CN103641755B - The preparation method of D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate - Google Patents
The preparation method of D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate Download PDFInfo
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Abstract
The present invention is directed to chemical field, relate to D, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, the method adopts iS-One legal system to obtain prussic acid gas mixture and methylthiopropionaldehyde is initial feed, obtain 2-2-hydroxy-4-methylthio butyronitrile system mineral alkali and be hydrolyzed to obtain D, L-2-hydroxy-4-methylthiobutyric acid salt, D, L-2-hydroxy-4-methylthiobutyric acid salt generates D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate with micro-metals salt chelating again.The method processing step is few, and cheaper starting materials is easy to get, intermediate stable in properties, and total cost of production is low; The yield of the D obtained, L-2-hydroxy-4-methylthiobutyric acid microelement chelate is high, purity is high, tap density is large; Can be used as animal feedstuff additive effectively to mix with feed, with the trace element in supplementary daily ration and amino acid, improve the production performance in animal body and immune performance, and can be used as pharmaceutical reagent use.
Description
Technical field
The present invention is directed to chemical field, relate to D, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, be specifically related to a kind of at D, D is prepared on the basis of L-2-hydroxy-4-methylthiobutyric acid salt production process, the method for L-2-hydroxy-4-methylthiobutyric acid microelement chelate.
Background technology
Methionine hydroxy analog (MHA) is also known as D, L-2-hydroxy-4-methylthiobutyric acid, it is a kind of methionine additive, have that toxicity is little, rumen digestibility is low, promote the synthesis of rumen microorganism, the protein saved in daily ration, the production performance improving cow, the production performance and immunological competence, the discharge of minimizing ammonia that improve animal, the feature such as contaminate environment is less, production technique is simple, price is lower, be the most economical effective a kind of amino acid source of animal.Although methionine hydroxy analog has above-mentioned advantage, commercially replacing more expensive amino acid gradually, still there is following problem in it:
(1) there is stronger corrodibility and irritating smell, store, transport, use inconvenience, expensive dedicated liquid charging system must be used;
(2) viscosity is very large, not easily mixes in feed pre-mixing material;
(3) meet water and release a large amount of heats, cause feed fermentation of generating heat in storage and transport process to become sour; Acidity is very large, and pH is about 1, and other composition generation acid-base reactions easily and in feed or premixing feedstuff, damage the nutritive ingredient in feed.
100 for many years, 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.
Methionine hydroxy analog micro-metals series inner complex, i.e. D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate is compound metal trace element necessary for growth of animal and methionine hydroxy analog effect being generated Chelating state, is a kind of trace element replenisher close to natural form in animal body.Compared with inorganic salt, there is good chemical stability and biochemical stability, be a kind of desirable high-efficiency feed additive, overcome the weak point of methionine hydroxy analog completely.
At present, methionine hydroxy analog and the inorganic salt of methionine hydroxy analog micro-metals inner complex product many employings outsourcing of commercial type are raw material, the methionine hydroxy analog inner complex granularity of synthesis is little, filter cake is sticky, dehydration is difficult, drying time is long, and production process dust is large, and particularly production cost is higher.
D, the production cost of L-2-hydroxy-4-methylthiobutyric acid microelement chelate mainly concentrates on D, on the cost of L-2-hydroxy-4-methylthiobutyric acid, reduce D, the production cost of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, just D must be reduced, the production cost of L-2-hydroxy-4-methylthiobutyric acid.At present, China
D, L-2-hydroxy-4-methylthiobutyric acid mainly dependence on import, and main manufacturer is An Disu, Degussa and SUMITOMO CHEMICAL.In prior art, D, L-2-hydroxy-4-methylthiobutyric acid main production is: highly purified 3-methylthiopropionaldehyde and High Purity Hydrogen cyanic acid react, and obtains 2-2-hydroxy-4-methylthio butyronitrile, 2-2-hydroxy-4-methylthio butyronitrile is hydrolyzed under mineral acid, obtains MHA.But this production technique production cost is all higher, particularly, in order to obtain high yield, all need purer prussic acid, and prussic acid is excessive often, the rectifying purifying that prussic acid is extra and excessive use all can cause the increase of cost, the increase of this cost, particularly in technical scale, huge financial loss will be caused; Moreover being not suitable for of reaction system also can increase the weight of the burden that subsequent purification is separated, reduce the yield of product.
In addition, due to commercially available D, L-2-hydroxy-4-methylthiobutyric acid is a kind of mixture, wherein contain dimer and the polymer thereof of about 22%, and these polymers exist mainly with the form of ester or acid anhydrides, cause these polymers to be difficult to react with micro-metals, be finally adsorbed on its surface, product is difficult to drying, and then affects product quality.
For these reasons, the present invention explores and a kind of on the basis of D, L-2-hydroxy-4-methylthiobutyric acid salt production process, prepares D, the method for L-2-hydroxy-4-methylthiobutyric acid microelement chelate.
Summary of the invention
In view of this, the invention provides a kind of D, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, the method cheaper starting materials is easy to get, intermediate stable in properties, processing step is few, total cost of production is low, and the yield of the D obtained, L-2-hydroxy-4-methylthiobutyric acid microelement chelate is high, purity is high, have powder crystal formation, tap density is large.
For achieving the above object, technical scheme of the present invention is:
The preparation method of D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate, comprises the following steps:
A, with methane, ammonia and oxygen for raw material, adopt iS-One method composition principle, be prepared into prussic acid gas mixture I; Described prussic acid gas mixture I obtains prussic acid gas mixture II through deamination process;
B, described prussic acid gas mixture II under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile system with methylthiopropionaldehyde;
C, described 2-2-hydroxy-4-methylthio butyronitrile system mineral alkali MOH are hydrolyzed, and obtain D, L-2-hydroxy-4-methylthiobutyric acid salt; Described MOH is one or more in LiOH, NaOH and KOH;
D, described D, L-2-hydroxy-4-methylthiobutyric acid salt and micro-metals salt carry out chelatropic reaction, generate D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate.
Described iS-One method (Andrussow method) is the industrial process completed the 1950's, is the main method of producing prussic acid.The main raw material that it adopts has methane, ammonia and oxygen, therefore is again methane oxidation proceses of ammonia.This method is under the condition more than normal pressure, l000 DEG C, material mixed gas is led to the silk screen that people is made up of platinum, rhodium alloy catalyst platinum and rhodium, or the wire-mesh catalyst bed be made up of platinum iridium alloy, and the oxidative ammonolysis carried out, its reaction formula is 2CH
4+ 2NH
3+ 3O
2→ 2HCN+6H
2o.At present, this technology is very ripe, has special prussic acid synthetic tower for the preparation of hydrocyanic acid gas.
Described deamination process refers to and passes in acid by prussic acid gas mixture I standby for iS-One legal system, sloughs the operation of ammonia.The Main Function that described acid rises is absorbing ammonia G&W steam, therefore preferably sulfuric acid, and further preferred mass mark is the sulfuric acid of 75% ~ 90%.The prussic acid gas mixture of the present invention before and after deamination process all can be used for the preparation of 2-2-hydroxy-4-methylthio butyronitrile, and prussic acid gas mixture II character just after deamination process is more excellent.Industrially, special acid tower can be set for deamination process.
Further, described prussic acid gas mixture I is preferably made up of the component of following mass percent: hydrocyanic acid gas 8.8% ± 2%, water vapour 3.9% ± 2%, ammonia 1.6% ± 2%, hydrogen 1.1% ± 2%, nitrogen 76.0% ± 2%, oxygen 1.5% ± 2%, carbon monoxide 5.6% ± 2%, carbonic acid gas 1.1% ± 2%, methane 0.4% ± 2%.Described prussic acid gas mixture II is preferably made up of the component of following mass percent: hydrocyanic acid gas 9.4% ± 2%, hydrogen 1.6% ± 2%, nitrogen 79.4% ± 2%, oxygen 1.7% ± 2%, carbon monoxide 5.8% ± 2%, carbonic acid gas 1.5% ± 2%, methane 0.6% ± 2%.
Described prussic acid gas mixture II is particularly suitable as the raw material of preparation 2-2-hydroxy-4-methylthio butyronitrile.Its reaction is except obtained 2-2-hydroxy-4-methylthio butyronitrile, also containing residual qualities mark in reaction solution is the prussic acid of 0.05% ~ 0.5% and the water of 2% ~ 5%, just because of the existence of residual hydrogen cyanic acid and water, this system (namely 2-2-hydroxy-4-methylthio butyronitrile is together with reaction solution) can long-term storage and not decomposing.The reaction system of 2-2-hydroxy-4-methylthio butyronitrile also can be adjusted to pH with acid further and 2 ~ 4 to deposit, like this, even if still keep longer stability at normal temperatures.The acid of described adjustment pH can be sulfuric acid, phosphoric acid etc., massfraction preferably 85%.2-2-hydroxy-4-methylthio butyronitrile system, without the need to carrying out any separation and purification, can be directly used in D, the production of L-2-hydroxy-4-methylthiobutyric acid salt.
Further, described methylthiopropionaldehyde is not purified methylthiopropionaldehyde, wherein containing the heavy constituent of the methylthiopropionaldehyde of massfraction 94.5% ~ 96%, the light constituent of massfraction 3.5% ~ 5.3% and massfraction 0.2% ~ 0.5%; Described light constituent is thiomethyl alcohol, methyl alcohol, propenal and water; Described restructuring is divided into dipolymer and the trimer of methylthiopropionaldehyde.
Step B is the nucleophilic addition under base catalysis.The alkali of described katalysis is organic bases and/or mineral alkali; The consumption of the alkali of described katalysis is the pH maintaining reaction system is 4.0 ~ 6.5, and preferred pH is 5.0 ~ 5.5.The preferred low-molecular-weight amine compound of described organic bases, the further aminated compounds of preferred 3 ~ 20 carbon atoms, this compounds with methylthiopropionaldehyde arbitrarily than mixing, can be conducive to fast reaction speed.The aminated compounds of described 3 ~ 20 carbon atoms comprises triethylamine, tri-isopropanolamine, DMA, imidazoles, picoline, pyridine etc., use wherein one or more can, particularly preferably triethylamine and/or pyridine.Described mineral alkali is one or more in metal hydroxides, metal cyanides, metal carbonate and alkali metal bicarbonate salt, or is ammonia.Described metallic hydrogen oxidation compound, as sodium hydroxide or potassium hydroxide; Metal cyanides, as sodium cyanide or potassium cyanide; Metal carbonate, as sodium carbonate or salt of wormwood; Alkali metal bicarbonate salt, as sodium bicarbonate or saleratus.Independent a kind of mineral alkali or mixed base can.
Further, in the alkali of described katalysis, also add acid, form mixture or the damping fluid of bronsted lowry acids and bases bronsted lowry; Described acid comprises mineral acid and organic acid.Adding or the formation of damping fluid of acid, reaction system can be made to maintain in more stable pH value range.Described organic acid is the one in acetic acid, formic acid, citric acid, Phenylsulfonic acid, trifluoromethanesulfonic acid etc.; Described mineral acid is sulfuric acid or phosphoric acid.The damping fluid formed is as Trisodium Citrate-sodium hydrate buffer solution, sodium succinate-sodium hydrate buffer solution, acetic acid-sodium hydrate buffer solution etc., optimization citric acid-sodium hydrate buffer solution.
In described step B, the mol ratio of prussic acid and methylthiopropionaldehyde is 1:1.0 ~ 1.05; Reaction pressure is 0.09 ~ 0.5MPa, namely can react at the environment of negative pressure to malleation, for considering of equipment requirements and reaction efficiency, and preferably 0.1 ~ 0.3MPa, more preferably 0.1 ~ 0.15MPa; Temperature of reaction is 30 ~ 80 DEG C, preferably 35 ~ 60 DEG C, more preferably 40 ~ 45 DEG C.
In described step C, described MOH is mineral alkali, preferred sodium hydroxide.When being hydrolyzed 2-2-hydroxy-4-methylthio butyronitrile, the mol ratio of described 2-2-hydroxy-4-methylthio butyronitrile and MOH is 1:1.2 ~ 2.5, and preferred molar ratio is 1:1.5 ~ 2; The massfraction of MOH is 30% ~ 50%, and preferred mass mark is 35% ~ 45%; Hydrolysising reacting temperature controls at 70 ~ 110 DEG C, and preferable temperature is 80 ~ 100 DEG C.Available HPLC detects the residual volume of 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide, until can't detect the terminal that 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide be considered as reacting, the usual reaction times needs 2h ~ 5h, and the preferred reaction time is 3h ~ 4h.
In described step D, described micro-metals salt preferred solubility micro-metals salt, one or more more preferably in zinc chloride, zinc sulfate, zinc acetate, zinc carbonate, cupric chloride, copper sulfate, neutralized verdigris, copper carbonate, iron protochloride, ferrous sulfate, iron protocarbonate, Iron diacetate, manganous chloride, manganous sulfate, manganese acetate, manganous carbonate, cobalt chloride, rose vitriol, Cobaltous diacetate, cobaltous carbonate, chromium chloride, chromium sulphate, chromium acetate, chromium carbonate, single nickel salt, nickel acetate, nickelous carbonate, nickelous chloride etc.The D that this chelatropic reaction obtains after can directly using above-mentioned 2-2-hydroxy-4-methylthio butyronitrile system to be hydrolyzed, L-2-hydroxy-4-methylthiobutyric acid salt brine solution.Further, the D that preferred steps C obtains, L-2-hydroxy-4-methylthiobutyric acid salt is together with its reaction solution after organic solvent extraction, and the aqueous phase obtained and D, L-2-hydroxy-4-methylthiobutyric acid salt brine solution, be directly used in step D and micro-metals reactant salt.Described organic solvent is immiscible with water or in water the solubleness organic solvent that is less than 5% preferably, as toluene, benzene, m-xylene, ethyl acetate, ether, methylene dichloride, chloroform etc.; Further, the volume ratio of organic solvent and hydrolyzed solution is 0.5 ~ 2:1.Described D, L-2-hydroxy-4-methylthiobutyric acid salt brine solution with micro-metals reactant salt before, as far as possible ammonia in hydrolyzed solution is got rid of clean.
Further, the chelatropic reaction of described step D, the mol ratio of preferred D, L-2-hydroxy-4-methylthiobutyric acid salt and micro-metals salt is 1:0.35 ~ 0.80, and temperature of reaction is 50 ~ 90 DEG C, and the reaction times is 0.5 ~ 2 hour.
Further, the D that described step D obtains, L-2-hydroxy-4-methylthiobutyric acid microelement chelate also comprises re-crystallization step, that is: by the D of step D gained, the crystallizing agent of L-2-hydroxy-4-methylthiobutyric acid microelement chelate and its quality 50ppm ~ 3000ppm is in water medium, be heated to 60 ~ 90 DEG C, dissolve completely, crystallisation by cooling, be separated, dried crystals, obtains the D of high purity and high-bulk-density, L-2-hydroxy-4-methylthiobutyric acid microelement chelate.The consumption of described water medium, is preferably adjusted to the amount of 70% ~ 90% of its saturation concentration by the concentration of D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate, in the solution of this concentration, the crystal quality that recrystallization goes out is best, and crystalline rate is also high; Preferred use deionized water.Crystallisation by cooling temperature preferably 0 ~ 10 DEG C.Wherein, described crystallizing agent has the character of tensio-active agent, such crystallizing agent and water effect, can form the cellular template of uniform pore diameter, rule, when crystallization, namely forms the crystal that size is even, profile is regular gradually in a template.One or more in described crystallizing agent optimization citric acid, sodium laurylsulfonate, lactic acid, Walocel MT 20.000PV, Natvosol and Aluctyl.
The present invention separately provides one to utilize D, D prepared by L-2-hydroxy-4-methylthiobutyric acid microelement chelate production equipment, the method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, the method is simple to operate, controllability is strong, production cost is low, obtained D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate yield is high, purity is high, and have powder crystal formation, tap density is large.
For achieving the above object, technical scheme of the present invention is:
Utilize D, D prepared by L-2-hydroxy-4-methylthiobutyric acid microelement chelate production equipment, the method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, described production equipment comprises prussic acid synthetic tower, acid tower, the first reactor, the second reactor, crystallization kettle and tripping device; Fill the sulfuric acid that massfraction is 75% ~ 90% in described acid tower, the air outlet of prussic acid synthetic tower is communicated with the inlet mouth of acid tower by pipeline, and the air outlet of acid tower is communicated with the first reactor by the pipeline being provided with throttling valve;
A, with methane, ammonia and oxygen for raw material, adopt iS-One method composition principle, prepare prussic acid gas mixture I by prussic acid synthetic tower; Described prussic acid gas mixture I passes into acid tower and sloughs ammonia and water vapour, obtains prussic acid gas mixture II;
B, described prussic acid gas mixture II, under throttle valve control, pass in the methylthiopropionaldehyde in the first reactor with the speed of 250 ~ 350L/min, under the katalysis of alkali, fully react to obtain the reaction system of 2-2-hydroxy-4-methylthio butyronitrile;
C, described 2-2-hydroxy-4-methylthio butyronitrile system are hydrolyzed with mineral alkali MOH in the second reactor, and after reaction terminates, with organic solvent extraction, the aqueous phase obtained is D, L-2-hydroxy-4-methylthiobutyric acid salt brine solution; Described MOH is one or more in LiOH, NaOH and KOH;
D, described D, L-2-hydroxy-4-methylthiobutyric acid salt brine solution and micro-metals salt fully carry out chelatropic reaction in crystallization kettle, through tripping device removing insolubles, filtrate crystallisation by cooling, be separated to obtain D again, L-2-hydroxy-4-methylthiobutyric acid microelement chelate crude product and filtrate, use cold water washing crude product; Merging filtrate and washings, be circulated to the chelatropic reaction of D, L-2-hydroxy-4-methylthiobutyric acid salt when producing next time; Again in crystallization kettle, the crystallizing agent of the D after described washing, L-2-hydroxy-4-methylthiobutyric acid microelement chelate crude product and its quality 50ppm ~ 3000ppm dissolves completely in water medium, cooling recrystallization, be separated through tripping device, obtain crystal and recrystallization filtrate; Described recrystallization filtrate is circulated to the washing of crude product when producing next time; Described crystal proceeds to drying plant, dry, obtains the D of high purity and high-bulk-density, L-2-hydroxy-4-methylthiobutyric acid microelement chelate.
Described tripping device can be whizzer, suction filter, gets rid of worry machine etc.Reactor used in the present invention is not limited to this, as the preparation of 2-2-hydroxy-4-methylthio butyronitrile and the preparation of D, L-2-hydroxy-4-methylthiobutyric acid salt also can be carried out in same reactor; Certainly, after the chelating of D, L-2-hydroxy-4-methylthiobutyric acid salt brine solution and micro-metals salt also can complete in independent reactor, recrystallization in crystallization kettle is transferred to.The reaction conditions optimized in preceding method, is also applicable to the method for this part band production equipment.
Advantageous Effects of the present invention is:
The prussic acid gas mixture adopting iS-One legal system standby and not purified methylthiopropionaldehyde, raw material, without the need to rectifying purifying, is saved the production time, is improve production efficiency, also reduce production cost; The 2-2-hydroxy-4-methylthio butyronitrile system prepared, stable in properties, can long-term storage, is more conducive to the production of subsequent product.2-2-hydroxy-4-methylthio butyronitrile system just can be directly used in D without the need to separation and purification, the preparation of L-2-hydroxy-4-methylthiobutyric acid salt, obtained D, L-2-hydroxy-4-methylthiobutyric acid salt also can be directly used in D together with its reaction solution, the preparation of L-2-hydroxy-4-methylthiobutyric acid microelement chelate.
Method processing step of the present invention is few, and total cost of production is low, and the yield of the D obtained, L-2-hydroxy-4-methylthiobutyric acid microelement chelate is high, and purity is high, and have powder crystal formation, tap density is large.The problems such as solve in actual production process, D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate yield is low, and purity is not high, and filter cake is sticky, and hard-pumped is filtered, and after drying, finished product is loose, and density is little, fluency difference.Can be used as animal feedstuff additive, effectively mix with feed, supplement the trace element in daily ration and amino acid, improve the production performance in animal body and immune performance; Further, due to its high purity and high-bulk-density, also can be used as pharmaceutical reagent and use.
Accompanying drawing explanation
Fig. 1 is D, L-2-hydroxy-4-methylthiobutyric acid 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 1-8 is the preparation of 2-2-hydroxy-4-methylthio butyronitrile; Embodiment 9 ~ 14 is the preparation of D, L-2-hydroxy-4-methylthiobutyric acid salt; Embodiment 15 ~ 20 is the preparation of D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate.
Embodiment 1
Detect from prussic acid synthetic tower prussic acid gas mixture I out, consisting of of prussic acid gas mixture I: hydrocyanic acid gas 8.87%, water vapour 3.88%, ammonia 1.64%, hydrogen 1.13%, nitrogen 76.01%, oxygen 1.48%, carbon monoxide 5.67%, carbonic acid gas 1.13%, methane 0.39%.
Prussic acid gas mixture I through 75% sulfuric acid tower absorb ammonia in gas mixture and water vapour thereof after, consisting of of the prussic acid gas mixture II obtained: hydrocyanic acid gas 9.35%, hydrogen 1.57%, nitrogen 79.44%, oxygen 1.71%, carbon monoxide 5.79%, carbonic acid gas 1.50%, methane 0.64%.
Embodiment 2
Prussic acid gas mixture II being passed into 223.3g massfraction is in the methylthiopropionaldehyde of 94.5%, containing 3.3g pyridine in methylthiopropionaldehyde.React under normal pressure, controlling temperature of reaction is 45 DEG C, and draft speed is 300L/min, and tail gas sodium hydroxide absorbs, and monitors the residual volume of methylthiopropionaldehyde with HPLC.When methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 270.64g, 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.5%.
Embodiment 3
Prussic acid gas mixture II being passed into 223.3g massfraction is in the methylthiopropionaldehyde of 94.5%, contains the water of 2.2g pyridine and 10g in methylthiopropionaldehyde.Under 0.15MPa, controlling temperature of reaction is 42 DEG C, and draft speed is 280L/min, and tail gas sodium hydroxide absorbs, and monitors the residual volume of methylthiopropionaldehyde with HPLC.When methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 279.54g, 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.07%.
Embodiment 4
Prussic acid gas mixture II being passed into 247.2g massfraction is in the methylthiopropionaldehyde of 94.5%, contains the water of 2.2g pyridine and 15g in methylthiopropionaldehyde.Under 0.5MPa, controlling temperature of reaction is 45 DEG C, and draft speed is 280L/min, and tail gas sodium hydroxide absorbs, and monitors the residual volume of methylthiopropionaldehyde with HPLC.When methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 294.54g, 2-2-hydroxy-4-methylthio butyronitrile is 98%, prussic acid remnants 0.07%.
Embodiment 5
Prussic acid gas mixture II being passed into 227.3g massfraction is in the methylthiopropionaldehyde of 94.5%, contains the water of 3.3g pyridine and 4g in methylthiopropionaldehyde.Under 0.09MPa, controlling temperature of reaction is 80 DEG C, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 DEG C.Monitor the residual volume of methylthiopropionaldehyde with HPLC, when methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 277.4g, 2-2-hydroxy-4-methylthio butyronitrile is 97%, prussic acid remnants 0.06%, moisture content 2%.
Embodiment 6
Prussic acid gas mixture II being passed into 237.3g massfraction is in the methylthiopropionaldehyde of 94.5%, containing 8.5g water in methylthiopropionaldehyde, adds a certain amount of catalyzer sodium carbonate in mixed system, keeps the pH of system to be 5.5 passing in prussic acid gas mixture process.Under 0.5MPa, controlling temperature of reaction is 30 DEG C, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 DEG C.Monitor the residual volume of methylthiopropionaldehyde with HPLC, when methylthiopropionaldehyde residual volume is less than 0.2%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 287.4g, 2-2-hydroxy-4-methylthio butyronitrile is 96%, prussic acid remnants 0.06%, moisture content 3%.
Embodiment 7
Prussic acid gas mixture II being passed into 233.3g massfraction is in the methylthiopropionaldehyde of 94.5%, containing 8.5g water in methylthiopropionaldehyde, in mixed system, adds a certain amount of catalyst of triethylamine, keeps the pH of system to be 5.5 passing in prussic acid gas mixture process.React under normal pressure, controlling temperature of reaction is 40 DEG C, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 DEG C.Monitor the residual volume of methylthiopropionaldehyde with HPLC, when methylthiopropionaldehyde residual volume is less than 0.2%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 287.4g, 2-2-hydroxy-4-methylthio butyronitrile is 96%, prussic acid remnants 0.06%, moisture content 3%.
Embodiment 8
Prussic acid gas mixture II being passed into 223.3g massfraction is in the methylthiopropionaldehyde of 94.5%, adds the damping fluid of a certain amount of sodium hydroxide and citric acid formation, in logical prussic acid gas mixture process, keep the pH of system to be 5.0 in mixed system.React under normal pressure, controlling temperature of reaction is 45 DEG C, and draft speed is 350L/min, and tail gas carries out burning disposal, and incineration temperature is higher than 1000 DEG C.Monitor the residual volume of methylthiopropionaldehyde with HPLC, when methylthiopropionaldehyde residual volume is less than 0.5%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 287.4g, 2-2-hydroxy-4-methylthio butyronitrile is 97%, prussic acid remnants 0.06%, moisture content 2%.The 2-2-hydroxy-4-methylthio butyronitrile obtained is divided into two parts together with reaction solution (i.e. 2-2-hydroxy-4-methylthio butyronitrile system).Portion wherein adds 8.5g water, preserves 120 days, have no decomposition under 3 DEG C of conditions; Another part adds 8.5g water wherein, and be then 3 with the sulfuric acid acidation of 85% to pH, preserve 120 days under 20 DEG C of conditions, 2-2-hydroxy-4-methylthio butyronitrile rate of decomposition is 0.1%.
Embodiment 9
With vigorous stirring, the 2-2-hydroxy-4-methylthio butyronitrile (270.64g, 98% content) embodiment 2 obtained slowly adds (3mol) in the aqueous sodium hydroxide solution of 45%, and hydrolysising reacting temperature 100 DEG C, produces a large amount of ammonias, Ammonia recovery.After 2-2-hydroxy-4-methylthio butyronitrile dropwises, 100 DEG C of insulation reaction, then the residual volume of efficient liquid phase chromatographic analysis 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide is used, until do not detect that 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide are considered as the terminal reacted.Ammonia in hydrolyzed solution is got rid of as far as possible, the D obtained, the hydrating solution of the L-2-hydroxy-4-methylthiobutyric acid sodium extracted with diethyl ether of 1 times of volume, organic phase concentration and recovery organic solvent ether, aqueous phase is that the aqueous solution of D, L-2-hydroxy-4-methylthiobutyric acid sodium amounts to 495g, D, the content of L-2-hydroxy-4-methylthiobutyric acid sodium is the yield of 68.8%, D, L-2-hydroxy-4-methylthiobutyric acid sodium is 99.5%.
Embodiment 10
With vigorous stirring, the 2-2-hydroxy-4-methylthio butyronitrile (279.54g, 98% content) embodiment 3 obtained slowly adds (4.18mol) in the aqueous sodium hydroxide solution of 45%, and hydrolysising reacting temperature 80 DEG C, produces a large amount of ammonias, Ammonia recovery.After 2-2-hydroxy-4-methylthio butyronitrile dropwises, 110 DEG C of insulation reaction, then the residual volume of efficient liquid phase chromatographic analysis 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide is used, until do not detect that 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide are considered as the terminal reacted.Ammonia in hydrolyzed solution is got rid of as far as possible, the D obtained, the hydrating solution of L-2-hydroxy-4-methylthiobutyric acid sodium extracts with the toluene of 1 times of volume, organic phase concentration and recovery organic solvent toluene, aqueous phase is that the aqueous solution of D, L-2-hydroxy-4-methylthiobutyric acid sodium amounts to 650g, D, the content of L-2-hydroxy-4-methylthiobutyric acid sodium is the yield of 55%, D, L-2-hydroxy-4-methylthiobutyric acid sodium is 99.5%.
Embodiment 11
With vigorous stirring, the 2-2-hydroxy-4-methylthio butyronitrile (294.54g, 98% content) embodiment 4 obtained slowly adds (4.4mol) in the aqueous sodium hydroxide solution of 40%, and hydrolysising reacting temperature 100 DEG C, produces a large amount of ammonias, Ammonia recovery.After 2-2-hydroxy-4-methylthio butyronitrile dropwises, 110 DEG C of insulation reaction, then the residual volume of efficient liquid phase chromatographic analysis 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide is used, until do not detect that 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide are considered as the terminal reacted.Ammonia in hydrolyzed solution is got rid of as far as possible, the D obtained, the hydrating solution of L-2-hydroxy-4-methylthiobutyric acid sodium extracts with the benzene of 1 times of volume, organic phase concentration and recovery organic solvent-benzene, aqueous phase is that the aqueous solution of D, L-2-hydroxy-4-methylthiobutyric acid sodium amounts to 680g, D, the content of L-2-hydroxy-4-methylthiobutyric acid sodium is the yield of 55.1%, D, L-2-hydroxy-4-methylthiobutyric acid sodium is 99%.
Embodiment 12
With vigorous stirring, the 2-2-hydroxy-4-methylthio butyronitrile (277.4g, 97% content) embodiment 5 obtained slowly adds (3.7mol) in the aqueous sodium hydroxide solution of 35%, and hydrolysising reacting temperature 110 DEG C, produces a large amount of ammonias, Ammonia recovery.After 2-2-hydroxy-4-methylthio butyronitrile dropwises, 110 DEG C of insulation reaction, then the residual volume of efficient liquid phase chromatographic analysis 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide is used, until do not detect that 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide are considered as the terminal reacted.Ammonia in hydrolyzed solution is got rid of as far as possible, the D obtained, the hydrating solution of the L-2-hydroxy-4-methylthiobutyric acid sodium dichloromethane extraction of 0.5 times of volume, organic phase concentration and recovery organic solvent dichloromethane, aqueous phase is that the aqueous solution of D, L-2-hydroxy-4-methylthiobutyric acid sodium amounts to 640g, D, the content of L-2-hydroxy-4-methylthiobutyric acid sodium is the yield of 54.6%, D, L-2-hydroxy-4-methylthiobutyric acid sodium is 99%.
Embodiment 13
With vigorous stirring, the 2-2-hydroxy-4-methylthio butyronitrile (287.4g, 96% content) embodiment 6 obtained slowly adds (5.0mol) in the potassium hydroxide aqueous solution of 50%, and hydrolysising reacting temperature 70 DEG C, produces a large amount of ammonias, Ammonia recovery.After 2-2-hydroxy-4-methylthio butyronitrile dropwises, 100 DEG C of insulation reaction, then the residual volume of efficient liquid phase chromatographic analysis 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide is used, until do not detect that 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide are considered as the terminal reacted.Ammonia in hydrolyzed solution is got rid of as far as possible, the D obtained, the hydrating solution of the L-2-hydroxy-4-methylthiobutyric acid potassium extraction into ethyl acetate of 1.5 times of volumes, organic phase concentration and recovery organic solvent ethyl acetate, aqueous phase is that the aqueous solution of D, L-2-hydroxy-4-methylthiobutyric acid potassium amounts to 805g, D, the content of L-2-hydroxy-4-methylthiobutyric acid potassium is the yield of 48.7%, D, L-2-hydroxy-4-methylthiobutyric acid potassium is 99%.
Embodiment 14
With vigorous stirring, the 2-2-hydroxy-4-methylthio butyronitrile (287.4g, 96% content) embodiment 7 obtained slowly adds (2.6mol) in the potassium hydroxide aqueous solution of 30%, and hydrolysising reacting temperature 110 DEG C, produces a large amount of ammonias, Ammonia recovery.After 2-2-hydroxy-4-methylthio butyronitrile dropwises, 110 DEG C of insulation reaction, then the residual volume of efficient liquid phase chromatographic analysis 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide is used, until do not detect that 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide are considered as the terminal reacted.Ammonia in hydrolyzed solution is got rid of as far as possible, the D obtained, the hydrating solution of the L-2-hydroxy-4-methylthiobutyric acid potassium chloroform extraction of 0.5 times of volume, organic phase concentration and recovery organic solvents, chloroform, aqueous phase is that the aqueous solution of D, L-2-hydroxy-4-methylthiobutyric acid potassium amounts to 730g, D, the content of L-2-hydroxy-4-methylthiobutyric acid potassium is the yield of 53.7%, D, L-2-hydroxy-4-methylthiobutyric acid potassium is 99%.
The preparation of embodiment 152-hydroxy-4-methylthiobutyric acid zinc
By the D that embodiment 9 obtains, the aqueous solution 495g of L-2-hydroxy-4-methylthiobutyric acid sodium is heated to 65 DEG C, under vigorous stirring, 30% solder(ing)acid 727g(1.584mol is dripped) with 2 hours, dropwise, continue 65 DEG C of stirring reactions 1 hour, filter insoluble solids, then filtrate be cooled to 5 DEG C, filter, cold water washing filter cake, merging filtrate and washings are circulated to next batch reaction, the D obtained, L-2-hydroxy-4-methylthiobutyric acid zinc filter cake adds water heating just to dissolving completely, Heating temperature is 80 DEG C, and then add a small amount of water by its saturated D, L-2-hydroxy-4-methylthiobutyric acid zinc solution dilutes, concentration after dilution is 85% of former saturation concentration, add the Natvosol of 100ppm again (with D, L-2-hydroxy-4-methylthiobutyric acid zinc meter), stirring is cooled to 0 DEG C, separate out a large amount of white crystals, filter, 100 DEG C of vacuum dryings obtain white powder D, L-2-hydroxy-4-methylthiobutyric acid zinc crystal 332.3g, yield 92%, purity is that 99.6%(HPLC detects), tap density (g/ml) is 0.68.Recrystallization filtrate is circulated to the washing of next batch inner complex filter cake.
The preparation of embodiment 162-hydroxy-4-methylmercapto copper butyrate
By the D that embodiment 10 obtains, the aqueous solution 650g of L-2-hydroxy-4-methylthiobutyric acid sodium is heated to 65 DEG C, under vigorous stirring, 20% copper chloride solution 1253g(1.455mol is dripped with 2 hours) (filtrate that copper chloride solution embodiment 15 merges and washings preparation), dropwise, continue 65 DEG C of stirring reactions 1 hour, filter insoluble solids, then filtrate be cooled to 5 DEG C, filter, with the recrystallization filtrate washing leaching cake of embodiment 15, merging filtrate and washings are circulated to next batch reaction, the D obtained, L-2-hydroxy-4-methylmercapto copper butyrate filter cake adds water heating just to dissolving completely, Heating temperature is 90 DEG C, and then add a small amount of water by its saturated D, L-2-hydroxy-4-methylmercapto copper butyrate solution dilution, concentration after dilution is 85% of former saturation concentration, add the Walocel MT 20.000PV of 100ppm again (with D, L-2-hydroxy-4-methylmercapto copper butyrate meter), stirring is cooled to 0 DEG C, separate out a large amount of blue colored crystals, filter, 100 DEG C of vacuum dryings obtain blue powder shape D, L-2-hydroxy-4-methylmercapto copper butyrate crystal 347.4g, yield 92%, purity is that 99.5%(HPLC detects), tap density (g/ml) is 0.70.Recrystallization filtrate is circulated to the washing of next batch inner complex filter cake.
The preparation of embodiment 172-hydroxy-4-methylthiobutyric acid ferrous iron
By the D that embodiment 11 obtains, the aqueous solution 680g of L-2-hydroxy-4-methylthiobutyric acid sodium is heated to 65 DEG C, under vigorous stirring, 20% ferrous chloride aqueous solution 1115.6g(1.743mol is dripped with 2 hours) (filtrate that ferrous chloride aqueous solution embodiment 16 merges and washings preparation), nitrogen protection, dropwise, continue 65 DEG C of stirring reactions 1 hour, filter insoluble solids, then filtrate be cooled to 5 DEG C, filter, with the recrystallization filtrate washing leaching cake of embodiment 16, merging filtrate and washings are circulated to next batch reaction, the D obtained, the ferrous filter cake of L-2-hydroxy-4-methylthiobutyric acid adds water heating just to dissolving completely, nitrogen protection, Heating temperature is 90 DEG C, and then add a small amount of water by its saturated D, L-2-hydroxy-4-methylthiobutyric acid ferrous iron solution dilutes, concentration after dilution is 90% of former saturation concentration, add the citric acid of 100ppm again (with D, L-2-hydroxy-4-methylthiobutyric acid ferrous iron meter), stirring is cooled to 0 DEG C, separate out a large amount of brown crystals, filter, 100 DEG C of vacuum dryings obtain D, L-2-hydroxy-4-methylthiobutyric acid ferrous brown powder shape crystal 356.2g, yield 92%, purity is that 99.6%(HPLC detects), tap density (g/ml) is 0.69.Recrystallization filtrate is circulated to the washing of next batch inner complex filter cake.
The preparation of embodiment 182-hydroxy-4-methylmercapto chromium butyrate
By the D that embodiment 12 obtains, the aqueous solution 640g of L-2-hydroxy-4-methylthiobutyric acid sodium is heated to 75 DEG C, under vigorous stirring, 30% chromium trichloride aqueous solution 375g(0.711mol is dripped with 2 hours) (filtrate that chromium trichloride aqueous solution embodiment 17 merges and washings preparation), nitrogen protection, dropwise, continue 75 DEG C of stirring reactions 1 hour, filter insoluble solids, then filtrate be cooled to 5 DEG C, filter, with the recrystallization filtrate washing leaching cake of embodiment 17, merging filtrate and washings are circulated to next batch reaction, the D obtained, L-2-hydroxy-4-methylmercapto chromium butyrate filter cake adds water heating just to dissolving completely, nitrogen protection, Heating temperature is 90 DEG C, and then add a small amount of water by its saturated D, L-2-hydroxy-4-methylmercapto chromium butyrate solution dilution, concentration after dilution is 90% of former saturation concentration, add the Natvosol of 50ppm again (with D, L-2-hydroxy-4-methylmercapto chromium butyrate meter), stirring is cooled to 0 DEG C, separate out a large amount of red-purple crystal, filter, 100 DEG C of vacuum dryings obtain D, L-2-hydroxy-4-methylmercapto chromium butyrate amaranth flour powder crystal 308.4g, yield 91%, purity is that 99.7%(HPLC detects), tap density (g/ml) is 0.71.Recrystallization filtrate is circulated to the washing of next batch inner complex filter cake.
The preparation of embodiment 192-hydroxy-4-methylthiobutyric acid cobalt
By the D that embodiment 13 obtains, the aqueous solution 805g of L-2-hydroxy-4-methylthiobutyric acid potassium is heated to 50 DEG C, under vigorous stirring, 30% cobalt dichloride aqueous solution 705.2g(1.625mol is dripped with 2 hours) (filtrate that cobalt dichloride aqueous solution embodiment 18 merges and washings preparation), dropwise, continue 50 DEG C of stirring reactions 2 hours, filter insoluble solids, then filtrate be cooled to 5 DEG C, filter, with the recrystallization filtrate washing leaching cake of embodiment 18, merging filtrate and washings are circulated to next batch reaction, the D obtained, L-2-hydroxy-4-methylthiobutyric acid cobalt filter cake adds water heating just to dissolving completely, Heating temperature is 70 DEG C, and then add a small amount of water by its saturated D, L-2-hydroxy-4-methylthiobutyric acid cobalt liquor dilutes, concentration after dilution is 75% of former saturation concentration, add the sodium laurylsulfonate of 2500ppm again (with D, L-2-hydroxy-4-methylthiobutyric acid cobalt meter), stirring is cooled to 8 DEG C, separate out a large amount of white crystals, filter, 100 DEG C of vacuum dryings obtain D, L-2-hydroxy-4-methylthiobutyric acid cobalt white powder crystal 368.4g, yield 98%, purity is that 99%(HPLC detects), tap density (g/ml) is 0.72.Recrystallization filtrate is circulated to the washing of next batch inner complex filter cake.
The preparation of embodiment 202-hydroxy-4-methylthiobutyric acid nickel
By the D that embodiment 14 obtains, the aqueous solution 730g of L-2-hydroxy-4-methylthiobutyric acid potassium is heated to 90 DEG C, under vigorous stirring, 30% nickel chloride aqueous solution 614.4g(1.422mol is dripped with 2 hours) (filtrate that nickel chloride aqueous solution embodiment 19 merges and washings preparation), dropwise, continue 90 DEG C of stirring reactions 0.5 hour, filter insoluble solids, then filtrate be cooled to 5 DEG C, filter, with the recrystallization filtrate washing leaching cake of embodiment 19, merging filtrate and washings are circulated to next batch reaction, the D obtained, L-2-hydroxy-4-methylthiobutyric acid nickel filter cake adds water heating just to dissolving completely, Heating temperature is 85 DEG C, and then add a small amount of water its saturated DL-2-hydroxy-4-methylthiobutyric acid nickel solution is diluted, concentration after dilution is 70% of former saturation concentration, add the Aluctyl of 1000ppm again (with D, L-2-hydroxy-4-methylthiobutyric acid nickel meter), stirring is cooled to 5 DEG C, separate out a large amount of green crystals, filter, 100 DEG C of vacuum dryings obtain D, L-2-hydroxy-4-methylthiobutyric acid nickel green powder crystal 363.6g, yield 97%, purity is that 99%(HPLC detects), tap density (g/ml) is 0.69.Recrystallization filtrate is circulated to the washing of next batch inner complex filter cake.
Embodiment 21 utilizes D, and L-2-hydroxy-4-methylthiobutyric acid microelement chelate production equipment prepares D, L-2-hydroxyl-4-methylmercapto manganese butyrate
As shown in Figure 1, D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate production equipment comprises prussic acid synthetic tower 1, acid tower 2, first reactor 3, second reactor 4, crystallization kettle 5 and tripping device 6-suction filter; Fill the sulfuric acid that massfraction is 75% ~ 90% in described acid tower 2, the air outlet of prussic acid synthetic tower 1 is communicated with by the inlet mouth of pipeline with acid tower 2, and the air outlet of acid tower 2 is communicated with the first reactor 3 by the pipeline being provided with throttling valve.
According to the requirement of iS-One method synthesis prussic acid, send into raw material to prussic acid synthetic tower 1, react to obtain prussic acid gas mixture I, prussic acid gas mixture I passes into acid tower 2 and sloughs ammonia and water vapour, obtains prussic acid gas mixture II.Prussic acid gas mixture II is under throttle valve control, and passing into 223.3kg massfraction in the first reactor 3 with the speed of 350L/min is in the methylthiopropionaldehyde of 94.5%, containing 3.3kg pyridine and 4kg water in methylthiopropionaldehyde.Under 0.09MPa, controlling temperature of reaction is 80 DEG C, and tail gas sodium hydroxide absorbs, and monitors the residual volume of methylthiopropionaldehyde with HPLC.When methylthiopropionaldehyde residual volume is less than 0.2%, be reaction end, can stop passing into.Altogether the content of weak yellow liquid 287.4kg, 2-2-hydroxy-4-methylthio butyronitrile is 97%, prussic acid remnants 0.06%, moisture content 2%.
In the second reactor 4, under vigorous stirring, the 2-2-hydroxy-4-methylthio butyronitrile obtained (287.4kg, 97% content) is slowly added (3000mol) in the aqueous sodium hydroxide solution of 45%, and hydrolysising reacting temperature 100 DEG C, produces a large amount of ammonias, Ammonia recovery.After 2-2-hydroxy-4-methylthio butyronitrile dropwises, 100 DEG C of insulation reaction, then the residual volume of efficient liquid phase chromatographic analysis 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide is used, until do not detect that 2-2-hydroxy-4-methylthio butyronitrile and 2-2-hydroxy-4-methylthio butyramide are considered as the terminal reacted.Ammonia in hydrolyzed solution is got rid of as far as possible, the D obtained, the hydrating solution of the L-2-hydroxy-4-methylthiobutyric acid sodium extracted with diethyl ether of 1 times of volume, organic phase concentration and recovery organic solvent ether, aqueous phase is that the aqueous solution of D, L-2-hydroxy-4-methylthiobutyric acid sodium amounts to 520.1kg, D, the content of L-2-hydroxy-4-methylthiobutyric acid sodium is the yield of 69.7%, D, L-2-hydroxy-4-methylthiobutyric acid sodium is 99%.
In crystallization kettle 5, the aqueous solution 520.1kg of the D obtained, L-2-hydroxy-4-methylthiobutyric acid sodium is heated to 65 DEG C, under vigorous stirring, 30% manganous chloride aqueous solution 511.7kg(1220mol is dripped) with 2 hours, dropwise, continue, 65 DEG C of stirring reactions 1 hour, to filter insoluble solids, then filtrate be cooled to 5 DEG C, suction filtration, cold water washing filter cake, merging filtrate and washings are circulated to next batch reaction.D after washing, L-2-hydroxyl-4-methylmercapto manganese butyrate filter cake proceeds in crystallization kettle 5 again, add water heating just to dissolving completely, Heating temperature is 90 DEG C, and then add a small amount of water by its saturated D, L-2-hydroxyl-4-methylmercapto manganese butyrate solution dilution, concentration after dilution is 90% of former saturation concentration, add the Natvosol of 100ppm again (with D, L-2-hydroxyl-4-methylmercapto manganese butyrate meter), stirring is cooled to 0 DEG C, separate out a large amount of white crystals, suction filtration, crystal is transferred to drying plant 100 DEG C of vacuum dryings and obtains D, L-2-hydroxyl-4-methylmercapto manganese butyrate white powder crystal 374.7kg, yield 97%, purity is that 99%(HPLC detects), tap density (g/ml) is 0.69.Recrystallization filtrate is circulated to the washing of next batch inner complex filter cake.
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 (11)
- The preparation method of 1.D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate, is characterized in that: comprise the following steps:A, with methane, ammonia and oxygen for raw material, adopt iS-One method composition principle, be prepared into prussic acid gas mixture I; Described prussic acid gas mixture I obtains prussic acid gas mixture II through deamination process;B, described prussic acid gas mixture II under the katalysis of alkali, fully react to obtain 2-2-hydroxy-4-methylthio butyronitrile system with methylthiopropionaldehyde;C, described 2-2-hydroxy-4-methylthio butyronitrile system mineral alkali MOH are hydrolyzed, and obtain D, L-2-hydroxy-4-methylthiobutyric acid salt; Described MOH is one or more in LiOH, NaOH and KOH;D, described D, L-2-hydroxy-4-methylthiobutyric acid salt and micro-metals salt carry out chelatropic reaction, generate D, L-2-hydroxy-4-methylthiobutyric acid microelement chelate.
- 2. D according to claim 1, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, is characterized in that: the deamination process described in steps A be prussic acid gas mixture I is passed into massfraction be 75% ~ 90% sulfuric acid carry out deamination process.
- 3. D according to claim 1, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, it is characterized in that: the methylthiopropionaldehyde described in step B is not purified methylthiopropionaldehyde, wherein containing the heavy constituent of the methylthiopropionaldehyde of massfraction 94.5% ~ 96%, the light constituent of massfraction 3.5% ~ 5.3% and massfraction 0.2% ~ 0.5%; Described light constituent is thiomethyl alcohol, methyl alcohol, propenal and water; Described restructuring is divided into dipolymer and the trimer of methylthiopropionaldehyde.
- 4. D according to claim 1, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, is characterized in that: in described step B, and the mol ratio of prussic acid and methylthiopropionaldehyde is 1:1.0 ~ 1.05, reaction pressure is 0.09 ~ 0.5MPa, and temperature of reaction is 30 ~ 80 DEG C.
- 5. D according to claim 1, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, it is characterized in that: in described step C, the massfraction of MOH is 30% ~ 50%, the mol ratio of 2-2-hydroxy-4-methylthio butyronitrile and MOH is 1:1.2 ~ 2.5, and temperature of reaction is 70 ~ 110 DEG C.
- 6. D according to claim 1, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, it is characterized in that: the micro-metals salt described in step D is zinc chloride, zinc sulfate, zinc acetate, zinc carbonate, cupric chloride, copper sulfate, neutralized verdigris, copper carbonate, iron protochloride, ferrous sulfate, iron protocarbonate, Iron diacetate, manganous chloride, manganous sulfate, manganese acetate, manganous carbonate, cobalt chloride, rose vitriol, Cobaltous diacetate, cobaltous carbonate, chromium chloride, chromium sulphate, chromium acetate, chromium carbonate, single nickel salt, nickel acetate, one or more in nickelous carbonate and nickelous chloride.
- 7. D according to claim 1, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, it is characterized in that: in described step D, D, the mol ratio of L-2-hydroxy-4-methylthiobutyric acid salt and micro-metals salt is 1:0.35 ~ 0.80, temperature of reaction is 50 ~ 90 DEG C, and the reaction times is 0.5 ~ 2 hour.
- 8. D according to claim 1, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, it is characterized in that: the D that step C obtains, L-2-hydroxy-4-methylthiobutyric acid salt together with its reaction solution after organic solvent extraction, the aqueous phase obtained and D, L-2-hydroxy-4-methylthiobutyric acid salt brine solution, is directly used in step D and micro-metals reactant salt.
- 9. the D according to any one of claim 1 to 8, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, it is characterized in that: also comprise re-crystallization step: the D of step D gained, the crystallizing agent of L-2-hydroxy-4-methylthiobutyric acid microelement chelate and its quality 50ppm ~ 3000ppm is in water medium, be heated to 60 ~ 90 DEG C, dissolve completely, crystallisation by cooling, be separated, dried crystals, obtain the D of high purity and high-bulk-density, L-2-hydroxy-4-methylthiobutyric acid microelement chelate.
- 10. D according to claim 9, the preparation method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, is characterized in that: described crystallizing agent is one or more in citric acid, sodium laurylsulfonate, lactic acid, Walocel MT 20.000PV, Natvosol and Aluctyl.
- 11. utilize D, D prepared by L-2-hydroxy-4-methylthiobutyric acid microelement chelate production equipment, the method of L-2-hydroxy-4-methylthiobutyric acid microelement chelate, is characterized in that: described production equipment comprises prussic acid synthetic tower (1), acid tower (2), the first reactor (3), the second reactor (4), crystallization kettle (5) and tripping device (6); The sulfuric acid that massfraction is 75% ~ 90% is filled in described acid tower (2), the air outlet of prussic acid synthetic tower (1) is communicated with by the inlet mouth of pipeline with acid tower (2), and the air outlet of acid tower (2) is communicated with the first reactor (3) by the pipeline being provided with throttling valve;A, with methane, ammonia and oxygen for raw material, adopt iS-One method composition principle, prepare prussic acid gas mixture I by prussic acid synthetic tower (1); Described prussic acid gas mixture I passes into acid tower (2) and sloughs ammonia and water vapour, obtains prussic acid gas mixture II;B, described prussic acid gas mixture II, under throttle valve control, pass in the methylthiopropionaldehyde in the first reactor (3) with the speed of 250 ~ 350L/min, under the katalysis of alkali, fully react to obtain the reaction system of 2-2-hydroxy-4-methylthio butyronitrile;C, described 2-2-hydroxy-4-methylthio butyronitrile system are hydrolyzed with mineral alkali MOH in the second reactor (4), and after reaction terminates, with organic solvent extraction, the aqueous phase obtained is D, L-2-hydroxy-4-methylthiobutyric acid salt brine solution; Described MOH is one or more in LiOH, NaOH and KOH;D, described D, L-2-hydroxy-4-methylthiobutyric acid salt brine solution and micro-metals salt fully carry out chelatropic reaction in crystallization kettle (5), through tripping device (6) removing insolubles, filtrate crystallisation by cooling, be separated to obtain D again, L-2-hydroxy-4-methylthiobutyric acid microelement chelate crude product and filtrate, use cold water washing crude product; Merging filtrate and washings, be circulated to the chelatropic reaction of D, L-2-hydroxy-4-methylthiobutyric acid salt when producing next time; Again in crystallization kettle (5), the crystallizing agent of the D after described washing, L-2-hydroxy-4-methylthiobutyric acid microelement chelate crude product and its quality 50ppm ~ 3000ppm dissolves completely in water medium, cooling recrystallization, be separated through tripping device (6), obtain crystal and recrystallization filtrate; Described recrystallization filtrate is circulated to the washing of crude product when producing next time; Described crystal proceeds to drying plant, dry, obtains the D of high purity and high-bulk-density, L-2-hydroxy-4-methylthiobutyric acid microelement chelate.
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| CN1771221A (en) * | 2003-04-09 | 2006-05-10 | 德古萨股份公司 | Process for the production of 2-hydroxy-4-methylthiobutyric acid ammonium salt |
| CN103224461A (en) * | 2013-04-22 | 2013-07-31 | 广州天科生物科技有限公司 | Preparation method of large granule crystal form methionine metal chelate and application thereof |
| CN103254104A (en) * | 2013-05-24 | 2013-08-21 | 长沙兴嘉生物工程股份有限公司 | Preparation method of microelement methionine hydroxy analogue chelate additive |
| CN103380109A (en) * | 2011-02-23 | 2013-10-30 | 赢创德固赛有限公司 | Storage-stable 2-hydroxy-4-(methylthio) butyric acid nitrile |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1771221A (en) * | 2003-04-09 | 2006-05-10 | 德古萨股份公司 | Process for the production of 2-hydroxy-4-methylthiobutyric acid ammonium salt |
| CN103380109A (en) * | 2011-02-23 | 2013-10-30 | 赢创德固赛有限公司 | Storage-stable 2-hydroxy-4-(methylthio) butyric acid nitrile |
| CN103224461A (en) * | 2013-04-22 | 2013-07-31 | 广州天科生物科技有限公司 | Preparation method of large granule crystal form methionine metal chelate and application thereof |
| CN103254104A (en) * | 2013-05-24 | 2013-08-21 | 长沙兴嘉生物工程股份有限公司 | Preparation method of microelement methionine hydroxy analogue chelate additive |
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Effective date of registration: 20160817 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. |