CN106565608A - Preparation method of highly-pure 5-(2-methylthioethyl)-hydantoin - Google Patents
Preparation method of highly-pure 5-(2-methylthioethyl)-hydantoin Download PDFInfo
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- hydantoin
- methylmercaptoethyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
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Abstract
The invention belongs to the field of chemical engineering, and relates to a preparation method of highly-pure 5-(2-methylthioethyl)-hydantoin. The method concretely comprises the following steps: synthesizing an carbonate or bicarbonate-containing 5-(2-methylthioethyl)-hydantoin mixed aqueous solution from cyanide, methylthiopropanal, ammonia and an aqueous carbon dioxide solution , adjusting the pH value of the carbonate or bicarbonate-containing 5-(2-methylthioethyl)-hydantoin mixed aqueous solution to 3.0-7.0, and carrying out cooling crystallization, suction filtration, water washing and drying to obtain white 5-(2-methylthioethyl)-hydantoin crystals with the purity being 99% or above and the yield reaching 90% or above. The method realizes purification of the 5-(2-methylthioethyl)-hydantoin product through simple and convenient operation, and has the characteristics of simplicity in operation, full reaction, high purity and high yield of the product, and low energy consumption.
Description
Technical field
The invention belongs to chemical field, is related to a kind of preparation method of high-purity 5- (2-methylmercaptoethyl)-hydantoin.
Background technology
5- (2-methylmercaptoethyl)-hydantoin and abbreviation glycolylurea, are widely used in medication chemistry, are to prepare DL- first sulfur ammonia
Acid and the key intermediate of medicine.
In theory, the preparation of 5- (2-methylmercaptoethyl)-hydantoin is known, it is, in general, that starting material can be with
It is divided three classes：
1) methylthiopropionaldehyde, hydrocyanic acid, carbon dioxide and ammonia (or ammonium hydrogen carbonate)；
2) methylthiopropionaldehyde, Cyanogran. or potassium cyanide, carbon dioxide and ammonia (or ammonium hydrogen carbonate)；
3) 2- 2-hydroxy-4-methylthios butyronitrile and carbon dioxide and ammonia (or ammonium hydrogen carbonate).
Specifically such as, The Chemistry of the Hydantoins.Chem.Rev.46 (1950) 422-425 are described
The hydantoin for replacing is prepared with corresponding aldehyde or ketone with alkali metal cyanide and ammonium carbonate reaction, reaction can be using chemistry meter
The amount for calculating ratio is carried out under the conditions of 80 DEG C and 0.3MPa, it is possible to use excess of ammonia is warming up to 60 DEG C at ambient pressure and carries out.In addition
The method that one kind prepares 5- (2-methylmercaptoethyl)-hydantoin, methylthiopropionaldehyde is dissolved in containing ammonia, carbon dioxide and hydrocyanic acid
Or in the aqueous solution of its salt, then the reactant mixture is heated to into 100 DEG C, react at ambient pressure, obtain 5- (2- methylmercaptan ethyls
Base)-hydantoin aqueous solution.In Japan Patent JP48-005763, with methylthiopropionaldehyde and hydrocyanic acid or its salt and bicarbonate
Ammonium in the presence of ammonia, is reacted 1.5 hours at 80 DEG C, and 5- (2-methylmercaptoethyl)-hydantoin aqueous solution, yield is obtained
98.5%.Also disclose that in SU740770 that methylthiopropionaldehyde, Cyanogran. and ammonium hydrogen carbonate are obtained 5- (2- methylmercaptan ethyls in water
Base)-hydantoin aqueous solution.
But no matter which kind of process prepares 5- (2-methylmercaptoethyl)-hydantoin, the 5- for obtaining (2- methylmercaptan ethyls
Base)-hydantoin is all mixture, its 5- (2-methylmercaptoethyl)-hydantoin content only has 10%-20%, in addition,
Also the polymer containing methylthiopropionaldehyde, sodium carbonate and unreacted ammonium carbonate etc., to be obtained high-purity, 5- in high yield
(2-methylmercaptoethyl)-hydantoin then needs to be further purified, and in above-mentioned document, also has no efficient purification process operation.
Therefore, all costly, the current market price is the highly purified 5- of commodity (2-methylmercaptoethyl)-hydantoin product price
Per 1 gram of RMB about more than 1,000.
For these reasons and prior art, it is still desirable to the further system to 5- (2-methylmercaptoethyl)-hydantoin
Preparation Method is improved.
The content of the invention
In view of this, it is an object of the invention to provide a kind of system of high-purity 5- (2-methylmercaptoethyl)-hydantoin
Preparation Method, can be readily derived 5- (2-methylmercaptoethyl)-hydantoin product, and the generation of control by-product, improves very well
The quality and yield of 5- (2-methylmercaptoethyl)-hydantoin.
For achieving the above object, the technical scheme is that：
A kind of preparation method of high-purity 5- (2-methylmercaptoethyl)-hydantoin, the step of including being carried out as follows：
(1) with cyanide salt, methylthiopropionaldehyde, ammonia and arbon dioxide solution as raw material, synthesis is containing carbonate or carbon
5- (the 2-methylmercaptoethyl)-hydantoin mixed aqueous solution of sour hydrogen salt；
(2) 5- containing carbonate or bicarbonate (2-methylmercaptoethyl)-hydantoin mixed aqueous solution is adjusted
PH to 3.0-7.0, then crystallisation by cooling, sucking filtration, washing, drying obtain 5- (2-methylmercaptoethyl)-hydantoin white knot
It is brilliant.
The method obtains 5- (2-methylmercaptoethyl)-hydantoin white crystals that purity is more than 99%, 5- (2- first sulfur
Base ethyl) yield of-hydantoin can reach more than 90%.
The chemical equation being related to is following (by taking Cyanogran. as an example)：
Due in the 5- containing carbonate (2-methylmercaptoethyl)-hydantoin aqueous solution, actually 5- (2- methylmercaptan ethyls
Base)-hydantoin be with salt (such as sodium salt or potassium salt) form exist because 5- (2-methylmercaptoethyl)-hydantoin exists
Dissolubility in water only has 1g/1000ml water (20 DEG C), therefore, the 5- containing carbonate (2-methylmercaptoethyl)-hydantoin
In aqueous solution, the existence form of 5- (2-methylmercaptoethyl)-hydantoin is following (by taking sodium carbonate as an example)：
Further, described preparation method, in the step (2), adjusts pH to 4.0-5.5.
Preferably, pH is adjusted using acid, described acid is mineral acid and/or organic acid, preferred mineral acid such as hydrochloric acid,
Sulphuric acid, phosphoric acid etc., particularly preferred hydrochloric acid.Acid adding speed is controlled during acid adding, due to containing carbonate in feed liquid, therefore, in acid adding
And when, substantial amounts of carbon dioxide will be produced, slug phenomenon will easily be produced.
Further, described preparation method, in the step (1), cyanide salt be cyaniding saline solution, concentration at least 20%
More than.
Preferably, described preparation method, in the step (1), described cyanide salt is Cyanogran., Cyanogas (Am. Cyanamid)., cyaniding
One or more in potassium.
Preferably, the cyanide salt is Cyanogran. and/or potassium cyanide.
Further, described carbonate is sodium carbonate and/or potassium carbonate, and bicarbonate is sodium bicarbonate and/or bicarbonate
Potassium.
Further, described preparation method, in the step (1), the cyano group of the cyanide salt, methylthiopropionaldehyde, dioxy
Change carbon, the molar ratio of ammonia is 1.01-1.05：1.0：1.2-2.0：1.5-2.5.
Further, described preparation method, it is in the step (1), described to synthesize the reaction of continuous three-level gradient increased temperature, the
, from 30 DEG C of gradient increased temperatures to 65 DEG C, from 65 DEG C of gradient increased temperatures to 100 DEG C, the third level is anti-for second level reaction temperature for first order reaction temperature
Temperature is answered from 100 DEG C of gradient increased temperatures to 115 DEG C；In 1.0-2.0Mpa, total reaction time is 10-30 minutes for reaction pressure control.
Preferably, the continuous three-level gradient increased temperature reaction is carried out in thtee-stage shiplock static mixing reactor, wherein the
The discharging opening of one-level static mixing reactor is connected with the charging aperture of second level static mixing reactor, and second level static mixing is anti-
The discharging opening of device is answered to connect with the charging aperture of third level static mixing reactor.By 3- methylthiopropionaldehydes, cyanide salt, carbon dioxide
Being passed through in thtee-stage shiplock static mixing reactor with the aqueous solution of ammonia carries out continuous third-order reaction, the pressure in thtee-stage shiplock reactor
From 30 DEG C of gradient increased temperatures to 65 DEG C, the temperature in device is answered in the second level to temperature of the power control in 1.0-2.0Mpa, the first stage reactor
, from 65 DEG C of gradient increased temperatures to 100 DEG C, the temperature in third level reactor is from 100 DEG C of gradient increased temperatures to 115 DEG C, anti-from the third level for degree
Answer the liquid that device discharging opening flows out send into the complete carbon dioxide of atmospheric steam stripping tower separation and recovery unreacted and ammonia, from tower
The liquid that bottom is flowed out is the 5- containing carbonate or bicarbonate (2-methylmercaptoethyl)-hydantoin mixed aqueous solution,
The gaseous mixture discharged from tower top prepares the aqueous solution of carbon dioxide and ammonia for recovery, and circulates for 5- (2- methylmercaptan ethyls
Base)-hydantoin aqueous solution preparation.
In order to realize 5- (2-methylmercaptoethyl)-hydantoin in high yield, in building-up process, the 3rd section of reaction temperature control
System is very crucial, and temperature is too high, and part 5- (2-methylmercaptoethyl)-hydantoin can then can under sodium carbonate or potassium carbonate effect
The following hydrolysis of generation, by taking sodium carbonate as an example, hydrolysis formula is as follows：
When carbonate is potassium carbonate, above-mentioned hydrolysis hydrolysis is more, therefore, the temperature control of the 3rd section of reaction is
It is very crucial, temperature more than 120 DEG C, when carbonate be potassium salt when, obtain be 5- (2-methylmercaptoethyl)-hydantoin,
The mixed liquor of methionine potassium, affects follow-up 5- (2-methylmercaptoethyl)-hydantoin purity.
Further, described preparation method, in the step (1), the described 5- containing carbonate or bicarbonate
(2-methylmercaptoethyl)-hydantoin mixed aqueous solution pH is 8.0-10, wherein 5- (2-methylmercaptoethyl)-hydantoin quality
It is 4%-15% that percent is the mass percent of 10%-20%, carbonate or bicarbonate.
Further, the described 5- containing carbonate or bicarbonate (2-methylmercaptoethyl)-hydantoin mixing
Aqueous solution also contains methionine salt and formates.
Further, described preparation method, in the step (2), chilling temperature is controlled at 10 DEG C -40 DEG C.
Particularly preferably chilling temperature is controlled at 10 DEG C -15 DEG C.
Further, described preparation method, in the step (2), the baking temperature is 50 DEG C -120 DEG C.
Preferably, the baking temperature is 80 DEG C -100 DEG C.
Further, described preparation method, in the step (2), by (the 2- first of the 5- containing carbonate or bicarbonate
Sulfenyl ethyl)-hydantoin mixed aqueous solution adjusts pH to 3.0-7.0 again after first being decolourized, and bleaching temperature is 40 DEG C -60
℃。
The decolouring can adopt activated carbon or NF membrane to be decolourized.It is preferred that decolourized using activated carbon, activated carbon
0.1%-0.5% of the consumption for feed liquid.
Beneficial effects of the present invention：
This method can realize 5- (2-methylmercaptoethyl)-hydantoin product purification by simply and easily operation,
With reaction simple to operate, abundant, product purity and the low feature of high income, energy consumption.
Specific embodiment
In order that the object, technical solutions and advantages of the present invention are clearer, below the preferred embodiments of the present invention are entered
The detailed description of row.
Embodiment 1
By the aqueous solution of carbon dioxide and ammonia, (carbon dioxide containing weight/mass percentage composition 13% and quality percentage contain successively
The ammonia of amount 8%), the methylthiopropionaldehyde of the sodium cyanide solution of weight/mass percentage composition 30% and weight/mass percentage composition 99.5% adds
To in first order static mixing reactor, material high efficient mixed in certain pressure condition in the static mixer of thtee-stage shiplock
Under (1.0-2.0Mpa) carry out the reaction of continuous three-level gradient increased temperature, first order reaction temperature from 30 DEG C of gradient increased temperatures to 65 DEG C, the
Secondary response temperature from 65 DEG C of gradient increased temperatures to 100 DEG C, third level reaction temperature from 100 DEG C of gradient increased temperatures to 115 DEG C, from the 3rd
The liquid that level static mixing reactor discharging opening flows out sends into atmospheric steam stripping tower point after pressure release to 0.8-1.0Mpa
From the complete carbon dioxide of unreacted and ammonia is reclaimed, the liquid flowed out from bottom of towe is (the 2- methylmercaptan ethyls of the 5- containing sodium carbonate
Base)-hydantoin aqueous solution, the aqueous solution of carbon dioxide and ammonia is prepared for recovery and circulate use from the gaseous mixture of tower top discharge
In the preparation of 5- (2-methylmercaptoethyl)-hydantoin aqueous solution.
The 5- containing sodium carbonate (2-methylmercaptoethyl) flowed out from bottom of towe-hydantoin aqueous solution adds 0.1% work
Property charcoal, desolventing technology is carried out under the conditions of 45 DEG C, filter activity charcoal obtains almost colourless transparent liquid, its pH be 9.5,5-
The weight/mass percentage composition of (2-methylmercaptoethyl)-hydantoin is 13%, and the weight/mass percentage composition of sodium carbonate is 4.1%, 5- (2-
Methylmercaptoethyl)-hydantoin yield 97% (in terms of methylthiopropionaldehyde).Above-mentioned water white liquid is added into concentrated hydrochloric acid,
Acid adding speed is controlled, slug is prevented, when pH is down to 7.0, substantial amounts of white solid occurs, hydrochloric acid is continuously added until pH
4.5 are down to, are considered as terminal.Feed liquid after neutralization is cooled to into 10 DEG C, stirred crystallization, sucking filtration, solid are washed with a small amount of clear water,
Then dry, drying temperature is controlled at 90 DEG C, obtain 5- (the 2-methylmercaptoethyl)-hydantoin white that purity is 99.5% brilliant
Body, yield are 96.5%.
Comparative example 1
A patent is applied for before Chongqing Unisplendour Tianhua Methionine Co., Ltd.《The preparation facilitiess of glycolylurea and side
Method》, the method that thtee-stage shiplock static mixing reactor prepares glycolylurea is disclosed, by 3- methylthiopropionaldehydes, Cyanogran., carbon dioxide
Being passed through in thtee-stage shiplock static mixing reactor with the aqueous solution of ammonia carries out continuous third-order reaction, the pressure in thtee-stage shiplock reactor
From 40 DEG C of gradient increased temperatures to 80 DEG C, the temperature in device is answered in the second level to temperature of the power control in 1.4-2.6MPa, the first stage reactor
, from 80 DEG C of gradient increased temperatures to 120 DEG C, the temperature in third level reactor is from 120 DEG C of gradient increased temperatures to 160 DEG C for degree.With phase of the present invention
Than the condition control of third-order reaction is had any different, and arranges a comparative example accordingly.
By the aqueous solution of carbon dioxide and ammonia, (carbon dioxide containing weight/mass percentage composition 13% and quality percentage contain successively
The ammonia of amount 8%), the methylthiopropionaldehyde of the sodium cyanide solution of weight/mass percentage composition 30% and weight/mass percentage composition 99.5% adds
To in first order static mixing reactor, material high efficient mixed in certain pressure condition in the static mixer of thtee-stage shiplock
Under (1.4-2.6MPa) carry out the reaction of continuous three-level gradient increased temperature, first order reaction temperature from 40 DEG C of gradient increased temperatures to 80 DEG C, the
Secondary response temperature from 80 DEG C of gradient increased temperatures to 120 DEG C, third level reaction temperature from 120 DEG C of gradient increased temperatures to 160 DEG C, from the 3rd
The liquid that level static mixing reactor discharging opening flows out sends into atmospheric steam stripping tower point after pressure release to 0.8-1.0Mpa
From the complete carbon dioxide of unreacted and ammonia is reclaimed, the liquid flowed out from bottom of towe is (the 2- methylmercaptan ethyls of the 5- containing sodium carbonate
Base)-hydantoin aqueous solution, the aqueous solution of carbon dioxide and ammonia is prepared for recovery and circulate use from the gaseous mixture of tower top discharge
In the preparation of 5- (2-methylmercaptoethyl)-hydantoin aqueous solution.
The 5- containing sodium carbonate (2-methylmercaptoethyl) flowed out from bottom of towe-hydantoin aqueous solution adds 0.1% work
Property charcoal, desolventing technology is carried out under the conditions of 45 DEG C, filter activity charcoal obtains almost colourless transparent liquid, its pH be 9.5,5-
The weight/mass percentage composition of (2-methylmercaptoethyl)-hydantoin is 14%, and the weight/mass percentage composition of sodium carbonate is 6%, 5- (2- first
Sulfenyl ethyl)-hydantoin yield 93% (in terms of methylthiopropionaldehyde).Above-mentioned water white liquid is added into concentrated hydrochloric acid, control
Acid adding speed is made, slug is prevented, when pH is down to 7.0, substantial amounts of white solid occurs, hydrochloric acid is continuously added until pH is down to
4.5, it is considered as terminal.Feed liquid after neutralization is cooled to into 10 DEG C, stirred crystallization, sucking filtration, solid are washed with a small amount of clear water, then
Drying, drying temperature are controlled at 90 DEG C, obtain 5- (2-methylmercaptoethyl)-hydantoin white crystal that purity is 99%, are received
Rate is 90%.(please data are supplemented)
Embodiment 2
By the aqueous solution of carbon dioxide and ammonia, (carbon dioxide containing weight/mass percentage composition 13% and quality percentage contain successively
The ammonia of amount 8%), the methylthiopropionaldehyde of the cyaniding aqueous solutions of potassium of weight/mass percentage composition 40% and weight/mass percentage composition 99.3% adds
To in first order static mixing reactor, material high efficient mixed in certain pressure condition in the static mixer of thtee-stage shiplock
Under carry out the reaction of continuous three-level gradient increased temperature, first order reaction temperature from 30 DEG C of gradient increased temperatures to 65 DEG C, second level reaction temperature
From 65 DEG C of gradient increased temperatures to 100 DEG C, third level reaction temperature is from 100 DEG C of gradient increased temperatures to 115 DEG C, anti-from third level static mixing
Answer the liquid that device discharging opening flows out that atmospheric steam stripping tower separation and recovery unreacted is sent into after pressure release to 0.8-1.0Mpa
Complete carbon dioxide and ammonia, the liquid flowed out from bottom of towe are the 5- containing potassium carbonate (2-methylmercaptoethyl)-hydantoin water
Solution, the gaseous mixture discharged from tower top prepare the aqueous solution of carbon dioxide and ammonia for recovery and circulate for 5- (2- methyl mercaptos
Ethyl)-hydantoin aqueous solution preparation.
The 5- containing potassium carbonate (2-methylmercaptoethyl) flowed out from bottom of towe-hydantoin aqueous solution adds 0.1% work
Property charcoal, desolventing technology is carried out under the conditions of 45 DEG C, filter activity charcoal obtains almost colourless transparent liquid, its pH be 10.0,5-
The weight/mass percentage composition of (2-methylmercaptoethyl)-hydantoin is 11%, and the weight/mass percentage composition of potassium carbonate is 4.1%, egg ammonia
The weight/mass percentage composition of sour potassium is 4% and the weight/mass percentage composition of potassium formate is acyl in 0.05%, 5- (2-methylmercaptoethyl)-second
Urea yield 85% (in terms of methylthiopropionaldehyde).Above-mentioned water white liquid is added into concentrated hydrochloric acid, acid adding speed is controlled, is prevented
, when pH is down to 7.0, there is substantial amounts of white solid in slug, continuously adds hydrochloric acid and is down to 4.5 up to pH, is considered as terminal.By in
Feed liquid with after is cooled to 40 DEG C, and stirred crystallization, sucking filtration, solid are washed with a small amount of clear water, are then dried, drying temperature control
At 90 DEG C, 5- (2-methylmercaptoethyl)-hydantoin white crystal that purity is 99.2% is obtained, wherein the matter containing methionine
Amount percentage composition is 90% for the yield of 0.6%, 5- (2-methylmercaptoethyl)-hydantoin.
Comparative example 2
By the aqueous solution of carbon dioxide and ammonia, (carbon dioxide containing weight/mass percentage composition 13% and quality percentage contain successively
The ammonia of amount 8%), the methylthiopropionaldehyde of the cyaniding aqueous solutions of potassium of weight/mass percentage composition 40% and weight/mass percentage composition 99.3% adds
To in first order static mixing reactor, material high efficient mixed in certain pressure condition in the static mixer of thtee-stage shiplock
Under (1.4-2.6MPa) carry out the reaction of continuous three-level gradient increased temperature, first order reaction temperature from 40 DEG C of gradient increased temperatures to 80 DEG C, the
Secondary response temperature from 80 DEG C of gradient increased temperatures to 120 DEG C, third level reaction temperature from 120 DEG C of gradient increased temperatures to 160 DEG C, from the 3rd
The liquid that level static mixing reactor discharging opening flows out sends into atmospheric steam stripping tower point after pressure release to 0.8-1.0Mpa
From the complete carbon dioxide of unreacted and ammonia is reclaimed, the liquid flowed out from bottom of towe is (the 2- methylmercaptan ethyls of the 5- containing potassium carbonate
Base)-hydantoin aqueous solution, the aqueous solution of carbon dioxide and ammonia is prepared for recovery and circulate use from the gaseous mixture of tower top discharge
In the preparation of 5- (2-methylmercaptoethyl)-hydantoin aqueous solution.
The 5- containing potassium carbonate (2-methylmercaptoethyl) flowed out from bottom of towe-hydantoin aqueous solution adds 0.1% work
Property charcoal, desolventing technology is carried out under the conditions of 45 DEG C, filter activity charcoal obtains almost colourless transparent liquid, its pH be 10,5-
The weight/mass percentage composition of (2-methylmercaptoethyl)-hydantoin is 13%, and the weight/mass percentage composition of potassium carbonate is 7%, methionine
The weight/mass percentage composition of potassium is 2% and the weight/mass percentage composition of potassium formate is that 7%, 5- (2-methylmercaptoethyl)-hydantoin is received
Rate 91% (in terms of methylthiopropionaldehyde).Above-mentioned water white liquid is added into concentrated hydrochloric acid, acid adding speed is controlled, punching is prevented
, when pH is down to 7.0, there is substantial amounts of white solid in material, continuously adds hydrochloric acid and is down to 4.5 up to pH, is considered as terminal.Will neutralization
Feed liquid afterwards is cooled to 40 DEG C, and stirred crystallization, sucking filtration, solid are washed with a small amount of clear water, are then dried, and drying temperature control exists
90 DEG C, 5- (2-methylmercaptoethyl)-hydantoin white crystal that purity is 99% is obtained, yield is 90%.(please data are entered
Row is supplemented)
Embodiment 3
By the aqueous solution of carbon dioxide and ammonia, (carbon dioxide containing weight/mass percentage composition 13% and quality percentage contain successively
The ammonia of amount 8%), the methylthiopropionaldehyde of the sodium cyanide solution of weight/mass percentage composition 30% and weight/mass percentage composition 99.5% adds
To in first order static mixing reactor, material high efficient mixed in certain pressure condition in the static mixer of thtee-stage shiplock
Under carry out the reaction of continuous three-level gradient increased temperature, first order reaction temperature from 30 DEG C of gradient increased temperatures to 65 DEG C, second level reaction temperature
From 65 DEG C of gradient increased temperatures to 100 DEG C, third level reaction temperature is from 100 DEG C of gradient increased temperatures to 115 DEG C, anti-from third level static mixing
Answer the liquid that device discharging opening flows out that atmospheric steam stripping tower separation and recovery unreacted is sent into after pressure release to 0.8-1.0Mpa
Complete carbon dioxide and ammonia, the liquid flowed out from bottom of towe are the 5- containing sodium carbonate (2-methylmercaptoethyl)-hydantoin water
Solution, the gaseous mixture discharged from tower top prepare the aqueous solution of carbon dioxide and ammonia for recovery and circulate for 5- (2- methyl mercaptos
Ethyl)-hydantoin aqueous solution preparation.
The 5- containing sodium carbonate (2-methylmercaptoethyl) flowed out from bottom of towe-hydantoin aqueous solution adds 0.1% work
Property charcoal, desolventing technology is carried out under the conditions of 45 DEG C, filter activity charcoal obtains almost colourless transparent liquid, its pH be 9.5,5-
The weight/mass percentage composition of (2-methylmercaptoethyl)-hydantoin is 13%, and the weight/mass percentage composition of sodium carbonate is 4.1%, 5- (2-
Methylmercaptoethyl)-hydantoin yield 97% (in terms of methylthiopropionaldehyde).Above-mentioned water white liquid is added into mass fraction
For 60% aqueous sulfuric acid, acid adding speed is controlled, slug is prevented, when pH is down to 7.0, substantial amounts of white solid occur,
Continuously add hydrochloric acid and 5.0 are down to up to pH, be considered as terminal.Feed liquid after neutralization is cooled to into 35 DEG C, stirred crystallization, sucking filtration, Gu
Body is washed with a small amount of clear water, is then dried, and drying temperature is controlled at 90 DEG C, obtains 5- (the 2- methyl mercaptos that purity is 99.5%
Ethyl)-hydantoin white crystal, yield is 94.5%.
Comparative example 3
By the aqueous solution of carbon dioxide and ammonia, (carbon dioxide containing weight/mass percentage composition 13% and quality percentage contain successively
The ammonia of amount 8%), the methylthiopropionaldehyde of the sodium cyanide solution of weight/mass percentage composition 30% and weight/mass percentage composition 99.5% adds
To in first order static mixing reactor, material high efficient mixed in certain pressure condition in the static mixer of thtee-stage shiplock
Under carry out the reaction of continuous three-level gradient increased temperature, first order reaction temperature from 30 DEG C of gradient increased temperatures to 65 DEG C, second level reaction temperature
From 65 DEG C of gradient increased temperatures to 100 DEG C, third level reaction temperature is from 100 DEG C of gradient increased temperatures to 115 DEG C, anti-from third level static mixing
Answer the liquid that device discharging opening flows out that atmospheric steam stripping tower separation and recovery unreacted is sent into after pressure release to 0.8-1.0Mpa
Complete carbon dioxide and ammonia, the liquid flowed out from bottom of towe are the 5- containing sodium carbonate (2-methylmercaptoethyl)-hydantoin water
Solution, the gaseous mixture discharged from tower top prepare the aqueous solution of carbon dioxide and ammonia for recovery and circulate for 5- (2- methyl mercaptos
Ethyl)-hydantoin aqueous solution preparation.
The 5- containing sodium carbonate (2-methylmercaptoethyl) flowed out from bottom of towe-hydantoin aqueous solution adds 0.1% work
Property charcoal, desolventing technology is carried out under the conditions of 45 DEG C, filter activity charcoal obtains almost colourless transparent liquid, its pH be 9.5,5-
The weight/mass percentage composition of (2-methylmercaptoethyl)-hydantoin is 13%, and the weight/mass percentage composition of sodium carbonate is 4.1%, 5- (2-
Methylmercaptoethyl)-hydantoin yield 97% (in terms of methylthiopropionaldehyde).Above-mentioned water white liquid is added into mass fraction
For 60% aqueous sulfuric acid, acid adding speed is controlled, slug is prevented, until pH is down to 3.0, be considered as terminal.After neutralization
Feed liquid is cooled to 35 DEG C, and stirred crystallization, sucking filtration, solid are washed with a small amount of clear water, are then dried, and drying temperature is controlled 90
DEG C, 5- (2-methylmercaptoethyl)-hydantoin white crystal that purity is 95% is obtained, yield is 83%.
Finally illustrate, above example is only unrestricted to illustrate technical scheme, although with reference to compared with
Good embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent, and without deviating from the objective and scope of technical solution of the present invention, which all should be covered at this
In the middle of the right of invention.
Claims (10)
1. a kind of preparation method of high-purity 5- (2-methylmercaptoethyl)-hydantoin, it is characterised in that including what is be carried out as follows
Step：
(1) with cyanide salt, methylthiopropionaldehyde, ammonia and arbon dioxide solution as raw material, synthesis is containing carbonate or bicarbonate
5- (the 2-methylmercaptoethyl)-hydantoin mixed aqueous solution of salt；
(2) by the 5- containing carbonate or bicarbonate (2-methylmercaptoethyl)-hydantoin mixed aqueous solution adjust pH to
3.0-7.0, then crystallisation by cooling, sucking filtration, washing, drying obtain 5- (2-methylmercaptoethyl)-hydantoin white crystals.
2. preparation method according to claim 1, it is characterised in that in the step (2), adjusts pH to 4.0-5.5.
3. preparation method according to claim 1, it is characterised in that in the step (1), cyanide salt are that cyanide salt is water-soluble
Liquid, concentration at least more than 20%.
4. the preparation method according to claim 1 or 3, it is characterised in that in the step (1), described cyanide salt is
One or more in Cyanogran., Cyanogas (Am. Cyanamid)., potassium cyanide.
5. preparation method according to claim 1, it is characterised in that in the step (1), the cyano group of the cyanide salt,
Methylthiopropionaldehyde, carbon dioxide, the molar ratio of ammonia are 1.01-1.05：1.0：1.2-2.0：
1.5-2.5。
6. preparation method according to claim 1, it is characterised in that in the step (1), described to synthesize continuous three-level
Gradient increased temperature reacts, and, from 30 DEG C of gradient increased temperatures to 65 DEG C, second level reaction temperature is from 65 DEG C of gradient increased temperatures for first order reaction temperature
To 100 DEG C, third level reaction temperature is from 100 DEG C of gradient increased temperatures to 115 DEG C；Reaction pressure is controlled in 1.0-2.0Mpa, overall reaction
Time is 10-30 minutes.
7. preparation method according to claim 1, it is characterised in that in the step (1), it is described containing carbonate or
The 5- (2-methylmercaptoethyl) of person's bicarbonate-hydantoin mixed aqueous solution pH be 8.0-10, wherein 5- (2- methylmercaptan ethyls
Base)-hydantoin mass percent for 10%-20%, carbonate or bicarbonate mass percent be 4%-15%.
8. preparation method according to claim 1, it is characterised in that in the step (2), chilling temperature control is 10
℃-40℃。
9. preparation method according to claim 1, it is characterised in that in the step (2), the baking temperature are 50
℃-120℃。
10. preparation method according to claim 1, it is characterised in that in the step (2), will containing carbonate or
5- (the 2-methylmercaptoethyl)-hydantoin mixed aqueous solution of bicarbonate adjusts pH again to 3.0-7.0 after first being decolourized, take off
Color temperature is 40 DEG C -60 DEG C.
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