 1, tripping device 2 is connected with hydroxymethylation tank 3, described washing device 5 is connected with described tripping device 2, described drying installation 6 is connected with described washing device 5, described shredding unit 7 is connected with described drying installation 6,
Saponification liquor after the decolouring that Example 1 is mentioned 114 kilograms, analyzes the composition of saponification liquor: D, the mass percentage of L-Methionine sodium is 15%, and sodium carbonate mass percentage is 10%, and surplus is water.
Above-mentioned saponification liquor after decolouring is joined in retort 1, and Zinc Chloride Anhydrous 25310 grams (187mol) is added in retort 1, then 90 DEG C are heated to, temperature of reaction is kept to be 90 DEG C, react 1 hour, after question response terminates, send into tripping device 2 and be separated removing solid insoluble zinc carbonate, the filtrate of gained is cooled to 0 DEG C of crystallization, then filter through tripping device 2 and obtain white D, L-Methionine zinc solid and filtrate 1, described filtrate 1 is sent in liquid storage tank 4 and is stored, when another preparation taking turns N-methylol zinc methionine starts, described filtrate 1 mixes with saponification liquor, the preparation of N-methylol zinc methionine is taken turns for another,
By D obtained above, hydroxymethylation tank 3 sent into by L-Methionine zinc solid, adds the water of 1 times of quality, stirs, then in hydroxymethylation tank 3, adds the formaldehyde solution 10 kilograms (100mol) of 30%, keeps temperature to be 23 DEG C, reacts 1 hour.After reaction terminates, send in tripping device 2 and be separated to obtain N-methylol zinc methionine solid and filtrate 2; Gained N-methylol zinc methionine solid sends into washing device 5 with sending in drying installation 6 after cold water washing, 105 DEG C of vacuum-dryings, N-methylol-the D pulverizing in shredding unit 7 and obtain white powder is sent into after dry, 19.26 kilograms, L-Methionine zinc, yield 90%, purity is 99%, and wherein methionine content is 76.5%, Zn content is 8.7%, and formaldehyde content is 12.7%.Gained filtrate 2 is sent in liquid storage tank 4 and is stored, and takes turns in the preparation process of N-methylol zinc methionine continue and formaldehyde reaction, for the preparation of N-methylol zinc methionine at another.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. utilize D, the saponification liquor that L-Methionine is produced prepares N-methylol-D, and the method for L-Methionine microelement chelate, is characterized in that, comprises the step of carrying out as follows:
(1) with D, the saponification liquor that L-Methionine is produced is raw material, and with solubility micro-metals reactant salt, reaction terminates rear filtration, and gained filtrate crystallisation obtains D, L-Methionine microelement chelate; Described D, the saponification liquor that L-Methionine is produced is by D, after L-Methionine production intermediate material 5-(2-methylthio ethyl)-glycolylurea adds sodium hydroxide, be heated to 130 DEG C ~ 165 DEG C hydrolysis gained, described saponification liquor is composed of the following components: mass percent is the Sodium L-methioninate of 15% ~ 19%, mass percent is the sodium carbonate of 9% ~ 13%, and the water medium of surplus;
(2) by the D of step (1) gained, L-Methionine microelement chelate carries out hydroxymethylation with formaldehyde in water medium, filters to obtain N-methylol-D, L-Methionine microelement chelate after reaction terminates.
2. preparation N-methylol-D according to claim 1, the method of L-Methionine microelement chelate, it is characterized in that: in described step (1), described solubility micro-metals salt is the trace metal salts of the solubility of iron, copper, zinc, manganese, cobalt, nickel and chromium.
3. preparation N-methylol-D according to claim 1 and 2, the method for L-Methionine microelement chelate, is characterized in that: in described step (1), and described solubility micro-metals salt is excessive.
4. preparation N-methylol-D according to claim 1, the method of L-Methionine microelement chelate, it is characterized in that: in described step (1), the temperature of described saponification liquor and described solubility micro-metals reactant salt is 60 DEG C ~ 90 DEG C, and the reaction times is 1 ~ 3 hour.
5. preparation N-methylol-D according to claim 1, the method for L-Methionine microelement chelate, is characterized in that: in described step (1), and described crystallization is that gained filtrate is cooled to 0 DEG C ~ 10 DEG C crystallizations.
6. preparation N-methylol-D according to claim 1, the method of L-Methionine microelement chelate, it is characterized in that: in described step (2), described D, the mol ratio that L-Methionine microelement chelate and formaldehyde carry out hydroxymethylation is 1.0 ~ 1.2:1.
7. preparation N-methylol-D according to claim 1, the method of L-Methionine microelement chelate, it is characterized in that: in described step (2), described D, L-Methionine microelement chelate and formaldehyde carry out hydroxymethylation temperature and control at 20 DEG C ~ 30 DEG C, and the reaction times is 0.5 ~ 2 hour.
8. preparation N-methylol-D according to claim 1, the method of L-Methionine microelement chelate, it is characterized in that: the D described in described step (2), L-Methionine microelement chelate and formaldehyde carry out after hydroxymethylation terminates, filtering, gained N-methylol-D, L-Methionine microelement chelate cold water washing, then dry, pulverize, obtain Powdered N-methylol-D, L-Methionine microelement chelate.
9. utilize D, L-Methionine produces saponification liquor cyclic production N-methylol-D, the method of L-Methionine microelement chelate, described D, it is by D that L-Methionine produces saponification liquor, and L-Methionine is produced intermediate material 5-(2-methylthio ethyl)-glycolylurea and produced through basic hydrolysis, described D, it is composed of the following components that L-Methionine produces saponification liquor: mass percent is the Sodium L-methioninate of 15% ~ 19%, and mass percent is the sodium carbonate of 9% ~ 13%, and the water medium of surplus; It is characterized in that, comprise the following steps:
A is with D, and it is raw material that L-Methionine produces saponification liquor, and with solubility micro-metals reactant salt, reaction terminates rear filtration, gained filtrate crystallisation, obtains D after filtration, L-Methionine microelement chelate and filtrate 1; Described filtrate 1 takes turns N-methylol-D at another, and with D in the preparation process of L-Methionine microelement chelate, L-Methionine is produced saponification liquor mixing and continued to participate in reaction;
The D of gained in step B A, L-Methionine microelement chelate carries out hydroxymethylation with formaldehyde in water medium, filters to obtain N-methylol-D, L-Methionine microelement chelate and filtrate 2 after reaction terminates; Gained filtrate 2 takes turns N-methylol-D at another, continues to carry out hydroxymethylation with formaldehyde in the preparation process of L-Methionine microelement chelate.
10. utilize N-methylol-D, N-methylol-D prepared by L-Methionine microelement chelate production equipment, the method of L-Methionine microelement chelate, it is characterized in that: described N-methylol-D, L-Methionine microelement chelate production equipment, comprise D, L-Methionine produces the retort (1) of saponification liquor and solubility micro-metals reactant salt, tripping device (2), hydroxymethylation tank (3), liquid storage tank (4), washing device (5), drying installation (6) and shredding unit (7), described retort (1) is communicated with tripping device (2) respectively by being with the reflux line of valve with hydroxymethylation tank (3), described liquid storage tank (4) respectively with retort (1), tripping device (2) is connected with hydroxymethylation tank (3), described washing device (5) is connected with described tripping device (2), described drying installation (6) is connected with described washing device (5), described shredding unit (7) is connected with described drying installation (6),
A adds D in retort (1), L-Methionine produces saponification liquor raw material, then solubility micro-metals salt is added, after question response terminates, send into tripping device (2) and be separated removing solid matter, gained filtrate crystallisation, then D is separated through tripping device (2), L-Methionine microelement chelate and filtrate 1, described filtrate 1 is sent in liquid storage tank (4) and is stored, another takes turns N-methylol-D, when the preparation of L-Methionine microelement chelate starts, described filtrate 1 takes turns N-methylol-D at another, with D in the preparation process of L-Methionine microelement chelate, L-Methionine is produced saponification liquor mixing and is continued to participate in reaction, described saponification liquor is through basic hydrolysis gained by 5-(2-methylthio ethyl)-glycolylurea, described D, it is composed of the following components that L-Methionine produces saponification liquor: mass percent is the Sodium L-methioninate of 15% ~ 19%, and mass percent is the sodium carbonate of 9% ~ 13%, and the water medium of surplus,
The D of gained in b step a, L-Methionine microelement chelate sends into hydroxymethylation tank (3), hydroxymethylation is carried out with formaldehyde in water medium, reaction terminates to be separated to obtain N-methylol-D, L-Methionine microelement chelate and filtrate 2 in rear feeding tripping device (2); Gained N-methylol-D, it is dry with sending into after cold water washing in drying installation (6) that L-Methionine microelement chelate sends into washing device (5), send into after drying in shredding unit (7) to pulverize and obtain Powdered N-methylol-D, L-Methionine microelement chelate; Gained filtrate 2 is sent in liquid storage tank (4) and is stored, N-methylol-D is taken turns at another, continue in the preparation process of L-Methionine microelement chelate to carry out hydroxymethylation with formaldehyde, for the preparation of N-methylol-D, L-Methionine microelement chelate.
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Effective date of registration: 20160729 Address after: 755000 the Ningxia Hui Autonomous Region central defender, Shapotou District, Guangzhou Road West Patentee after: NINGXIA ZIGUANG TIANHUA METHIONINE CO., LTD. Address before: 402161 Yongchuan District, Chongqing Chemical Road, No. 426 Patentee before: Chongqing Unisplendour Chemical Co., Ltd. |