CN101348452A - Preparation of homocystine - Google Patents
Preparation of homocystine Download PDFInfo
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- CN101348452A CN101348452A CNA2007100700920A CN200710070092A CN101348452A CN 101348452 A CN101348452 A CN 101348452A CN A2007100700920 A CNA2007100700920 A CN A2007100700920A CN 200710070092 A CN200710070092 A CN 200710070092A CN 101348452 A CN101348452 A CN 101348452A
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Abstract
A method for preparing homocystine is disclosed. The method capable of eliminating a great amount of pollutants, recycling useful materials, and reducing preparation cost comprises following steps that: methionine together with a 5 to 18mol/L sulfuric acid and a 0 to 50 percent (by weight) halogen acid is heated to and kept at a temperature of 100 to 150 DEG C for 0.5 to 20 hours, with the molar ratio of methionine to sulphuric acid to halogen acid being 1 to 2-6.5 to 0-4; after the reaction liquid is cooled down, the sulfuric acid in the reaction liquid is reclaimed through dialysis until the isoelectric point of homocystine is reached, and then the precipitate is filtrated, washed, and dried to obtain homocystine. The invention is suitable for the preparation of homocystine.
Description
Technical field
The present invention relates to a kind of amino acid whose preparation method who contains disulfide linkage, relate in particular to a kind of preparation method of homocystine.
Background technology
Homocystine is a kind of amino acid that contains disulfide linkage, and its structural formula is:
The product of homocystine reductive cyclization promptly is acid in the homocysteine sulphur, is the key intermediate of synthetic drugs Erdosteine, and the homocystine oxidation products promptly is a high-cysteic acid, is a kind of important medicine intermediate.
Synthetic about homocystine proposed with methionine(Met) and a large amount of excessive sulfuric acid heat and get and use till today altogether by Butz and du Vigneaud (J.Biol.Chem., 1932-33,99,135) the earliest.Yet this is not an ideal method, because the theoretical yield of homocystine also has only 50%, this is owing to produce a large amount of by product dimethyl sulfonium salt (S-methylmethionine hydrogen sulfate sulfonium).Another problem of this method is the not reacted sulfuric acid that will neutralize with a large amount of liquid caustic soda after the reaction, produce a large amount of sodium sulfate solids and the waste water that contains high concentration sodium sulfate, these two kinds of wastes all do not have treating method preferably at present, make it and can't recycle because of containing a large amount of organism and pigment in the solid sodium sulfate.Though and contained organism is the amino acids material in the waste water, very easily biochemical, because of making microorganism, the sodium sulfate that contains high density can't under this environment, survive, so this part waste water also can't be used conventional disposal methods.These two kinds of wastes have all caused sizable harm to environment.
In addition, the another kind of method of having reported is that methionine(Met) gets homocysteine with the sodium Metal 99.5 demethylating in liquefied ammonia, reoxidizes to obtain homocystine (DE-A-3309761 and 2547672).Obviously, but the good method that this neither a suitability for industrialized production because be not easy in the transportation of liquefied ammonia and sodium Metal 99.5, use and the aftertreatment, requires very harsh to operational condition.
US 4,550,199 disclose a kind of method for preparing homocystine with the homocysteine double sodium salt with hydrogen peroxide oxidation, but the homocysteine double sodium salt is still made with sodium Metal 99.5 in liquefied ammonia by methionine(Met), and there is no the supply of homocysteine double sodium salt on the market, so do not have the industrialization practical value yet.
EP 844,239 disclose a kind of method that tool industrial applications is worth before the present invention, it introduces haloid acid when methionine(Met) and sulfuric acid are warm altogether, be meant Hydrogen bromide generally speaking, the by product dimethyl sulfonium salt that produces is converted into methionine(Met) again, the yield of homocystine can be brought up to more than 92% like this.But this method equally need be with liquid caustic soda neutralize not reacted sulfuric acid and hydrobromic nitration mixture, produce a large amount of sodium sulfate and Sodium Bromide solid waste and contain the sodium sulfate of high density and the waste water of Sodium Bromide, these two kinds of wastes are because of contains sodium sulfate and two kinds of salt of Sodium Bromide, the difficulty of handling is more much more difficult than a kind of salt of independent contains sodium sulfate, and is also much bigger to the harm of environment.
But the nitration mixture of methionine(Met) and sulfuric acid or sulfuric acid and haloid acid heat altogether prepares the method that homocystine is present unique suitability for industrialized production, but this method will produce the waste water of a large amount of solid waste and supersalinity, and environment is caused serious harm.
Summary of the invention
The present invention will solve prior art can produce a large amount of solid waste and supersalinity with the common hot preparation homocystine of the nitration mixture of methionine(Met) and sulfuric acid or sulfuric acid and haloid acid waste water, to environment cause serious harm problem, the preparation method of homocystine of the present invention is provided for this reason, this law gained reaction solution can or only need add the alkali neutralization of relatively small amount without alkali neutralization, sulfuric acid that recovery obtains or sulfuric acid and haloid acid can be back to production again, not only eliminated a large amount of pollutents, also reclaim useful material, reduced preparation cost.
For addressing the above problem, its special character of the technical solution used in the present invention is to be total to heat 0.5～20 hour with the nitration mixture that the haloid acid of methionine(Met) and 5～15mol/L sulfuric acid or 5～15mol/L sulfuric acid and 30～50% is formed under 100～150 ℃ of temperature, after the reaction solution cooling, sulfuric acid in dialysis recovery reaction solution is to the iso-electric point of homocystine, precipitate after filtration, the washing, the oven dry, homocystine.
Described dialysis can be electrodialysis, also can be diffusion dialysis and electrodialysis.
Described reaction solution can add the iso-electric point that alkali is neutralized to homocystine after dialysis, precipitate after filtration, the washing, the oven dry, homocystine.
Described reaction solution decolours for good after dialysis again.
Its device of described diffusion dialysis is made up of at least one diffusion dialysis film, at least one former liquid chamber and at least one recovery chamber, and the diffusion dialysis film is clipped in former liquid chamber and reclaims between the chamber; Described electrodialysis unit is made up of the cathode compartment of at least one cationic exchange membrane or at least one Bipolar Membrane, at least one anion-exchange membrane, at least one dense chamber, at least one light chamber, at least one built-in anodic anolyte compartment and at least one built-in negative electrode.
Described cationic exchange membrane is homogeneous phase cation exchange film or out-phase cationic exchange membrane; Described anion-exchange membrane is homogeneous-phase anion exchange film or out-phase anion-exchange membrane.
Described alkali is the combination of a kind of in sodium hydroxide, potassium hydroxide, hydrated barta, ammoniacal liquor, liquefied ammonia, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, volatile salt, bicarbonate of ammonia, the barium carbonate or at least two kinds.
Described methionine(Met) is a kind of in D-methionine(Met), L-methionine(Met) or the DL-methionine, and correspondingly, described homocystine is a kind of in D-homocystine, L-homocystine or the DL-homocystine.
Described haloid acid is ...
Description of drawings
Fig. 1 contains the unitary diffusion of a plurality of diffusion dialysis to ooze the device synoptic diagram;
Fig. 2 is the electrodialyzer synoptic diagram of two circulating systems;
Fig. 3 is the electrodialyzer synoptic diagram of four circulating systems;
Fig. 4 is two circulating system electrodialyzer synoptic diagram with Bipolar Membrane.
Be labeled as among the figure: 1 reaction solution, 2 water or dilute sulphuric acid, 3 reaction solutions, 4 dilute sulphuric acids, 5 utmost point chamber liquid, 6 anolytes, 7 catholytes, the former liquid chamber of I, II reclaims the chamber, the light chamber of III, the dense chamber of IV, the V cathode compartment, VI anolyte compartment, M diffusion dialysis film, the A anion-exchange membrane, C cationic exchange membrane, AC Bipolar Membrane, the ca negative electrode, an anode, n represents repetition.
The invention will be further described for following structure accompanying drawing.
After methionine and sulfuric acid or sulfuric acid and halogen acids were total to heat, reactant liquor neutralized without alkali, directly enters diffusion Dialyzer is with the part of sulfuric acid in the diffusive dialysis method recovery reactant liquor or the nitration mixture of sulfuric acid and halogen acids; After this, Further slough and reclaim again the nitration mixture of sulfuric acid in the reactant liquor or sulfuric acid and halogen acids with electrodialysis methods extremely The isoelectric point of homocystine;
Reactant liquor also can without electrodialysis, be neutralized to the isoelectric point of homocystine again with alkali after the diffusion dialysis;
Reactant liquor also can be without diffusion dialysis, and removes and reclaim sulfuric acid or sulphur in the reactant liquor through electrodialysis The nitration mixture of acid and halogen acids is to the isoelectric point of homocystine;
Reactant liquor also can be without diffusion dialysis, and reclaims a part of sulfuric acid or sulfuric acid and halogen acids through electrodialysis Nitration mixture, be neutralized to again the isoelectric point of homocystine with alkali;
Expand analyse, electrolysis, neutralization.
Because homocystine is minimum in its isoelectric point place solubility, the homocystine in the reactant liquor is with solid form Separate out, filter the solid obtain homocystine, can dry after salt-free with the clear water washing and obtain finished product.
For color and luster and the purity that guarantees product, can be with the reactant liquor depickling to a certain degree the time, as in electric osmose Analyse front or alkali in and frontly decolour with charcoal absorption.
The present invention adopts the diffusion dialysis device, with the nitration mixture of methionine and sulfuric acid or sulfuric acid and halogen acids altogether after the heat Reactant liquor is made the nitration mixture of diffusion dialysis reclaim sulfuric acid or sulfuric acid and halogen acids. The diffusion dialysis device is by at least one expansion Dialyser, at least one former liquid chamber and at least one of loosing reclaims the chamber and forms, the diffusion dialysis film be clipped in former liquid chamber and Reclaim between the chamber. What form like this is a diffusion dialysis unit, and practical application can be by a plurality of such lists Unit forms, and namely a plurality of former liquid chambers and recovery chamber are stacked alternately, and separate with the diffusion dialysis film between them, form A diffusion dialysis device that is formed by a plurality of diffusion dialysis unit serial connection.
The present invention also adopts electric dialyzator, with described reactant liquor do electrodialysis reclaim wherein sulfuric acid or sulfuric acid and The nitration mixture of halogen acids. Electric dialyzator is by at least one cation-exchange membrane or at least one Bipolar Membrane, at least one Open the anode chamber of anion-exchange membrane, at least one dense chamber, at least one light chamber, at least one built-in anode Form with the cathode chamber of at least one built-in negative electrode. What form like this is an electrodialysis cell, actual answering With being formed by a plurality of such unit.
Described reactant liquor refers to the reactant liquor after the nitration mixture of methionine and sulfuric acid or sulfuric acid and halogen acids is total to heat, also Can refer to that above-mentioned reactant liquor is earlier after the nitration mixture of part of sulfuric acid or sulfuric acid and halogen acids has been reclaimed in diffusion dialysis Reactant liquor.
No matter methionine(Met) is D-, L-or DL-type, the nitration mixture of forming with the haloid acid of 5～15mol/L sulfuric acid or 5～15mol/L sulfuric acid and 30～50% was total to heat after 0.5～20 hour under 100～150 ℃ of temperature, the methionine(Met) demethylating, and take place oxidation generated corresponding D-, L-or DL-homocystine:
After reaction finishes, also contain very the sulfuric acid of high density or the nitration mixture of sulfuric acid and haloid acid in the reaction solution, the methionine(Met) that product homocystine, unreacted finish and other by product etc., these by products also all are the amino acids materials.In this strongly-acid medium, two amino in the homocystine combine with two hydrogen ions and form divalent cation (with HctH
2 2+Expression), other amino acid also all exists with cationic form.
As shown in Figure 1, a cell body is divided into two portions with a diffusion dialysis film M, one side wherein be called former liquid chamber I, the other side is called and reclaims chamber II, has so just formed a diffusion dialysis unit.As arranging in the following order by many diffusion dialysis films:
II M I M II M I M II …… I
So just formed a diffusion dialysis device of forming by a plurality of diffusion dialysis unit with industrialization practical value.
The diffusion dialysis film is a special anion-exchange membrane, and it has the anionic effect of seeing through.When the nitration mixture of methionine(Met) and sulfuric acid or sulfuric acid and the haloid acid reaction solution 1 after the heat altogether, enter the former liquid chamber I of diffusion dialysis device, after chamber II are reclaimed in pure water or dilute sulphuric acid 2 inputs, because the sulfate ion (SO in the indoor liquid of stoste
4 2-) or hydrogen sulfate ion (HSO
4 -) or halogen ion (X
-) the concentration solution indoor far above recovery, just exist an anion concentration poor in the both sides of diffusion dialysis film.Because negatively charged ion can very successfully see through the diffusion dialysis film, so the SO in the solution in the former liquid chamber I
4 2-Or HSO
4 -Or X
-Will under the concentration difference impellent, diffuse into and reclaim chamber II.In order to keep electric neutrality, negatively charged ion must carry positively charged ion and together enter when diffusing into the recovery chamber.Because the ionic channel size of diffusion dialysis film only allows hydrogen ion (H
+) pass through, and compare H
+The HctH that radius is much bigger
2 2+Deng having stayed former liquid chamber by the diffusion dialysis film.Like this, sulfuric acid in the former liquid chamber or haloid acid will constantly diffuse into the recovery chamber under the impellent of concentration difference, thereby have obtained recovery.
But it is also noted that the diffusion dialysis film is an anion-exchange membrane, it is to H
+Repulsive force is arranged, and when the anionic concentration difference impellent in diffusion dialysis film both sides equated hydrionic repulsive force with film, the diffusion dialysis process had just stopped.So diffusion dialysis can only be reclaimed the part of sulfuric acid in the reaction solution or the nitration mixture of sulfuric acid and haloid acid.The great advantage of diffusion dialysis is that energy consumption is low, only needs consumable liquid to carry required power, almost can ignore.But it is low that its disadvantage is the rate of recovery.
Reaction solution after the diffusion dialysis can be neutralized to the iso-electric point of homocystine with alkali, because homocystine is minimum and separate out from solution in iso-electric point place solubleness, as long as through simple filtering and with the clear water washing, salinity contained in the flush away homocystine gets product.For color and luster and the quality that guarantees product, the reaction solution after the diffusion dialysis also can be earlier with neutralizing with alkali after the charcoal absorption again.Described alkali can be one or two or more kinds the combination in sodium hydroxide, potassium hydroxide, hydrated barta, ammoniacal liquor, liquefied ammonia, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, volatile salt, bicarbonate of ammonia, the barium carbonate.
The nitration mixture of methionine(Met) and sulfuric acid or sulfuric acid and haloid acid altogether the reaction solution after the heat also can with electrodialytic method recovery wherein sulfuric acid or the nitration mixture of sulfuric acid and haloid acid.
As shown in Figure 2, the VI of anolyte compartment by cathode compartment V, the cationic exchange membrane C of a built-in negative electrode ca, light chamber III, anion-exchange membrane A, dense chamber IV, cationic exchange C, built-in anode an forms two traditional circulating system electrodialysis cell.It is right that cationic exchange membrane and anion-exchange membrane are called one group of film, and one group of film is to constituting an electrodialysis cell.If between cathode compartment and anolyte compartment, arrange pressing following particular order by many groups film:
V C III A IV C III A IV …… IV C VI
So just constituted one can industrial applications electrodialysis unit, it is right that electrodialysis unit can reach up to a hundred groups of films.
In order to prevent the loss of homocystine, the invention provides another kind of electrodialytic scheme, four circulation electrodialysis systems as shown in Figure 3.It forms the electrodialysis cell of one four circulating system by the VI of anolyte compartment of cathode compartment V, the anion-exchange membrane A of built-in negative electrode ca, light chamber III, anion-exchange membrane A, dense chamber IV, cationic exchange membrane C, built-in anode an.A plurality of such unit can be formed one through in parallel or series connection can be for the electrodialysis unit of industrial applications.This electrodialysis system is compared with traditional electrodialysis system, there is a maximum difference just to be that the both sides of light chamber III all are anion-exchange membrane A, another difference is that anolyte 6 is different with catholyte 7, anolyte 6 adopts sulphuric acid soln, catholyte 7 adopts sodium hydroxide solution, and traditional electrodialytic anolyte is identical with catholyte.Also have in the electrodialysis unit that a difference is made up of a plurality of electrodialysis cell, each electrodialysis cell all must comprise an anolyte compartment and a cathode compartment, and traditional electrodialysis only needs at the two ends of electrodialysis unit an anolyte compartment to be set and a cathode compartment gets final product.
The reaction solution 3 that the nitration mixture of methionine(Met) and sulfuric acid or sulfuric acid and haloid acid is total to after the heat enters light chamber III, dilute sulphuric acid 4 enters dense chamber IV, and sulphuric acid soln 6 enters the VI of anolyte compartment, and sodium hydroxide solution 7 enters cathode compartment V, behind logical upward direct current between anode and the negative electrode, the OH in the cathode compartment V
-Under the promotion of electrical forces, see through anion-exchange membrane A and enter into light chamber III, with light indoor H
+Neutralization is H
2O, and light indoor SO
4 2-Or HSO
4 -Or X
-Also under the promotion of electrical forces, see through anion-exchange membrane A and enter into dense chamber IV, the H in the VI of anolyte compartment
+Also under the promotion of electrical forces, see through cationic exchange membrane C and enter into dense chamber.Like this, sulfuric acid in the light indoor reaction solution or haloid acid just constantly enter into dense chamber and obtain accumulation in dense chamber.Because light indoor both sides all are anion-exchange membranes, so the homocystine in the reaction solution (existing with cationic form) can not run off.Yet because each unit of electrodialysis of four circulating systems all comprises an anode and a negative electrode, so each electrodialysis cell all wants brine electrolysis, all wants the ionization energy and the polarization of electrode energy of consume water.And what unit traditional electrodialysis comprises and all has only an anode and a negative electrode, so can the loss-rate traditional electrodialysis of the electrodialysis of four circulating systems is much higher.
Guarantee again that in order to cut down the consumption of energy homocystine does not run off, the present invention provides another kind of scheme again, promptly adopts two circulating systems of Bipolar Membrane.As shown in Figure 4, this electrodialysis system is in full accord with traditional electrodialysis in form, just the anode membrane in the traditional electrical dialysis is replaced with Bipolar Membrane.So its arrangement mode is:
V AC III A IV AC III A IV …… IV AC VI
Bipolar Membrane is the laminate of anion-exchange membrane and cationic exchange membrane, the difference of it and one pole anion-exchange membrane and one pole cationic exchange membrane be can be in electrodialytic electric field catalytic pyrolysis water effectively, therefore be used to provide H
+And OH
-
The two circulation electrodialysis systems that adopt Bipolar Membrane are identical with the recovery principle of the sulfuric acid of above-mentioned four circulation electrodialysis systems or haloid acid, and difference only is that it has adopted Bipolar Membrane splitting water generation H
+And OH
-, replace relying in the above-mentioned four circulation electrodialysis systems water electrolysis of anode and negative electrode to produce H
+And OH
-In whole electrodialysis system, only need an anode and a negative electrode like this, needn't anode and negative electrode be set all in each electrodialysis cell, more compact structure, energy consumption is lower, operates simpler.
Usually, any film that is usually used in electrodialytic method can be used for the present invention, preferably use commercially available ion-exchange membrane.These ion-exchange membranees are made up of the organic polymer with ionic side chain.Cationic exchange membrane contains sulfonate radical or carboxyl in polymeric matrix, and anion-exchange membrane is with uncle or the quaternary amine base substituting group as polymeric base material.Cationic exchange membrane and anion-exchange membrane can be homogeneous, also can be out-phase, and body material can be the multipolymer of vinylbenzene and divinylbenzene, and perhaps other contains the matrix of inclined to one side fluorine or perfluor.
Electroosmose process can remove the sulfuric acid in the reaction solution or sulfuric acid and haloid acid clean fully theoretically and reclaim, but its maximum shortcoming is the energy consumption height, and along with constantly the carrying out of electrodialysis process, electrodialytic current efficiency constantly descends.So, though the iso-electric point of the direct electrodialysis depickling of reaction solution to homocystine can be separated out after-filtration with homocystine from solution, clean and obtain the homocystine finished product, say also improper from the economy angle.
In order to make electrodialytic current efficiency be unlikely to low, cut down the consumption of energy, can the sulfuric acid in the reaction solution or sulfuric acid and haloid acid be removed to a certain suitable point with electrodialytic method after, be neutralized to the iso-electric point of homocystine again with alkali.In using alkali, also can use the attached adsorption bleaching of gac earlier, to guarantee the quality and the color and luster of homocystine with preceding.
In sum, the diffusive dialysis method energy consumption is low, but the rate of recovery of acid is low, reclaim very not thorough, and the whole recovered acid of electroosmose process, but energy consumption height.If both are combined, then two kinds of methods can be had complementary advantages, and are the both economical and feasible a kind of embodiments of the present invention.
Reaction solution after the common heat of the nitration mixture of methionine(Met) and sulfuric acid or sulfuric acid and haloid acid continues to reclaim remaining sulfuric acid or sulfuric acid and haloid acid with electrodialytic method earlier with behind diffusive dialysis method recovery part sulfuric acid or sulfuric acid and the haloid acid again.Can certainly be earlier after diffusion dialysis, reclaim most sulfuric acid and sulfuric acid and haloid acid again after, with the neutralize iso-electric point of homocystine of alkali,, enhance productivity to cut down the consumption of energy.Certainly before electrodialysis or in the alkali and before, can decolour with charcoal absorption, to guarantee the quality and the color and luster of homocystine product.
The present invention has not only eliminated a large amount of pollutents, has also reclaimed useful material, has reduced preparation cost.
Embodiment
The sulphuric acid soln of 40g DL-methionine and 120ml 9mol/L was total to heat after 6 hours under 125～135 ℃ of temperature, be cooled to room temperature, add the dilution of 100ml water to reduce viscosity, the reaction solution that to obtain about 200ml sulfuric acid concentration be 4.5mol/L, this reaction solution enters the former liquid chamber of diffusion dialysis device as shown in Figure 1, the 300ml pure water enters the recovery chamber of diffusion dialysis device, after 24 hours diffusion dialysis, reclaim the chamber and obtain the sulfuric acid that the 250ml sulfuric acid concentration is 1.08mol/L, the sulfuric acid rate of recovery is about 30%.The reaction solution that former liquid chamber obtains is 250ml, and sulfuric acid concentration is about 2.5mol/L.The solution that former liquid chamber is obtained is after the charcoal absorption decolouring, and the sodium hydroxide solution with 30% is neutralized to pH value and is about about 7, consumes 30% sodium hydroxide solution 125ml altogether, filtration, clear water washs, dry homocystine 16.5g, yield is 46%.
The sulphuric acid soln of 40g DL-methionine and 120ml 14mol/L was total to heat after 3 hours under 105～115 ℃ of temperature, be cooled to room temperature, add the dilution of 100ml water to reduce viscosity, the reaction solution that to obtain about 200ml sulfuric acid concentration be 7.5mol/L, this reaction solution enters in the light chamber of electrodialysis unit as shown in Figure 2, and the sulphuric acid soln that 250ml concentration is about 0.3mol/L enters dense chamber, and utmost point chamber liquid is the sulphuric acid soln of 1mol/L, logical direct current is with 2A/dm
2Current density electrodialysis 48 hours, be recovered to the sulfuric acid that 340ml concentration is 3.56mol/L in dense chamber, the sulfuric acid rate of recovery is about 75%, mean current efficient is 52.4%.Solution in the light chamber is after charcoal absorption decolouring, and the pH about 7 that neutralizes of the sodium hydroxide solution with 30% consumes 30% sodium hydroxide solution 75ml altogether.Filter, the clear water washing, oven dry gets homocystine 11.05g, and yield is 30.8%.
The sulphuric acid soln of 40g DL-methionine and 120ml 6mol/L was total to heat after 18 hours under 135～145 ℃ of temperature, be cooled to room temperature, add the dilution of 100ml water to reduce viscosity, the reaction solution that to obtain about 200ml sulfuric acid concentration be 2.7mol/L, this reaction solution enters in the light chamber of electrodialysis unit as shown in Figure 3, and the sulphuric acid soln that 250ml concentration is about 0.3mol/L enters dense chamber, anolyte is the sulphuric acid soln of 1mol/L, catholyte is the sodium hydroxide solution of 1mol/L, and logical direct current is with 2A/dm
2Current density electrodialysis 65 hours, the pH value of solution to light chamber is about about 7.Be recovered to the sulfuric acid that 320ml concentration is 1.82mol/L in dense chamber, the sulfuric acid rate of recovery is about 92%, and mean current efficient is 34.7%.A large amount of homocystine solids have been separated out in the solution in the light chamber.Filter, the clear water washing, oven dry gets homocystine 16g, and yield is 44.6%.
The sulphuric acid soln of 40g DL-methionine and 120ml 9mol/L was total to heat after 6 hours under 125～135 ℃ of temperature, be cooled to room temperature, add the dilution of 100ml water to reduce viscosity, the reaction solution that to obtain about 200ml sulfuric acid concentration be 4.5mol/L, this reaction solution enters in the light chamber of electrodialysis unit shown in Figure 4, and the sulphuric acid soln that 250ml concentration is about 0.3mol/L enters dense chamber, and utmost point chamber liquid is the sulphuric acid soln of 1mol/L, logical direct current is with 2A/dm
2Current density electrodialysis 48 hours, be recovered to the sulfuric acid that 310ml concentration is 2.41mol/L in dense chamber, the sulfuric acid rate of recovery is about 74%, mean current efficient is 56.8%.Solution in the light chamber is after charcoal absorption decolouring, and the pH about 7 that neutralizes of the sodium hydroxide solution with 30% consumes 30% sodium hydroxide solution 47ml altogether.Filter, the clear water washing, oven dry gets homocystine 16.1g, and yield is 44.9%.
The sulphuric acid soln of 40g DL-methionine and 120ml 9mol/L was total to heat after 6 hours under 125～135 ℃ of temperature, be cooled to room temperature, add the dilution of 100ml water to reduce viscosity, the reaction solution that to obtain about 200ml sulfuric acid concentration be 4.5mol/L, this reaction solution enters the former liquid chamber of diffusion dialysis device as shown in Figure 1, the 300ml pure water enters the recovery chamber of diffusion dialysis device, after 24 hours diffusion dialysis, reclaim the chamber and obtain the sulfuric acid that the 250ml sulfuric acid concentration is 1.08mol/L, the sulfuric acid rate of recovery is about 30%.The solution that stoste is indoor enters the light chamber of electrodialysis unit as shown in Figure 3, and the sulphuric acid soln that 250ml concentration is about 0.3mol/L enters dense chamber, and anolyte is the sulphuric acid soln of 1mol/L, and catholyte is the sodium hydroxide solution of 1mol/L.Logical direct current is with 2A/dm
2Current density electrodialysis 36 hours, obtain the sulphuric acid soln that 290ml concentration is about 1.81mol/L in dense chamber, diffusion dialysis and electrodialytic sulfuric acid total yield are 80%, electrodialytic current efficiency is about 48.3%.Reaction solution in the light chamber is after charcoal absorption decolouring, and the pH value that neutralizes of the sodium hydroxide solution with 30% is about 7, consumes liquid caustic soda 36ml altogether.Filter, the clear water washing, dry homocystine 16.2g, yield is 45.2%.
The sulphuric acid soln of 40g DL-methionine and 120ml 9mol/L was total to heat after 6 hours under 125～135 ℃ of temperature, be cooled to room temperature, add the dilution of 100ml water to reduce viscosity, the reaction solution that to obtain about 200ml sulfuric acid concentration be 4.5mol/L, this reaction solution enters the former liquid chamber of diffusion dialysis device as shown in Figure 1, the 300ml pure water enters the recovery chamber of diffusion dialysis device, after 24 hours diffusion dialysis, reclaim the chamber and obtain the sulfuric acid that the 250ml sulfuric acid concentration is 1.08mol/L, the sulfuric acid rate of recovery is about 30%.The solution that stoste is indoor enters the light chamber of electrodialysis unit as shown in Figure 3, and the sulphuric acid soln that 250ml concentration is about 0.3mol/L enters dense chamber, and anolyte is the sulphuric acid soln of 1mol/L, and catholyte is the sodium hydroxide solution of 1mol/L.Logical direct current is with 2A/dm
2Current density electrodialysis 52 hours, obtain the sulphuric acid soln that 290ml concentration is about 2.28mol/L in dense chamber, diffusion dialysis and electrodialytic sulfuric acid total yield are 95%, electrodialytic current efficiency is about 32.8%.Filter and collect the throw out that light chamber generated, water cleans, and drying obtains the 16g homocystine.Yield is 44.6%.
40g methionine(Met) and 138.8g 47%HBr solution, 53.7g the vitriol oil of 18mol/L back flow reaction after 6 hours under 120 ℃ of temperature, be cooled to room temperature, reclaim wherein about 30% sulfuric acid and Hydrogen bromide with diffusion dialysis earlier, reclaim wherein about 50% sulfuric acid and Hydrogen bromide with electrodialysis unit shown in Figure 3 again, the total yield of acid is about 80%; After after the charcoal absorption decolouring, be neutralized to pH with 30% sodium hydroxide solution again is about 7 to reaction solution, consumes 30% sodium hydroxide solution 15ml altogether through recovered acid; Filter and collect the throw out that is generated, water cleans, and drying obtains the 32.4g homocystine.Yield is 90%.
Embodiment 8
Embodiment 9
Embodiment 10
Embodiment 10
Embodiment 11
Embodiment 12
Reference examples
The sulphuric acid soln of 40g DL-methionine and 120ml 9mol/L under 125～135 ℃ of temperature altogether heat be cooled to room temperature after 6 hours, directly be neutralized to pH value about 7 with 30% sodium hydroxide solution, consume 30% sodium hydroxide solution 180ml altogether.Filter, obtain homocystine 16.1g, yield 44.9% after making with extra care.
Claims (9)
1, the preparation method of homocystine, it is characterized in that: the haloid acid of the sulfuric acid of methionine(Met) and 5～18mol/L and 0～50% (weight) is total to heat 0.5～20 hour down at 100～150 ℃, the mol ratio of methionine(Met)/sulfuric acid/haloid acid is 1/2～6.5/0～4, after the reaction solution cooling, sulfuric acid in dialysis recovery reaction solution is to the iso-electric point of homocystine, precipitate after filtration, the washing, the oven dry, homocystine.
2, the preparation method of homocystine as claimed in claim 1 is characterized in that described dialysis is electrodialysis or diffusion dialysis and electrodialysis.
3, the preparation method of homocystine as claimed in claim 1 is characterized in that described reaction solution adds the iso-electric point that alkali is neutralized to homocystine after dialysis, precipitate after filtration, the washing, the oven dry, homocystine.
4, the preparation method of homocystine as claimed in claim 3 is characterized in that described dialysis is diffusion dialysis, electrodialysis or diffusion dialysis and electrodialysis.
5,, it is characterized in that described reaction solution is through the dialysis rear decoloring as the preparation method of claim 1 or 3 described homocystine.
6, the preparation method of homocystine as claimed in claim 2 is characterized in that its device of described diffusion dialysis reclaims the chamber by at least one diffusion dialysis film, at least one former liquid chamber and at least one and forms, and the diffusion dialysis film is clipped between former liquid chamber and the recovery chamber; Described electrodialysis unit is made up of the cathode compartment of at least one cationic exchange membrane or at least one Bipolar Membrane, at least one anion-exchange membrane, at least one dense chamber, at least one light chamber, at least one built-in anodic anolyte compartment and at least one built-in negative electrode.
7, the preparation method of homocystine as claimed in claim 6 is characterized in that described cationic exchange membrane is homogeneous phase cation exchange film or out-phase cationic exchange membrane; Described anion-exchange membrane is homogeneous-phase anion exchange film or out-phase anion-exchange membrane.
8, the preparation method of homocystine as claimed in claim 3 is characterized in that described alkali is the combination of a kind of in sodium hydroxide, potassium hydroxide, hydrated barta, ammoniacal liquor, liquefied ammonia, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, volatile salt, bicarbonate of ammonia, the barium carbonate or at least two kinds.
9, the preparation method of homocystine as claimed in claim 1, it is characterized in that described methionine(Met) is a kind of in D-methionine(Met), L-methionine(Met) or the DL-methionine, correspondingly, described homocystine is a kind of in D-homocystine, L-homocystine or the DL-homocystine.
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| CN2007100700920A CN101348452B (en) | 2007-07-20 | 2007-07-20 | Preparation of homocystine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103264995A (en) * | 2013-05-30 | 2013-08-28 | 山东天维膜技术有限公司 | Sulfuric acid recovery technique in process of producing cystine by adopting sulfuric acid method |
| CN111004209A (en) * | 2019-12-24 | 2020-04-14 | 浙江工业大学 | Continuous production method of DL-homocysteine thiolactone hydrochloride |
| CN111635344A (en) * | 2020-06-08 | 2020-09-08 | 九江中星医药化工有限公司 | Post-treatment method of homocystine reaction solution |
| CN112239421A (en) * | 2020-11-06 | 2021-01-19 | 江苏宝众宝达药业有限公司 | Method for synthesizing L-homocystine |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3620221B2 (en) * | 1996-11-25 | 2005-02-16 | 三菱化学株式会社 | Method for producing homocystin |
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2007
- 2007-07-20 CN CN2007100700920A patent/CN101348452B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103264995A (en) * | 2013-05-30 | 2013-08-28 | 山东天维膜技术有限公司 | Sulfuric acid recovery technique in process of producing cystine by adopting sulfuric acid method |
| CN111004209A (en) * | 2019-12-24 | 2020-04-14 | 浙江工业大学 | Continuous production method of DL-homocysteine thiolactone hydrochloride |
| CN111635344A (en) * | 2020-06-08 | 2020-09-08 | 九江中星医药化工有限公司 | Post-treatment method of homocystine reaction solution |
| CN112239421A (en) * | 2020-11-06 | 2021-01-19 | 江苏宝众宝达药业有限公司 | Method for synthesizing L-homocystine |
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| CN101348452B (en) | 2011-12-07 |
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