CN105130861A - Separation and purification method for methionine hydroxy analogue synthesized through hydrolysis of cyanohydrins - Google Patents

Separation and purification method for methionine hydroxy analogue synthesized through hydrolysis of cyanohydrins Download PDF

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Publication number
CN105130861A
CN105130861A CN201510449155.8A CN201510449155A CN105130861A CN 105130861 A CN105130861 A CN 105130861A CN 201510449155 A CN201510449155 A CN 201510449155A CN 105130861 A CN105130861 A CN 105130861A
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ammonium sulfate
methionine hydroxy
solid
water
organic layer
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Inventor
吴传隆
范倩玉
王用贵
李欧
胡欣
金海琴
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NINGXIA ZIGUANG TIANHUA METHIONINE CO., LTD.
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CHONGQING UNISPLENDOUR INTERNATIONAL CHEMICAL Co Ltd
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Priority to CN201510449155.8A priority Critical patent/CN105130861A/en
Publication of CN105130861A publication Critical patent/CN105130861A/en
Priority to RU2016130940A priority patent/RU2649012C2/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/26Separation; Purification; Stabilisation; Use of additives
    • C07C319/28Separation; Purification
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated

Abstract

The invention discloses a separation and purification method for methionine hydroxy analogue synthesized through hydrolysis of cyanohydrins. The method comprises the following steps: carrying out ammonification and neutralization on hydrolysate obtained by hydrolysis of 2-hydroxy-4-methylthiobutyronitrile under the action of sulfuric acid and containing the methionine hydroxy analogue, ammonium sulfate and ammonium bisulfate, allowing ammonium sulfate to be precipitated through supersaturation and carrying out layering so as to obtain an organic layer I and a water layer I containing ammonium sulfate solid; concentrating the organic layer I so as to allow ammonium sulfate solid to be precipitated, carrying out solid-liquid separation, diluting obtained liquid through addition of water so as to obtain the commercial grade methionine hydroxy analogue, mixing the precipitated ammonium sulfate solid with the water layer I containing ammonium sulfate solid, and carrying out layering so as to obtain an organic layer II and a water layer II containing the ammonium sulfate solid; and subjecting the water layer II to solid-liquid separation and drying obtained solid so as to obtain commercial grade ammonium sulfate. The method provided by the invention is simple and easily practicable and can obtain the high-quality methionine hydroxy analogue and the commercial grade ammonium sulfate, and the recovery rates of the high-quality methionine hydroxy analogue and the commercial grade ammonium sulfate are more than 99%; and in the whole process of the method, no organic solvent is used, no waste water containing salt or organic matters is discharged, and cost and energy consumption are low.

Description

The separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs
Technical field
The invention belongs to chemical technology field, relate to a kind of separation purification method of Chemicals.
Background technology
Methionine hydroxy analog (MethionineHydroxyAnalogue, MHA) be the liquid organic acid that a kind of acidity is very strong, water content 12%, comprise containing active methionine hydroxy analogs 88%(the MHA monomer that content is at least 65%, and content is no more than MHA dimer and the polymer of 23%).In Poultry farming, methionine hydroxy analog demonstrates and is similar to the known amino acid whose character playing stimulating growth effect, therefore becomes the important additives of animal-feed.
One of synthetic method of methionine hydroxy analog is initial cyanohydrin hydrolyis method, that methylthiopropionaldehyde and prussic acid are obtained by reacting 2-2-hydroxy-4-methylthio butyronitrile, the latter's hydration under effect of sulfuric acid generates 2-2-hydroxy-4-methylthio butyramide, more further under effect of sulfuric acid hydrolysis obtain the hydrolyzed solution comprising methionine hydroxy analog, ammonium sulfate and monoammonium sulfate.The existing a lot of report of the method for separation and purification methionine hydroxy analog from 2-2-hydroxy-4-methylthio butyronitrile hydrolyzed solution.Such as:
One method 2-2-hydroxy-4-methylthio butyronitrile hydrolyzed solution is added immiscible organic solvent such as ketone, the ether etc. with water extract, methionine hydroxy analog is extracted in organic solvent, then steam except organic solvent, obtain methionine hydroxy analog, and the aqueous phase of liquid containing ammonium sulfate is by concentrating under reduced pressure, crystallisation by cooling, obtain ammonium sulfate.The problem of the method is with an organic solvent to extract, and not only there is the loss of organic solvent, and organic solvent and methionine hydroxy analog can remain in aqueous phase, thus causes the COD of outer draining higher, and biochemistry is difficult to process; Also can contain organic solvent in the methionine hydroxy analog obtained, it must be distilled under high vacuum state or pass into steam wherein to reduce the content of organic solvent, these all cause the cost of the method and energy consumption higher.
One method be by the ammonification of 2-2-hydroxy-4-methylthio butyronitrile hydrolyzed solution and after layering in a heated condition, obtain organic layer and water layer; Be concentrated into by organic layer almost anhydrous, centrifugal, supernatant liquid thin up obtains methionine hydroxy analog, and lower floor's solid obtains ammonium sulfate through organic solvent washing, drying; By concentrated for water layer, crystallisation by cooling, filtration, solid obtains ammonium sulfate through organic solvent washing, drying; The organic solvent washing liquid of twice solid merges, and steams thin up after removing organic solvent and obtains methionine hydroxy analog.The problem of the method is to employ organic solvent, steam except organic solvent time, reclaim when organic solvent carries out dewatering rectifying and all can cause the loss of organic solvent, also can entrainment portions organic solvent in solid ammonium sulfate, these all cause the cost of the method higher; Same, steam and also can contain organic solvent except in the methionine hydroxy analog obtained after organic solvent, methionine hydroxy analog must be distilled under high vacuum state or pass into steam wherein to reduce the content of organic solvent, these all cause the energy consumption of the method higher; In addition, the method needs the rectifying device etc. that dewaters configuring organic solvent, and facility investment is also larger.
One method in 2-2-hydroxy-4-methylthio butyronitrile hydrolyzed solution, adds ammonium sulfate or monoammonium sulfate make layering obvious, obtains organic layer and water layer respectively; Water layer, through concentrated, crystallisation by cooling, obtains ammonium sulfate; Organic layer neutralizes through ammonification, is concentrated into almost anhydrous, sulfate precipitate ammonium, obtains methionine hydroxy analog.The problem of the method is: the amount that the ammonium sulfate obtained carries methionine hydroxy analog secretly is larger, especially the ammonium sulfate that separation and purification obtains from organic layer, the content of its methionine hydroxy analog reaches about 10%, such ammonium sulfate has niff, and tool is a bit sticky, be difficult to drying, be not almost worth, the loss that result also in methionine hydroxy analog is comparatively large, yield is lower.
One method adds monoammonium sulfate when 2-2-hydroxy-4-methylthio butyronitrile is hydrolyzed, gained hydrolyzed solution obtains organic layer and water layer by layering, organic layer obtains methionine hydroxy analog and monoammonium sulfate, ammonium sulfate respectively through concentrated, after gained monoammonium sulfate and ammonium sulfate mix with water layer, add the organic solvent miscible with water to deposit ammonium sulfate, and then be separated the solution obtaining ammonium sulfate and contain monoammonium sulfate.Although the method can obtain purer ammonium sulfate, and can recycling monoammonium sulfate, it use the organic solvent miscible with water as methyl alcohol etc., thus result in the problems such as the recovery difficulty of this organic solvent, usage quantity and loss amount are larger.Moreover, from organic layer, isolated ammonium sulfate contains a certain amount of methionine hydroxy analog, after this part ammonium sulfate mixes with water layer, when adding the organic solvent miscible with water as alcohol, alcohol and methionine hydroxy analog generation esterification must be caused, if now reclaim methionine hydroxy analog, then there are the quality problems of methionine hydroxy analog, if and arrange outward, then cause loss and the environmental issue of methionine hydroxy analog.
One method adds mineral alkali sodium hydroxide, layering in 2-2-hydroxy-4-methylthio butyronitrile hydrolyzed solution, obtains organic layer and water layer, and organic layer, through concentrating under reduced pressure, filters, obtains methionine hydroxy analog and solid sulfate salt respectively.The method can produce a large amount of reluctant solid wastes (being mainly ammonium sulfate and sodium sulfate) and brine waste (main contains sodium sulfate, ammonium sulfate and methionine hydroxy analog), and the process of the process of the not mentioned water layer of the method and the vitriol containing methionine hydroxy analog.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs, simple and easy to do, do not use any organic solvent, and the ammonium sulfate of by-product can reach commercially available requirement.
For achieving the above object, the invention provides following technical scheme:
The separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs, comprises the following steps:
1) 2-2-hydroxy-4-methylthio butyronitrile is hydrolyzed under effect of sulfuric acid comprising in the hydrolyzed solution ammonification of methionine hydroxy analog, ammonium sulfate and monoammonium sulfate and making the monoammonium sulfate in system change ammonium sulfate into of obtaining, ammonium sulfate supersaturation is separated out, layering, obtains organic layer iwith the water layer comprising ammonium sulfate solids i;
2) by organic layer iconcentrate and dewater, separate out ammonium sulfate solids, solid-liquid separation, gained liquid thin up obtains commercial grade methionine hydroxy analog, and gained ammonium sulfate solids is for subsequent use;
3) water layer of ammonium sulfate solids will be comprised iwith step 2) gained ammonium sulfate solids mixes, and layering, obtains organic layer iIwith the water layer comprising ammonium sulfate solids iI;
4) water layer of ammonium sulfate solids will be comprised iIcarry out solid-liquid separation, after gained solid drying, obtain commercial grade ammonium sulfate.
Contriver finds, saturated ammonium sulfate can impel methionine hydroxy analog and the better layering of aqueous phase, and when being heated to certain temperature, divides that to compare low temperature more obvious.Therefore, the inventive method utilizes methionine hydroxy analog solubleness in the saturated ammonium sulphate aqueous solution low, and the principle that solubleness is lower at relatively high temperatures, carrys out the methionine hydroxy analog of separation and purification initial cyanohydrin hydrolyis method synthesis better by the saturated ammonium sulphate aqueous solution and comparatively high temps.
Layering described in step 1) is preferably carried out under temperature 30 ~ 100 DEG C of conditions, more preferably carries out under temperature 50 ~ 80 DEG C of conditions.The obvious separation of higher temperature to each phase is favourable.Temperature is too low, and between organic layer and water layer, emulsification is obvious, can not layering completely; Temperature is too high, treats that layering solution is easily scrapped again.
Step 2) described in concentrated dewatering preferably adopt underpressure distillation mode, be concentrated into water content not higher than 5%, be more preferably concentrated into water content not higher than 3%.
Step 2) described in solid-liquid separation preferably adopt centrifugation, centrifugal rotational speed is not less than 1500r/min, and centrifuging temperature is 25 ~ 80 DEG C; Preferred, centrifugal rotational speed is not less than 2000r/min, and centrifuging temperature is 45 ~ 80 DEG C.Methionine hydroxy analog has viscosity, is not easy centrifugal when temperature is too low; And methionine hydroxy analog has the bad smell of sulfide, centrifugal when temperature is too high, this smell is easily overflowed again affects environment.
Preferably, step 3) to comprise the water layer of ammonium sulfate solids iwith step 2) after gained ammonium sulfate solids mixes, first agitator treating ammonium sulfate solids under 30 ~ 100 DEG C of conditions, then 30 ~ 100 DEG C of condition lower leafs.Preferred, step 3) to comprise the water layer of ammonium sulfate solids iwith step 2) after gained ammonium sulfate solids mixes, first agitator treating ammonium sulfate solids under 50 ~ 80 DEG C of conditions, then 50 ~ 80 DEG C of condition lower leafs.The obvious separation of higher temperature to each phase is favourable.Temperature is too low, and between organic layer and water layer, emulsification is obvious, can not layering completely; Temperature is too high, treats that layering solution is easily scrapped again.
Preferably, the organic layer obtained in step 3) iIwith lower batch of organic layer iapply mechanically.
Preferably, in step 4), the mother liquor of solid-liquid separation remainder and lower batch comprise the water layer of ammonium sulfate solids iapply mechanically.
Preferably, it is adopt following methods to obtain that the 2-hydroxy-4-methylthio of 2-described in step 1) butyronitrile is hydrolyzed the hydrolyzed solution comprising methionine hydroxy analog, ammonium sulfate and monoammonium sulfate obtained under effect of sulfuric acid: be the reaction solution that the hydrocyanic acid aqueous solution of 20wt% ~ 95wt% is obtained by reacting containing 2-2-hydroxy-4-methylthio butyronitrile under catalyst action by methylthiopropionaldehyde and concentration, catalyzer is one or more in sodium cyanide, potassium cyanide, sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood, and the molar ratio of methylthiopropionaldehyde and prussic acid is 1:1.0 ~ 1.1; Reaction solution containing 2-2-hydroxy-4-methylthio butyronitrile is that the reaction solution that hydration reaction obtains containing 2-2-hydroxy-4-methylthio butyramide occurs in the aqueous sulfuric acid of 65wt% ~ 85wt% again in concentration, it is further hydrolysis reaction occurs after 40wt% ~ 50wt% that gained reaction solution is diluted with water to sulfuric acid concentration, namely obtain the hydrolyzed solution comprising methionine hydroxy analog, ammonium sulfate and monoammonium sulfate, the molar ratio of 2-2-hydroxy-4-methylthio butyronitrile and sulfuric acid is 1:0.6 ~ 1.0.Adopt above-mentioned preferred synthetic method, by regulating the concentration of aqueous sulfuric acid in the concentration of hydrocyanic acid aqueous solution, hydration reaction and hydrolysis reaction, can ensure that 2-2-hydroxy-4-methylthio butyronitrile hydrolyzed solution is in ammonification and after making monoammonium sulfate change ammonium sulfate into, ammonium sulfate supersaturation, and then utilize methionine hydroxy analog solubleness in the saturated ammonium sulphate aqueous solution low, and the principle that solubleness is lower at relatively high temperatures, carrys out the methionine hydroxy analog of separation and purification initial cyanohydrin hydrolyis method synthesis better by the saturated ammonium sulphate aqueous solution and comparatively high temps.
Preferably, the reaction of described methylthiopropionaldehyde and hydrocyanic acid aqueous solution is carried out under temperature 20 ~ 40 DEG C, pH value 4.5 ~ 6.0 condition; Hydration reaction is carried out under temperature 40 ~ 70 DEG C of conditions; Hydrolysis reaction carries out under temperature 90 ~ 130 DEG C of conditions.
Preferably, step 2) described in the water of concentrated removing to be back in hydration reaction as the preparation water of aqueous sulfuric acid or/and as the diluting water of sulfuric acid in hydrolysis reaction.Step 2) in the concentrated water of condensation obtained contain a small amount of organic light constituent, as thiomethyl alcohol, Methyl disulfide etc., these organic light constituents do not affect the hydration of 2-2-hydroxy-4-methylthio butyronitrile and hydrolysis reaction, therefore this water of condensation can reuse to the hydration of 2-2-hydroxy-4-methylthio butyronitrile or/and in hydrolysis reaction, thus avoid the outer row of waste water, and these organic light constituents can also by passing into air or nitrogen is driven out of to avoid it to accumulate in system from system, the organic light constituent driven out of can be processed by burning.
Beneficial effect of the present invention is: the present invention utilizes methionine hydroxy analog solubleness in the saturated ammonium sulphate aqueous solution low, and the principle that solubleness is lower at relatively high temperatures, carrys out the methionine hydroxy analog of separation and purification initial cyanohydrin hydrolyis method synthesis better by the saturated ammonium sulphate aqueous solution and comparatively high temps.Adopt the method, methionine hydroxy analog does not almost lose, yield more than 99%, when being diluted to the concentration 88% of commodity requirement, the content analyzing wherein ammonium sulfate lower than 0.2%, far below the requirement of GB 1.5%; The rate of recovery of ammonium sulfate is greater than 99%, and content is more than 99%, and analyze the content of wherein methionine hydroxy analog lower than 100ppm, ammonium sulfate product is almost destitute of smell.The inventive method is simple and easy to do, the commercial grade ammonium sulfate that not only can obtain high-quality methionine hydroxy analog and can sell, avoid the generation of refuse, and whole process does not use any organic solvent, avoid the problem such as recovery and loss of organic solvent, also without saliferous, discharge containing organic wastewater.Compared with prior art, the cost of the inventive method and energy consumption all lower.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, below in conjunction with accompanying drawing, the invention will be further described:
Fig. 1 is the inventive method schematic diagram.
Embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.
Fig. 1 is the inventive method schematic diagram.As shown in the figure, methylthiopropionaldehyde and prussic acid are obtained by reacting 2-2-hydroxy-4-methylthio butyronitrile, the latter issues raw hydration reaction in effect of sulfuric acid and generates 2-2-hydroxy-4-methylthio butyramide, 2-2-hydroxy-4-methylthio butyramide is hydrolyzed under effect of sulfuric acid again, obtains the hydrolyzed solution comprising methionine hydroxy analog, ammonium sulfate and monoammonium sulfate; After making monoammonium sulfate wherein change ammonium sulfate into this hydrolyzed solution ammonification neutralization, due to ammonium sulfate supersaturation in the solution, can ammonium sulfate solids be separated out, at a certain temperature layering, can organic layer be obtained iwith the water layer comprising ammonium sulfate solids i; By organic layer iconcentrate solid-liquid separation after dewatering, methionine hydroxy analog (oily matter) and ammonium sulfate solids can be obtained respectively; By organic layer iisolated ammonium sulfate solids and the water layer comprising ammonium sulfate solids imixing, layering at a certain temperature, can obtain organic layer respectively iIwith the water layer comprising ammonium sulfate solids iI, organic layer iIcan with lower batch of organic layer iapply mechanically; The water layer of ammonium sulfate solids will be comprised iIsolid-liquid separation, can obtain ammonium sulfate solids and mother liquor, the water layer that mother liquor can comprise ammonium sulfate solids with lower batch iapply mechanically.
embodiment 1, initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs
In the reactor that can cool with pH electrode and thermometer, add the methylthiopropionaldehyde 420.2g(4mol of 99wt%), with sodium cyanide solution adjust ph to 5.0 ~ 5.5, vigorous stirring at 30 DEG C, cooling, slowly drip the hydrocyanic acid aqueous solution 189g(4.2mol of 60wt% again), controlling temperature of reaction and be no more than 40 DEG C, in dropping process, maintaining the pH value of reaction system about 5.5 by constantly adding sodium cyanide solution simultaneously.Hydrocyanic acid aqueous solution finishes, and removes cooling bath, and 30 DEG C are stirred 2 hours, obtain the reaction solution 611.2g containing 85.83wt%2-2-hydroxy-4-methylthio butyronitrile, in methylthiopropionaldehyde reaction yield for 99.96%.
Add the aqueous sulfuric acid 339.4g(3.0mol of 85wt% in the reactor), the above-mentioned obtained reaction solution 611.2g(4.0mol containing 85.83wt%2-2-hydroxy-4-methylthio butyronitrile is slowly added again under vigorous stirring and 50 DEG C of conditions), make temperature of reaction be no more than 60 DEG C by controlling feed rate in adition process.After reinforced, 50 DEG C of reactions change 2-2-hydroxy-4-methylthio butyramide into completely to 2-2-hydroxy-4-methylthio butyronitrile in about 30 minutes.Then it is 46% that the 213.1g that adds water in gained reaction solution is diluted to sulfuric acid concentration, is warming up to 100 DEG C of insulated and stirred about 3 little of 2-2-hydroxy-4-methylthio butyramide complete hydrolysis, obtains the hydrolyzed solution comprising methionine hydroxy analog, ammonium sulfate and monoammonium sulfate.
the separation and purification of embodiment 2, initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs
Hydrolyzed solution obtained for embodiment 1 is cooled to 40 DEG C, and make monoammonium sulfate acid in system just change neutral ammonium sulfate into 2mol gaseous ammonia or ammonia treatment, have ammonium sulfate solids to separate out, 60 DEG C of stratification, obtain organic layer respectively iwith the water layer of liquid containing ammonium sulfate solid i, its component and content as shown in table 1.
Table 1 organic layer iand water layer icomponent and content
Organic layer iprocess: by organic layer ibeing evaporated to moisture content is 3%, ammonium sulfate solids is had to separate out, at 60 DEG C, under different rotating speeds (1500 ~ 3500r/min) condition centrifugal 20 minutes, the centrifugal supernatant liquid separated is the yellowish brown liquid of oily, after testing, ammonium sulphate content is 0.2%, and methionine hydroxy analog content is 97.5%, being diluted with water to methionine hydroxy analog content is 88%, obtains commercial grade methionine hydroxy analog; The centrifugal lower floor's solid separated is ammonium sulfate, and in the centrifugal ammonium sulfate solids obtained of different rotating speeds, the content of methionine hydroxy analog is as shown in table 2.
The content of methionine hydroxy analog in the centrifugal ammonium sulfate solids obtained of table 2 different rotating speeds
Water layer iprocess: will from organic layer ithe water layer of isolated ammonium sulfate solids and liquid containing ammonium sulfate solid imixing, is warming up to 65 DEG C of insulated and stirred 30 minutes, is then incubated stratification, obtains organic layer respectively iIwith the water layer of liquid containing ammonium sulfate solid iI; Organic layer iI(containing methionine hydroxy analog) and lower batch of organic layer iapply mechanically; The water layer of liquid containing ammonium sulfate solid iIcentrifugal, the centrifugal solid drying separated, obtains commercial grade ammonium sulfate, and purity is more than 99%, reaches commercially available requirement, and through efficient liquid phase chromatographic analysis, in this ammonium sulfate, the content of methionine hydroxy analog is lower than 100ppm; The water layer of the centrifugal mother liquor (for the saturated ammonium sulphate aqueous solution) separated and lower batch of liquid containing ammonium sulfate solid iapply mechanically.
Organic layer ithe water of condensation of concentrating under reduced pressure gained can reuse to the hydration of embodiment 1 or/and hydrolysing step, as being the aqueous sulfuric acid of 85wt% for the preparation of concentration during hydration step, as adding with water with dilute sulphuric acid during hydrolysing step.
the separation and purification of embodiment 3, initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs
Hydrolyzed solution obtained for embodiment 1 is cooled to 40 DEG C, and make monoammonium sulfate acid in system just change neutral ammonium sulfate into 2mol gaseous ammonia or ammonia treatment, have ammonium sulfate solids to separate out, 30 DEG C of stratification, obtain organic layer respectively iwith the water layer of liquid containing ammonium sulfate solid i.
Organic layer iprocess: by organic layer ibeing evaporated to moisture content is 1%, ammonium sulfate solids is had to separate out, at 25 DEG C, under 1500r/min condition centrifugal 20 minutes, the centrifugal supernatant liquid separated is the yellowish brown liquid of oily, after testing, ammonium sulphate content is 0.2%, and methionine hydroxy analog content is 98.5%, being diluted with water to methionine hydroxy analog content is 88%, obtains commercial grade methionine hydroxy analog; The centrifugal lower floor's solid separated is ammonium sulfate, and wherein the content of methionine hydroxy analog is 12%.
Water layer iprocess: will from organic layer ithe water layer of isolated ammonium sulfate solids and liquid containing ammonium sulfate solid imixing, 30 DEG C of insulated and stirred 30 minutes, are then incubated stratification, obtain organic layer respectively iIwith the water layer of liquid containing ammonium sulfate solid iI; Organic layer iI(containing methionine hydroxy analog) and lower batch of organic layer iapply mechanically; The water layer of liquid containing ammonium sulfate solid iIcentrifugal, the centrifugal solid drying separated, obtains commercial grade ammonium sulfate, and purity is more than 99%, reaches commercially available requirement, and through efficient liquid phase chromatographic analysis, in this ammonium sulfate, the content of methionine hydroxy analog is lower than 100ppm; The water layer of the centrifugal mother liquor (for the saturated ammonium sulphate aqueous solution) separated and lower batch of liquid containing ammonium sulfate solid iapply mechanically.
Organic layer ithe water of condensation of concentrating under reduced pressure gained can reuse to the hydration of embodiment 1 or/and hydrolysing step, as being the aqueous sulfuric acid of 85wt% for the preparation of concentration during hydration step, as adding with water with dilute sulphuric acid during hydrolysing step.
the separation and purification of embodiment 4, initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs
Hydrolyzed solution obtained for embodiment 1 is cooled to 40 DEG C, and make monoammonium sulfate acid in system just change neutral ammonium sulfate into 2mol gaseous ammonia or ammonia treatment, have ammonium sulfate solids to separate out, 50 DEG C of stratification, obtain organic layer respectively iwith the water layer of liquid containing ammonium sulfate solid i.
Organic layer iprocess: by organic layer ibeing evaporated to moisture content is 3%, ammonium sulfate solids is had to separate out, at 45 DEG C, under 2000r/min condition centrifugal 20 minutes, the centrifugal supernatant liquid separated is the yellowish brown liquid of oily, after testing, ammonium sulphate content is 0.3%, and methionine hydroxy analog content is 98%, being diluted with water to methionine hydroxy analog content is 88%, obtains commercial grade methionine hydroxy analog; The centrifugal lower floor's solid separated is ammonium sulfate, and wherein the content of methionine hydroxy analog is 11%.
Water layer iprocess: will from organic layer ithe water layer of isolated ammonium sulfate solids and liquid containing ammonium sulfate solid imixing, 50 DEG C of insulated and stirred 30 minutes, are then incubated stratification, obtain organic layer respectively iIwith the water layer of liquid containing ammonium sulfate solid iI; Organic layer iI(containing methionine hydroxy analog) and lower batch of organic layer iapply mechanically; The water layer of liquid containing ammonium sulfate solid iIcentrifugal, the centrifugal solid drying separated, obtains commercial grade ammonium sulfate, and purity is more than 99%, reaches commercially available requirement, and through efficient liquid phase chromatographic analysis, in this ammonium sulfate, the content of methionine hydroxy analog is lower than 100ppm; The water layer of the centrifugal mother liquor (for the saturated ammonium sulphate aqueous solution) separated and lower batch of liquid containing ammonium sulfate solid iapply mechanically.
Organic layer ithe water of condensation of concentrating under reduced pressure gained can reuse to the hydration of embodiment 1 or/and hydrolysing step, as being the aqueous sulfuric acid of 85wt% for the preparation of concentration during hydration step, as adding with water with dilute sulphuric acid during hydrolysing step.
the separation and purification of embodiment 5, initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs
Hydrolyzed solution obtained for embodiment 1 is cooled to 40 DEG C, and make monoammonium sulfate acid in system just change neutral ammonium sulfate into 2mol gaseous ammonia or ammonia treatment, have ammonium sulfate solids to separate out, 80 DEG C of stratification, obtain organic layer respectively iwith the water layer of liquid containing ammonium sulfate solid i.
Organic layer iprocess: by organic layer ibeing evaporated to moisture content is 3%, ammonium sulfate solids is had to separate out, at 80 DEG C, under 2500r/min condition centrifugal 20 minutes, the centrifugal supernatant liquid separated is the yellowish brown liquid of oily, after testing, ammonium sulphate content is 0.3%, and methionine hydroxy analog content is 98%, being diluted with water to methionine hydroxy analog content is 88%, obtains commercial grade methionine hydroxy analog; The centrifugal lower floor's solid separated is ammonium sulfate, and wherein the content of methionine hydroxy analog is 10%.
Water layer iprocess: will from organic layer ithe water layer of isolated ammonium sulfate solids and liquid containing ammonium sulfate solid imixing, 80 DEG C of insulated and stirred 30 minutes, are then incubated stratification, obtain organic layer respectively iIwith the water layer of liquid containing ammonium sulfate solid iI; Organic layer iI(containing methionine hydroxy analog) and lower batch of organic layer iapply mechanically; The water layer of liquid containing ammonium sulfate solid iIcentrifugal, the centrifugal solid drying separated, obtains commercial grade ammonium sulfate, and purity is more than 99%, reaches commercially available requirement, and through efficient liquid phase chromatographic analysis, in this ammonium sulfate, the content of methionine hydroxy analog is lower than 100ppm; The water layer of the centrifugal mother liquor (for the saturated ammonium sulphate aqueous solution) separated and lower batch of liquid containing ammonium sulfate solid iapply mechanically.
Organic layer ithe water of condensation of concentrating under reduced pressure gained can reuse to the hydration of embodiment 1 or/and hydrolysing step, as being the aqueous sulfuric acid of 85wt% for the preparation of concentration during hydration step, as adding with water with dilute sulphuric acid during hydrolysing step.
the separation and purification of embodiment 6, initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs
Hydrolyzed solution obtained for embodiment 1 is cooled to 40 DEG C, and make monoammonium sulfate acid in system just change neutral ammonium sulfate into 2mol gaseous ammonia or ammonia treatment, have ammonium sulfate solids to separate out, 100 DEG C of stratification, obtain organic layer respectively iwith the water layer of liquid containing ammonium sulfate solid i.
Organic layer iprocess: by organic layer ibeing evaporated to moisture content is 5%, ammonium sulfate solids is had to separate out, at 80 DEG C, under 3500r/min condition centrifugal 20 minutes, the centrifugal supernatant liquid separated is the yellowish brown liquid of oily, after testing, ammonium sulphate content is 0.5%, and methionine hydroxy analog content is 97%, being diluted with water to methionine hydroxy analog content is 88%, obtains commercial grade methionine hydroxy analog; The centrifugal lower floor's solid separated is ammonium sulfate, and wherein the content of methionine hydroxy analog is 9.8%.
Water layer iprocess: will from organic layer ithe water layer of isolated ammonium sulfate solids and liquid containing ammonium sulfate solid imixing, 100 DEG C of insulated and stirred 30 minutes, are then incubated stratification, obtain organic layer respectively iIwith the water layer of liquid containing ammonium sulfate solid iI; Organic layer iI(containing methionine hydroxy analog) and lower batch of organic layer iapply mechanically; The water layer of liquid containing ammonium sulfate solid iIcentrifugal, the centrifugal solid drying separated, obtains commercial grade ammonium sulfate, and purity is more than 99%, reaches commercially available requirement, and through efficient liquid phase chromatographic analysis, in this ammonium sulfate, the content of methionine hydroxy analog is lower than 100ppm; The water layer of the centrifugal mother liquor (for the saturated ammonium sulphate aqueous solution) separated and lower batch of liquid containing ammonium sulfate solid iapply mechanically.
Organic layer ithe water of condensation of concentrating under reduced pressure gained can reuse to the hydration of embodiment 1 or/and hydrolysing step, as being the aqueous sulfuric acid of 85wt% for the preparation of concentration during hydration step, as adding with water with dilute sulphuric acid during hydrolysing step.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.

Claims (9)

1. the separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs, is characterized in that: comprise the following steps:
1) 2-2-hydroxy-4-methylthio butyronitrile is hydrolyzed under effect of sulfuric acid comprising in the hydrolyzed solution ammonification of methionine hydroxy analog, ammonium sulfate and monoammonium sulfate and making the monoammonium sulfate in system change ammonium sulfate into of obtaining, ammonium sulfate supersaturation is separated out, layering, obtains organic layer iwith the water layer comprising ammonium sulfate solids i;
2) by organic layer iconcentrate and dewater, separate out ammonium sulfate solids, solid-liquid separation, gained liquid thin up obtains commercial grade methionine hydroxy analog, and gained ammonium sulfate solids is for subsequent use;
3) water layer of ammonium sulfate solids will be comprised iwith step 2) gained ammonium sulfate solids mixes, and layering, obtains organic layer iIwith the water layer comprising ammonium sulfate solids iI;
4) water layer of ammonium sulfate solids will be comprised iIcarry out solid-liquid separation, after gained solid drying, obtain commercial grade ammonium sulfate.
2. the separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs as claimed in claim 1, is characterized in that: layering described in step 1) is carried out under temperature 30 ~ 100 DEG C of conditions; The water layer of ammonium sulfate solids will be comprised in step 3) iwith step 2) after gained ammonium sulfate solids mixes, first agitator treating ammonium sulfate solids under 30 ~ 100 DEG C of conditions, then 30 ~ 100 DEG C of condition lower leafs.
3. the separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs as claimed in claim 2, is characterized in that: layering described in step 1) is carried out under temperature 50 ~ 80 DEG C of conditions; The water layer of ammonium sulfate solids will be comprised in step 3) iwith step 2) after gained ammonium sulfate solids mixes, first agitator treating ammonium sulfate solids under 50 ~ 80 DEG C of conditions, then 50 ~ 80 DEG C of condition lower leafs.
4. the separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs as claimed in claim 1, is characterized in that: step 2) in, described concentrated dewatering adopts underpressure distillation mode, is concentrated into water content not higher than 5%; Described solid-liquid separation adopts centrifugation, and centrifugal rotational speed is not less than 1500r/min, and centrifuging temperature is 25 ~ 80 DEG C.
5. the separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs as claimed in claim 4, is characterized in that: step 2) in, described concentrated dewatering adopts underpressure distillation mode, is concentrated into water content not higher than 3%; Described solid-liquid separation adopts centrifugation, and centrifugal rotational speed is not less than 2000r/min, and centrifuging temperature is 45 ~ 80 DEG C.
6. the separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs as claimed in claim 1, is characterized in that: the organic layer obtained in step 3) iIwith lower batch of organic layer iapply mechanically, in step 4), the mother liquor of solid-liquid separation remainder and lower batch comprise the water layer of ammonium sulfate solids iapply mechanically.
7. the separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs as claimed in claim 1, it is characterized in that: the 2-hydroxy-4-methylthio of 2-described in step 1) butyronitrile be hydrolyzed under effect of sulfuric acid obtain comprise methionine hydroxy analog, the hydrolyzed solution of ammonium sulfate and monoammonium sulfate adopts following methods to obtain: be the reaction solution that the hydrocyanic acid aqueous solution of 20wt% ~ 95wt% is obtained by reacting containing 2-2-hydroxy-4-methylthio butyronitrile under catalyst action by methylthiopropionaldehyde and concentration, catalyzer is sodium cyanide, potassium cyanide, sodium hydroxide, potassium hydroxide, one or more in sodium carbonate and salt of wormwood, the molar ratio of methylthiopropionaldehyde and prussic acid is 1:1.0 ~ 1.1, reaction solution containing 2-2-hydroxy-4-methylthio butyronitrile is that the reaction solution that hydration reaction obtains containing 2-2-hydroxy-4-methylthio butyramide occurs in the aqueous sulfuric acid of 65wt% ~ 85wt% again in concentration, it is further hydrolysis reaction occurs after 40wt% ~ 50wt% that gained reaction solution is diluted with water to sulfuric acid concentration, namely obtain the hydrolyzed solution comprising methionine hydroxy analog, ammonium sulfate and monoammonium sulfate, the molar ratio of 2-2-hydroxy-4-methylthio butyronitrile and sulfuric acid is 1:0.6 ~ 1.0.
8. the separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs as claimed in claim 7, is characterized in that: the reaction of described methylthiopropionaldehyde and hydrocyanic acid aqueous solution is carried out under temperature 20 ~ 40 DEG C, pH value 4.5 ~ 6.0 condition; Hydration reaction is carried out under temperature 40 ~ 70 DEG C of conditions; Hydrolysis reaction carries out under temperature 90 ~ 130 DEG C of conditions.
9. the separation purification method of initial cyanohydrin hydrolyis method synthetic methionine hydroxy analogs as claimed in claim 7, is characterized in that: step 2) described in the water of concentrated removing to be back in hydration reaction as the preparation water of aqueous sulfuric acid or/and as the diluting water of sulfuric acid in hydrolysis reaction.
CN201510449155.8A 2015-07-28 2015-07-28 Separation and purification method for methionine hydroxy analogue synthesized through hydrolysis of cyanohydrins Pending CN105130861A (en)

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CN109232338A (en) * 2018-11-09 2019-01-18 禄丰天宝磷化工有限公司 A kind of isolation and purification method of methionine hydroxy analog
CN109232342A (en) * 2018-10-15 2019-01-18 禄丰天宝磷化工有限公司 A kind of preparation method of selenomethionine hydroxy analogs
CN110483348A (en) * 2019-09-03 2019-11-22 蓝星安迪苏南京有限公司 Mixture and preparation method thereof comprising methionine hydroxy analog and its oligomer
US11242316B2 (en) * 2017-03-16 2022-02-08 Adisseo France S.A.S. Method for manufacturing 2-hydroxy-4-(methylthio)butyric acid

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Publication number Priority date Publication date Assignee Title
US11242316B2 (en) * 2017-03-16 2022-02-08 Adisseo France S.A.S. Method for manufacturing 2-hydroxy-4-(methylthio)butyric acid
CN109232342A (en) * 2018-10-15 2019-01-18 禄丰天宝磷化工有限公司 A kind of preparation method of selenomethionine hydroxy analogs
CN109232338A (en) * 2018-11-09 2019-01-18 禄丰天宝磷化工有限公司 A kind of isolation and purification method of methionine hydroxy analog
CN110483348A (en) * 2019-09-03 2019-11-22 蓝星安迪苏南京有限公司 Mixture and preparation method thereof comprising methionine hydroxy analog and its oligomer
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CN110483348B (en) * 2019-09-03 2021-12-07 蓝星安迪苏南京有限公司 Mixtures comprising hydroxy analogues of methionine and oligomers thereof and process for preparing same

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