CN103497135B - One prepares N-methylol-D, the method for L-Methionine microelement chelate - Google Patents
One prepares N-methylol-D, the method for L-Methionine microelement chelate Download PDFInfo
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Abstract
The present invention is directed to chemical field, it relates to one prepares N-methylol-D, the method for L-Methionine microelement chelate, the method is first with D, and L-Methionine and trace elements metal salt reaction, obtain D, L-Methionine microelement chelate; The D obtained, L-Methionine microelement chelate in water medium with formaldehyde reaction, after completion of the reaction after filtration, cold water washing, dry, pulverize, obtain pulverous N-methylol-D, L-Methionine microelement chelate. The method has obtained the N-methylol-D of high purity, L-Methionine microelement chelate, and with short production cycle, efficiency of pcr product height, stability height, and the filtrate obtained is capable of circulation applies mechanically.
Description
Technical field
The present invention is directed to chemical field, it relates to one 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, biological value is low and mixture homogeneity is low etc.; 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 class first succeeded in developing the earliest by the U.S.'s ALBICN biological test room seventies in 20th century, 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 microelements aminophenol chelated has been carried out investigation and application, 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. The Chinese patent being 201110412988.9 such as number of patent application discloses the synthetic method of methionine(Met) metal (copper, zinc, cobalt) inner complex. Owing to amino acid is easily by ruminant tumor gastric microbiological deterioration, not utilized by organism by cud, utilization ratio is lower, limits the application of above-mentioned microelements aminophenol chelated.
How to meet high yield ruminating animal the demand of gal4 amino acid and trace element thereof has been become domestic and international dietician to be paid close attention to. Much research shows: adding rumen-bypass amino acid microelement chelate in its feed 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, other nutritive elements can not be damaged effect, to improve feed utilization ratio, reduce gal4 amino acid waste, reduce production cost, improve ruminating animal throughput 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 methionine hydroxy analog microelement chelate (application number be 201310199220.7 patent of invention disclose the preparation method of a kind of microelement methionine hydroxy analogue chelate additive) developed the application that comes into the market. but, in the existing method preparing methionine trace element chelate, all there is synthesis technique cycle length, receipts rate purity low, production cost height, product is low, stability is poor phenomenon.
Summary of the invention
In view of this, it is an object of the invention to provide one and prepare N-methylol-D, the method for L-Methionine microelement chelate, not only shorten synthesis technique, and improve synthetic ratio.
For achieving the above object, the technical scheme of the present invention is:
One prepares N-methylol-D, and the method for L-Methionine microelement chelate comprises the step carried out as follows:
(1) by D, L-Methionine adds water and mineral alkali, heating for dissolving obtains solution 1, is separately added to the water by the trace metal salts of solubility, and heating for dissolving obtains solution 2, described solution 1 and solution 2 are mixed to get reaction system, maintaining reaction system pH is 5.5��7.0, reacting by heating, and reaction is filtered after terminating, gained filtrate crystallization obtains D, L-Methionine microelement chelate; In the method for the invention, after the trace metal reactant salt of D, L-Methionine and solubility, filtering the filtrate obtained and continue to utilize, the solid matter obtained is mainly trace metal compound insolubles, discharges reaction system, free from environmental pollution.
(2) D of step (1) gained, L-Methionine microelement chelate carries out hydroxymethylation with formaldehyde in water medium, and reaction filters to obtain N-methylol-D, L-Methionine microelement chelate after terminating.
In the method for the invention, in step (1), reaction is filtered after terminating, gained filtrate also can without crystallization treatment, filtrate being cooled to 20 DEG C��30 DEG C, obtains containing D, the mixed serum of L-Methionine microelement chelate is directly used in next step and formaldehyde reaction carries out methylolation. Gained filtrate crystallization is preferably obtained D by the present invention, L-Methionine microelement chelate solid, and then carries out methylolation for next step and formaldehyde reaction.
Above-mentioned preparation N-methylol-D, the method reaction formula of L-Methionine microelement chelate is as follows:
Wherein: M is micro-metals, such as the one in iron, copper, zinc, manganese, cobalt, nickel and chromium.
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, in step (1), the trace metal salts of described solubility is the trace metal salts of the solubility of iron, copper, zinc, manganese, cobalt, nickel and chromium.
Further, described preparation N-methylol-D, the method of L-Methionine microelement chelate, in step (1), the trace metal salts of described solubility 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), in the trace metal salts reaction system of D, L-Methionine and solubility, micro-metals and D, the mol ratio of L-Methionine is 0.4��0.8:1.
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, in step (1), described mineral alkali is sodium hydroxide, described sodium hydroxide and D, and the mol ratio of L-Methionine is 0.8��1.2:1.
Further, described preparation N-methylol-D, the method for L-Methionine microelement chelate, in step (1), described solution 1 and solution 2 mix, and reacting by heating temperature 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), it is 1.0��1.2:1 that described D, L-Methionine microelement chelate and formaldehyde carry out the mol ratio of hydroxymethylation.
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 pulverous 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, it is with short production cycle, and wastage rate are low, receipts rate height;
N-methylol-D, the circulation producing method of L-Methionine microelement chelate, comprises the following steps:
A is by D, L-Methionine adds water and mineral alkali, and heating for dissolving obtains solution 1, is separately added to the water by the trace metal salts of solubility, heating for dissolving obtains solution 2, described solution 1 and solution 2 are mixed to get reaction system, and maintaining reaction system pH is 5.5��7.0, reacting by heating, reaction is filtered after terminating, gained filtrate crystallization, filters to obtain D, L-Methionine microelement chelate and filtrate 1; The recycle of described filtrate 1, takes turns N-methylol-D for another, the preparation of L-Methionine microelement chelate and D, and L-Methionine mixing continues to participate in reaction;
The D of gained in step B A, L-Methionine microelement chelate carries out hydroxymethylation with formaldehyde in water medium, and reaction filters to obtain N-methylol-D, L-Methionine microelement chelate and filtrate 2 after terminating; Gained filtrate 2 takes turns N-methylol-D at another, and the preparation process resume of L-Methionine microelement chelate and formaldehyde carry out hydroxymethylation.
Another method relates to produce N-methylol-D in specific recycle unit, L-Methionine microelement chelate, namely N-methylol-D is utilized, L-Methionine microelement chelate production equipment (as shown in Figure 1) prepares N-methylol-D, the production method of L-Methionine microelement chelate, described N-methylol-D, L-Methionine microelement chelate production equipment, comprise D, L-Methionine microelement chelate preparation feedback tank, tripping device, D, L-Methionine microelement chelate and formaldehyde carry out the retort of hydroxymethylation, liquid storage tank, washing device, drying installation and shredding unit, described D, L-Methionine microelement chelate preparation feedback tank and D, the retort that L-Methionine microelement chelate carries out hydroxymethylation with formaldehyde is connected with tripping device by the backflow pipeline of band valve respectively, described liquid storage tank respectively with D, L-Methionine microelement chelate preparation feedback tank, tripping device is connected with the retort carrying out hydroxymethylation, 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 is by D, L-Methionine adds water and mineral alkali, heating for dissolving obtains solution 1, separately the trace metal salts of solubility is added to the water, heating for dissolving obtains solution 2, described solution 1 and solution 2 are joined D, L-Methionine microelement chelate preparation feedback tank is mixed to get reaction system, maintaining reaction system pH is 5.5��7.0, reacting by heating, after question response terminates, send into separation in tripping device and remove solid matter, gained filtrate crystallization, then D it is separated to obtain 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 and D, L-Methionine mixes, N-methylol-D is taken turns for another, the preparation of L-Methionine microelement chelate,
The D of gained in b step a, L-Methionine microelement chelate sends into D, L-Methionine microelement chelate and formaldehyde carry out the retort of hydroxymethylation, water medium carries out hydroxymethylation with formaldehyde, reaction is sent into after terminating and is separated to obtain N-methylol-D, L-Methionine microelement chelate and filtrate 2 in tripping device; Gained N-methylol-D, L-Methionine microelement chelate is sent in drying installation dry after sending into washing device cold water washing, pulverize and obtain pulverous N-methylol-D, L-Methionine microelement chelate after dry in feeding shredding unit; Gained filtrate 2 is sent in liquid storage tank and is stored, and takes turns N-methylol-D at another, and the preparation process resume of L-Methionine microelement chelate and formaldehyde carry out hydroxymethylation, for the preparation of N-methylol-D, and L-Methionine microelement chelate.
The useful effect of the present invention: 1) the present invention provides one and prepares N-methylol-D, the method of L-Methionine microelement chelate, can effectively solve in actual production process, N-methylol-D, the production cycle of L-Methionine microelement chelate is long, receipts rate is low, production cost height, the problem that product purity is low, stability is poor; 2) the N-methylol-D that the preparation method of the present invention obtains, L-Methionine microelement chelate product purity height, 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 improve utilization ratio, the reduce methionine(Met) decomposition in cud, the absorption being beneficial to methionine(Met) of feed, reduce production cost, improve the throughput of 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 concrete condition in preferred embodiment, usually conveniently condition.
Embodiment 1N-methylol-D, the preparation of L-Methionine zinc
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get Zinc Chloride Anhydrous 108.8 grams (0.8mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by solder(ing)acid in the Sodium L-methioninate aqueous solution, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains white precipitate, filters, and obtains 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.Reaction takes out filter, cold water washing, 105 DEG C of vacuum-dryings after terminating, and pulverizes, obtains the N-methylol-D of white powder, 193 grams, L-Methionine zinc, receipts rate 91%, and purity is 99%, and wherein methionine content is 77.5%, and Zn content is 8.9%, and formaldehyde content is 12.6%.
Embodiment 2N-methylol-D, the preparation of L-Methionine ferrous iron
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get four water iron protochloride 158.4 grams (0.8mol) and it is dissolved in 650 grams of water, be heated to 60 DEG C. Being added by ferrous chloride aqueous solution in the Sodium L-methioninate aqueous solution, nitrogen protection, keep temperature of reaction to be 90 DEG C, system pH is 6.5, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains brown precipitation, 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. Reaction takes out filter, cold water washing, 105 DEG C of vacuum-dryings after terminating, pulverize, obtain the N-methylol-D of brown powder shape, ferrous 187.3 grams of L-Methionine, receipts rate 90%, purity is 99%, and wherein methionine content is 77.5%, and ferrous content is 8.8%, and formaldehyde content is 12.7%.
Embodiment 3N-methylol-D, the preparation of L-Methionine copper
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get copper chloride dihydrate 119 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by copper chloride solution in the Sodium L-methioninate aqueous solution, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains blue precipitation, filters, and obtains 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. Reaction takes out filter, cold water washing, 105 DEG C of vacuum-dryings after terminating, and pulverizes, obtains the N-methylol-D of blue powder shape, L-Methionine copper 190.5 grams, receipts rate 90%, and purity is 99%, and wherein methionine content is 77.5%, and copper content is 9.0%, and formaldehyde content is 12.5%.
Embodiment 4N-methylol-D, the preparation of L-Methionine manganese
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get tetrahydrate manganese chloride 158.4 grams (0.8mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by the Manganous chloride tetrahydrate aqueous solution in the Sodium L-methioninate aqueous solution, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains lightpink precipitation, filters, 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. Reaction takes out filter, cold water washing, 105 DEG C of vacuum-dryings after terminating, and pulverizes, obtains the N-methylol-D of white powder, 187.7 grams, L-Methionine manganese, receipts rate 90%, and purity is 99%, and wherein methionine content is 77.8%, and Fe content is 8.5%, and formaldehyde content is 12.7%.
Embodiment 5N-methylol-D, the preparation of L-Methionine cobalt
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get CoCL2 6H2O 168.3 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by cobalt chloride solution in the Sodium L-methioninate aqueous solution, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains white precipitate, filters, and obtains 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. Reaction takes out filter, cold water washing, 105 DEG C of vacuum-dryings after terminating, and pulverizes, obtains the N-methylol-D of white powder, L-Methionine cobalt 188.6 grams, receipts rate 90%, and purity is 99%, and wherein methionine content is 77.5%, and cobalt contents is 8.9%, and formaldehyde content is 12.6%.
Embodiment 6N-methylol-D, the preparation of L-Methionine chromium
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get chromium chloride hexahydrate 107.7 grams (0.4mol) and it is dissolved in 500 grams of water, nitrogen protection, be heated to 60 DEG C. Being added by the chromium trichloride aqueous solution in the Sodium L-methioninate aqueous solution, nitrogen protection, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains red-purple precipitation, filters, 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, keeps temperature to be 20 DEG C, and nitrogen protection, reacts 1 hour. Reaction takes out filter, cold water washing, 105 DEG C of vacuum-dryings after terminating, pulverize, obtain the pulverous N-methylol-D of red-purple, L-Methionine chromium 187.5 grams, receipts rate 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 7N-methylol-D, the preparation of L-Methionine nickel
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get Dehydrated nickel chloride 91.6 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by nickel chloride aqueous solution in the Sodium L-methioninate aqueous solution, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains green precipitation, filters, and obtains 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. Reaction takes out filter, cold water washing, 105 DEG C of vacuum-dryings after terminating, and pulverizes, obtains the N-methylol-D of green flour powder, 192.4 grams, L-Methionine nickel, receipts rate 92%, and purity is 99%, and wherein methionine content is 77.5%, and nickel content is 9.0%, and formaldehyde content is 12.5%.
Embodiment 8N-methylol-D, the cyclic production of L-Methionine zinc
The first round:
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings.Separately get Zinc Chloride Anhydrous 108.8 grams (0.8mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by solder(ing)acid in the Sodium L-methioninate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains white precipitate, filters, and obtains white D, L-Methionine zinc solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for the 2nd, and with D in the preparation process of L-Methionine zinc, L-Methionine mixing continues to participate in 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine zinc solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine zinc solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 193 grams, L-Methionine zinc, receipts rate 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 takes turns N-methylol-D the 2nd, the preparation process resume of L-Methionine zinc and formaldehyde reaction.
2nd takes turns:
Take 150.5 grams of (1.0mol) methionine(Met), add the filtrate 1 of first round gained, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get Zinc Chloride Anhydrous 95.2 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by solder(ing)acid in the Sodium L-methioninate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains white precipitate, filters, and obtains white D, L-Methionine zinc solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for next, and with D in the preparation process of L-Methionine zinc, L-Methionine mixing continues to participate in reaction;
By D obtained above, L-Methionine zinc solid joins in the filtrate 2 of first round gained, 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine zinc solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine zinc solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 195.2 grams, L-Methionine zinc, receipts rate 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 takes turns N-methylol-D at next, the preparation process resume of L-Methionine zinc and formaldehyde reaction.
Special instruction, in the above-mentioned methods, is no less than two productions taken turns, it is possible to significantly improve product rate, reduces production cost; In case of no particular description, the present embodiment in the technology of foregoing, can be continued to use the first round and/or the 2nd mode taken turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, the 2nd takes turns, three-wheel and fourth round, and often wheel throws material methionine(Met) 150.5 grams (1.0mol)), and N-methylol-D, the ultimate production of L-Methionine zinc is 783.6g, and product rate is 94%.
Embodiment 9N-methylol-D, the cyclic production of L-Methionine ferrous iron
The first round:
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings.Separately get four water iron protochloride 158.4 grams (0.8mol) and it is dissolved in 650 grams of water, be heated to 60 DEG C. Being added by ferrous chloride aqueous solution in the Sodium L-methioninate aqueous solution and mix, nitrogen protection, keep temperature of reaction to be 90 DEG C, system pH is 6.5; reacting 1 hour, filter, filtrate is cooled to 5 DEG C, obtains brown precipitation; filter, obtain brown D, the ferrous solid of L-Methionine and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for the 2nd, and with D in the preparation process of L-Methionine ferrous iron, L-Methionine mixing continues to participate in 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. Reaction is taken out and is filtered to obtain N-methylol-D after terminating, the ferrous solid of L-Methionine and filtrate 2, described N-methylol-D, the ferrous solid of L-Methionine through 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, receipts rate 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 takes turns N-methylol-D the 2nd, the preparation process resume of L-Methionine ferrous iron and formaldehyde reaction.
2nd takes turns:
Take 150.5 grams of (1.0mol) methionine(Met), add the filtrate 1 of first round gained, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get four water iron protochloride 158.4 grams (0.8mol) and it is dissolved in 650 grams of water, be heated to 60 DEG C. Being added by ferrous chloride aqueous solution in the Sodium L-methioninate aqueous solution and mix, nitrogen protection, keep temperature of reaction to be 90 DEG C, system pH is 6.5; reacting 1 hour, filter, filtrate is cooled to 5 DEG C, obtains brown precipitation; filter, obtain brown D, the ferrous solid of L-Methionine and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for next, and with D in the preparation process of L-Methionine ferrous iron, L-Methionine mixing continues to participate in reaction;
By D obtained above, the ferrous solid of L-Methionine joins in the filtrate 2 of first round gained, 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. Reaction is taken out and is filtered to obtain N-methylol-D after terminating, the ferrous solid of L-Methionine and filtrate 2, described N-methylol-D, the ferrous solid of L-Methionine through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of brown powder shape, ferrous 191.4 grams of L-Methionine, receipts rate 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 takes turns N-methylol-D at next, the preparation process resume of L-Methionine ferrous iron and formaldehyde reaction.
Special instruction, in the above-mentioned methods, is no less than two productions taken turns, it is possible to significantly improve product rate, reduces production cost; In case of no particular description, the present embodiment in the technology of foregoing, can be continued to use the first round and/or the 2nd mode taken turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, the 2nd takes turns, three-wheel and fourth round, and often wheel throws material methionine(Met) 150.5 grams (1.0mol)), and N-methylol-D, the ultimate production of L-Methionine ferrous iron is 767.8g, and product rate is 94.1%.
Embodiment 10N-methylol-D, the cyclic production of L-Methionine copper
The first round:
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings.Separately get copper chloride dihydrate 119 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by copper chloride solution in the Sodium L-methioninate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains blue precipitation, filters, and obtains blue D, L-Methionine copper solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for the 2nd, and with D in the preparation process of L-Methionine copper, L-Methionine mixing continues to participate in 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine copper solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine copper solid through 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, receipts rate 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 takes turns N-methylol-D the 2nd, the preparation process resume of L-Methionine copper and formaldehyde reaction.
2nd takes turns:
Take 150.5 grams of (1.0mol) methionine(Met), add the filtrate 1 of first round gained, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get copper chloride dihydrate 119 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by copper chloride solution in the Sodium L-methioninate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains blue precipitation, filters, and obtains blue D, L-Methionine copper solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for next, and with D in the preparation process of L-Methionine copper, L-Methionine mixing continues to participate in reaction;
By D obtained above, L-Methionine copper solid joins in the filtrate 2 of first round gained, 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine copper solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine copper solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of blue powder shape, L-Methionine copper 192.6 grams, receipts rate 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 takes turns N-methylol-D at next, the preparation process resume of L-Methionine copper and formaldehyde reaction.
Special instruction, in the above-mentioned methods, is no less than two productions taken turns, it is possible to significantly improve product rate, reduces production cost; In case of no particular description, the present embodiment in the technology of foregoing, can be continued to use the first round and/or the 2nd mode taken turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, the 2nd takes turns, three-wheel and fourth round, and often wheel throws material methionine(Met) 150.5 grams (1.0mol)), and N-methylol-D, the ultimate production of L-Methionine copper is 772.1g, and product rate is 93%.
Embodiment 11N-methylol-D, the cyclic production of L-Methionine manganese
The first round:
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings.Separately get tetrahydrate manganese chloride 158.4 grams (0.8mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added in the Sodium L-methioninate aqueous solution by the Manganous chloride tetrahydrate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains lightpink precipitation, filters, obtain D, L-Methionine manganese solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for the 2nd, and with D in the preparation process of L-Methionine manganese, L-Methionine mixing continues to participate in 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine manganese solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine manganese solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 187.7 grams, L-Methionine manganese, receipts rate 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 takes turns N-methylol-D the 2nd, the preparation process resume of L-Methionine manganese and formaldehyde reaction.
2nd takes turns:
Take 150.5 grams of (1.0mol) methionine(Met), add the filtrate 1 of first round gained, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get tetrahydrate manganese chloride 158.4 grams (0.8mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added in the Sodium L-methioninate aqueous solution by the Manganous chloride tetrahydrate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains lightpink precipitation, filters, obtain D, L-Methionine manganese solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for next, and with D in the preparation process of L-Methionine manganese, L-Methionine mixing continues to participate in reaction;
By D obtained above, L-Methionine manganese solid joins in the filtrate 2 of first round gained, stirs, to D, adds the formaldehyde solution 100 grams (1.0mol) of 30% in L-Methionine manganese slurries, keeps temperature to be 20 DEG C, reacts 1 hour. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine manganese solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine manganese solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, 188.9 grams, L-Methionine manganese, receipts rate 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 takes turns N-methylol-D at next, the preparation process resume of L-Methionine manganese and formaldehyde reaction.
Special instruction, in the above-mentioned methods, is no less than two productions taken turns, it is possible to significantly improve product rate, reduces production cost; In case of no particular description, the present embodiment in the technology of foregoing, can be continued to use the first round and/or the 2nd mode taken turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, the 2nd takes turns, three-wheel and fourth round, and often wheel throws material methionine(Met) 150.5 grams (1.0mol)), and N-methylol-D, the ultimate production of L-Methionine manganese is 756.8g, and product rate is 93%.
Embodiment 12N-methylol-D, the cyclic production of L-Methionine cobalt
The first round:
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings.Separately get CoCL2 6H2O 168.3 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by cobalt chloride solution in the Sodium L-methioninate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains white precipitate, filters, obtains D, L-Methionine cobalt solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for the 2nd, and with D in the preparation process of L-Methionine cobalt, L-Methionine mixing continues to participate in 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine cobalt solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine cobalt solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, L-Methionine cobalt 188.6 grams, receipts rate 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 takes turns N-methylol-D the 2nd, the preparation process resume of L-Methionine cobalt and formaldehyde reaction.
2nd takes turns:
Take 150.5 grams of (1.0mol) methionine(Met), add the filtrate 1 of first round gained, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get CoCL2 6H2O 168.3 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by cobalt chloride solution in the Sodium L-methioninate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains white precipitate, filters, and obtains white D, L-Methionine cobalt solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for next, and with D in the preparation process of L-Methionine cobalt, L-Methionine mixing continues to participate in reaction;
By D obtained above, L-Methionine cobalt solid joins in the filtrate 2 of first round gained, 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine cobalt solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine cobalt solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of white powder, L-Methionine cobalt 192.8 grams, receipts rate 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 takes turns N-methylol-D at next, the preparation process resume of L-Methionine cobalt and formaldehyde reaction.
Special instruction, in the above-mentioned methods, is no less than two productions taken turns, it is possible to significantly improve product rate, reduces production cost; In case of no particular description, the present embodiment in the technology of foregoing, can be continued to use the first round and/or the 2nd mode taken turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, the 2nd takes turns, three-wheel and fourth round, and often wheel throws material methionine(Met) 150.5 grams (1.0mol)), and N-methylol-D, the ultimate production of L-Methionine cobalt is 771g, and product rate is 94%.
Embodiment 13N-methylol-D, the cyclic production of L-Methionine chromium
The first round:
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings.Separately get chromium chloride hexahydrate 107.7 grams (0.4mol) and it is dissolved in 500 grams of water, nitrogen protection, be heated to 60 DEG C. Being added in the Sodium L-methioninate aqueous solution by the chromium trichloride aqueous solution and mix, nitrogen protection, keep temperature of reaction to be 90 DEG C, system pH is 7.0; reacting 1 hour, filter, filtrate is cooled to 5 DEG C, obtains red-purple precipitation; filter, obtain red-purple D, L-Methionine chromium solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for the 2nd, and with D in the preparation process of L-Methionine chromium, L-Methionine mixing continues to participate in 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine chromium solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine chromium solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the pulverous N-methylol-D of red-purple, L-Methionine chromium 187.5 grams, receipts rate 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 takes turns N-methylol-D the 2nd, the preparation process resume of L-Methionine chromium and formaldehyde reaction.
2nd takes turns:
Take 150.5 grams of (1.0mol) methionine(Met), add the filtrate 1 of first round gained, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get chromium chloride hexahydrate 107.7 grams (0.4mol) and it is dissolved in 500 grams of water, nitrogen protection, be heated to 60 DEG C. Being added in the Sodium L-methioninate aqueous solution by the chromium trichloride aqueous solution and mix, nitrogen protection, keep temperature of reaction to be 90 DEG C, system pH is 7.0; reacting 1 hour, filter, filtrate is cooled to 5 DEG C, obtains red-purple precipitation; filter, obtain red-purple D, L-Methionine chromium solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for next, and with D in the preparation process of L-Methionine chromium, L-Methionine mixing continues to participate in reaction;
By D obtained above, L-Methionine chromium solid joins in the filtrate 2 of first round gained, 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine chromium solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine chromium solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the pulverous N-methylol-D of red-purple, L-Methionine chromium 183.5 grams, receipts rate 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 takes turns N-methylol-D at next, the preparation process resume of L-Methionine chromium and formaldehyde reaction.
Special instruction, in the above-mentioned methods, is no less than two productions taken turns, it is possible to significantly improve product rate, reduces production cost; In case of no particular description, the present embodiment in the technology of foregoing, can be continued to use the first round and/or the 2nd mode taken turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, the 2nd takes turns, three-wheel and fourth round, and often wheel throws material methionine(Met) 150.5 grams (1.0mol)), and N-methylol-D, the ultimate production of L-Methionine chromium is 752.3g, and product rate is 94%.
Embodiment 14N-methylol-D, the cyclic production of L-Methionine nickel
The first round:
Take 150.5 grams of (1.0mol) methionine(Met), add water 600 grams, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings.Separately get Dehydrated nickel chloride 91.6 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by nickel chloride aqueous solution in the Sodium L-methioninate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains green precipitation, filters, and obtains green D, L-Methionine nickel solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for the 2nd, and with D in the preparation process of L-Methionine nickel, L-Methionine mixing continues to participate in 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine nickel solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine nickel solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of green flour powder, 192.4 grams, L-Methionine nickel, receipts rate 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 takes turns N-methylol-D the 2nd, the preparation process resume of L-Methionine nickel and formaldehyde reaction.
2nd takes turns:
Take 150.5 grams of (1.0mol) methionine(Met), add the filtrate 1 of first round gained, add 40 grams, sodium hydroxide, be heated to 80 DEG C of dissolvings. Separately get Dehydrated nickel chloride 91.6 grams (0.7mol) and it is dissolved in 600 grams of water, be heated to 60 DEG C. Being added by nickel chloride aqueous solution in the Sodium L-methioninate aqueous solution and mix, keep temperature of reaction to be 90 DEG C, system pH is 7.0, reacts 1 hour, filters, and filtrate is cooled to 5 DEG C, obtains green precipitation, filters, and obtains green D, L-Methionine nickel solid and filtrate 1. Gained filtrate 1 recycle, takes turns N-methylol-D for next, and with D in the preparation process of L-Methionine nickel, L-Methionine mixing continues to participate in reaction;
By D obtained above, L-Methionine nickel solid joins in the filtrate 2 of first round gained, 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. Reaction is taken out and is filtered to obtain N-methylol-D, L-Methionine nickel solid and filtrate 2 after terminating, described N-methylol-D, L-Methionine nickel solid through cold water washing, 105 DEG C of vacuum-dryings, pulverize, obtain the N-methylol-D of green flour powder, 194.5 grams, L-Methionine nickel, receipts rate 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 takes turns N-methylol-D at next, the preparation process resume of L-Methionine nickel and formaldehyde reaction.
Special instruction, in the above-mentioned methods, is no less than two productions taken turns, it is possible to significantly improve product rate, reduces production cost; In case of no particular description, the present embodiment in the technology of foregoing, can be continued to use the first round and/or the 2nd mode taken turns, carry out taking turns cyclic production more.
Under aforesaid method, 4 take turns production (first round, the 2nd takes turns, three-wheel and fourth round, and often wheel throws material methionine(Met) 150.5 grams (1.0mol)), and N-methylol-D, the ultimate production of L-Methionine nickel is 785.1g, and product rate is 95%.
Embodiment 15 utilizes N-methylol-D, and N-methylol-D produced by L-Methionine microelement chelate production equipment, L-Methionine copper
Utilize N-methylol-D, N-methylol-D prepared by L-Methionine microelement chelate production equipment, the production method of L-Methionine copper, described N-methylol-D, L-Methionine microelement chelate production equipment, comprise D, L-Methionine microelement chelate preparation feedback tank 1, tripping device 2, D, the retort 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 connected with tripping device 2 by the backflow pipeline of band valve respectively with retort 3, described liquid storage tank 4 respectively with retort 1, tripping device 2 is connected with retort 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,Described tripping device 2 is for taking out filter machine.
Take 15 kilograms of (about 100mol) methionine(Met), add water 60 kilograms, add 4 kilograms, sodium hydroxide, be heated to 80 DEG C and dissolve to obtain solution 1. separately get copper chloride dihydrate 11.9 grams (about 70mol) and it is dissolved in 60 kg water, it is heated to 60 DEG C and dissolves to obtain solution 2, described solution 1 and solution 2 are joined in retort 1 and mix, temperature of reaction is kept to be 90 DEG C, system pH is 7.0, react 1 hour, after question response terminates, send into tripping device 2 and it is separated removing solid insoluble, the filtrate of gained is cooled to 5 DEG C of crystallizations, then blue D is obtained through tripping device 2 separation, L-Methionine copper solid 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 the micro-copper of L-Methionine starts, described filtrate 1 and D, L-Methionine mixes, N-methylol-D is taken turns for another, the preparation of L-Methionine copper,
By D obtained above, retort 3 sent into by L-Methionine copper solid, adds the water of 1 times of quality, stirs, then to the D in retort 3, adds the formaldehyde solution 10 kilograms (about 100mol) of 30% in L-Methionine copper slurries, keeps temperature to be 20 DEG C, reacts 1 hour. After reaction terminates, send in tripping device 2 and it is separated to obtain N-methylol-D, L-Methionine copper solid and filtrate 2; Gained N-methylol-D, L-Methionine copper 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 obtaining blue powder shape is sent into, L-Methionine copper 19 kilograms, receipts rate 87% after dry, 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 sent in liquid storage tank 4 and is stored, and takes turns N-methylol-D at another, the preparation process resume of L-Methionine copper and formaldehyde reaction, for the preparation of N-methylol-D, and L-Methionine copper.
What finally illustrate is, above embodiment is only in order to illustrate the technical scheme of the present invention and unrestricted, although with reference to better embodiment to invention has been detailed explanation, it will be understood by those within the art that, the technical scheme of the present invention can be modified or equivalent replacement, and not departing from objective and the scope of technical solution of the present invention, it all should be encompassed in the middle of the right of the present invention.
Claims (11)
1. prepare N-methylol-D, the method for L-Methionine microelement chelate for one kind, it is characterised in that, comprise the step carried out as follows:
(1) by D, L-Methionine adds water and mineral alkali, heating for dissolving obtains solution 1, is separately added to the water by the trace metal salts of solubility, and heating for dissolving obtains solution 2, described solution 1 and solution 2 are mixed to get reaction system, maintaining reaction system pH is 5.5��7.0, reacting by heating, and reaction is filtered after terminating, gained filtrate crystallization obtains D, L-Methionine microelement chelate;
(2) by the D of step (1) gained, L-Methionine microelement chelate carries out hydroxymethylation with formaldehyde in water medium, and reaction filters to obtain N-methylol-D, L-Methionine microelement chelate after terminating; In described step (1), the trace metal salts of described solubility is the salt of the solubility of iron, copper, zinc, manganese, cobalt, nickel and chromium.
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), the trace metal salts of described solubility 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.
3. preparation N-methylol-D according to claim 1 and 2, the method of L-Methionine microelement chelate, it is characterized in that: in described step (1), D, in the trace metal salts reaction system of L-Methionine and solubility, micro-metals and D, the mol ratio of L-Methionine is 0.4��0.8:1.
4. preparation N-methylol-D according to claim 1 and 2, the method of L-Methionine microelement chelate, it is characterised in that: in described step (1), described mineral alkali is sodium hydroxide, described sodium hydroxide and D, the mol ratio of L-Methionine is 0.8��1.2:1.
5. preparation N-methylol-D according to claim 1 and 2, the method of L-Methionine microelement chelate, it is characterised in that: in described step (1), described solution 1 and solution 2 mix, reacting by heating temperature is 60 DEG C��90 DEG C, and the reaction times is 1��3 hour.
6. preparation N-methylol-D according to claim 1 and 2, the method for L-Methionine microelement chelate, it is characterised in that: crystallization described in described step (1) is that filtrate is cooled to 0 DEG C��10 DEG C crystallizations.
7. preparation N-methylol-D according to claim 1 and 2, the method of L-Methionine microelement chelate, it is characterized in that: in described step (2), described D, the mol ratio of L-Methionine microelement chelate and formaldehyde reaction is 1.0��1.2:1.
8. preparation N-methylol-D according to claim 1 and 2, the method of L-Methionine microelement chelate, it is characterized in that: in described step (2), described D, L-Methionine microelement chelate and formaldehyde reaction temperature control at 20 DEG C��30 DEG C, and the reaction times is 0.5��2 hour.
9. preparation N-methylol-D according to claim 1 and 2, the method of L-Methionine microelement chelate, it is characterized in that: the D described in described step (2), after L-Methionine microelement chelate and formaldehyde reaction terminate, filter, gained N-methylol-D, L-Methionine microelement chelate cold water washing, then dry, pulverize, obtain powder shape N-methylol-D, L-Methionine microelement chelate.
10.N-methylol-D, the circulation producing method of L-Methionine microelement chelate, it is characterised in that, comprise the following steps:
A is by D, L-Methionine adds water and mineral alkali, and heating for dissolving obtains solution 1, is separately added to the water by the trace metal salts of solubility, heating for dissolving obtains solution 2, described solution 1 and solution 2 are mixed to get reaction system, and maintaining reaction system pH is 5.5��7.0, reacting by heating, reaction is filtered after terminating, gained filtrate crystallization, filters to obtain D, L-Methionine microelement chelate and filtrate 1; The recycle of described filtrate 1, takes turns N-methylol-D for another, and with D in the preparation process of L-Methionine microelement chelate, L-Methionine mixing continues 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, and reaction filters to obtain N-methylol-D, L-Methionine microelement chelate and filtrate 2 after terminating; Gained filtrate 2 takes turns N-methylol-D at another, and the preparation process resume of L-Methionine microelement chelate and formaldehyde carry out hydroxymethylation.
11. 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 microelement chelate preparation feedback tank (1), tripping device (2), D, L-Methionine microelement chelate and formaldehyde carry out the retort (3) of hydroxymethylation, liquid storage tank (4), washing device (5), drying installation (6) and shredding unit (7), described retort (1) is connected with tripping device (2) by the backflow pipeline of band valve respectively with retort (3), described liquid storage tank (4) respectively with retort (1), tripping device (2) is connected with retort (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 is by D, L-Methionine adds water and mineral alkali, heating for dissolving obtains solution 1, separately the trace metal salts of solubility is added to the water, heating for dissolving obtains solution 2, described solution 1 and solution 2 are joined in retort (1) and is mixed to get reaction system, maintaining reaction system pH is 5.5��7.0, reacting by heating, after question response terminates, send into tripping device (2) separation and remove solid matter, gained filtrate crystallization, then D it is separated to obtain 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 and D, L-Methionine mixes, N-methylol-D is taken turns for another, the preparation of L-Methionine microelement chelate,
B is by the D of gained in step a, L-Methionine microelement chelate sends into retort (3), water medium carries out hydroxymethylation with formaldehyde, reaction is sent into after terminating and is separated to obtain N-methylol-D, L-Methionine microelement chelate and filtrate 2 in 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 dry shredding unit (7) is pulverized and obtain pulverous 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, the preparation process resume of L-Methionine microelement chelate and formaldehyde carry out hydroxymethylation, for the preparation of N-methylol-D, and L-Methionine microelement chelate.
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Effective date of registration: 20160801 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. |