WO2003050071A1 - Process for the preparation of methionine - Google Patents

Process for the preparation of methionine Download PDF

Info

Publication number
WO2003050071A1
WO2003050071A1 PCT/EP2002/008742 EP0208742W WO03050071A1 WO 2003050071 A1 WO2003050071 A1 WO 2003050071A1 EP 0208742 W EP0208742 W EP 0208742W WO 03050071 A1 WO03050071 A1 WO 03050071A1
Authority
WO
WIPO (PCT)
Prior art keywords
methionine
process according
employed
compounds
sodium
Prior art date
Application number
PCT/EP2002/008742
Other languages
French (fr)
Other versions
WO2003050071A8 (en
Inventor
Christoph Weckbecker
Horst Krull
Jürgen Bilz
Klaus Huthmacher
Hans Joachim Hasselbach
Original Assignee
Degussa Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Degussa Ag filed Critical Degussa Ag
Priority to US10/497,949 priority Critical patent/US7179938B2/en
Priority to AU2002321293A priority patent/AU2002321293A1/en
Priority to DE60232268T priority patent/DE60232268D1/en
Priority to MXPA04005443A priority patent/MXPA04005443A/en
Priority to KR1020047008821A priority patent/KR100874836B1/en
Priority to AT02754978T priority patent/ATE430725T1/en
Priority to CA002469526A priority patent/CA2469526A1/en
Priority to EP02754978A priority patent/EP1451139B1/en
Priority to JP2003551098A priority patent/JP4213038B2/en
Priority to BR0214781-5A priority patent/BR0214781A/en
Priority to IL16238202A priority patent/IL162382A0/en
Publication of WO2003050071A1 publication Critical patent/WO2003050071A1/en
Publication of WO2003050071A8 publication Critical patent/WO2003050071A8/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/26—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/26—Separation; Purification; Stabilisation; Use of additives
    • C07C319/28—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, 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
    • C07C323/51—Thiols, 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
    • C07C323/57—Thiols, 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 further substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C323/58—Thiols, 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 further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton

Definitions

  • the invention relates to a process for the preparation of methionine of high bulk density, in which a mixture which comprises a compound which has a foaming action and a compound which influences crystallization is added to the hydrolysis solution, and to the mixture itself.
  • JP 09000241 thus describes that the addition of various additives from the family of nitrogen-containing polyoxyalkylenes in the fermentative production of amino acids leads to a reduction in foaming.
  • JP 09000241 relates to the preparation of defoa er mixtures which are composed of fats or oils and the reaction products of fatty acids or derivatives thereof and polyalcohols with alkylene oxides . These mixtures are suitable for use in fermentations . It is known that the yield of lysine and tryptophan production can be increased if silicone are used as foam-destroying additives, instead of sunflower oil. The influence of various silicone oils is investigated by comparison in Khim.-Farm. Zh (1972), 6(5), 27-30.
  • Methionine is in general precipitated out of these solutions in the form of very flat leaflets, separating off of which proceeds only very slowly and therefore uneconomically.
  • the present invention is based on the object of minimizing the formation of foam in the methionine process and at the same time positively influencing the crystal habit of the methionine which has precipitated out after the recrystallization.
  • n an integer from 9 to 19, preferably 15 to 17,
  • n a distribution in the range from 1 to 10, wherein the maximum is preferably 5 to 8, in particular 6 to 7 ,
  • modified celluloses in particular methylcellulose, methylhydroxycellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose and sodium carboxymethylhydroxypropylcellulose in a weight ratio of 1:10 to 10:1, preferably 1:3 to 3:1.
  • the fatty acid contents in compounds according to formula (1) are preferably of natural origin, and are saturated or unsaturated, depending on the meaning of x.
  • the mixture is advantageously employed in the form of an aqueous solution or emulsion with a total additive content of 1 to 5 wt.%, in particular 2 to 4 wt.%, based on the total amount.
  • hydroxycelluloses dissolved in water can lead to highly viscous solutions, it is advantageous to use low molecular weight hydroxycelluloses with a viscosity of ⁇ 300 mPas (as a 2% solution in water) .
  • the viscosity can furthermore also be adjusted via the degree of dilution.
  • an aqueous solution or emulsion of the additives (1) and (2) with a viscosity of between 5 and 5000 mPas, based on a 2% solution of the additives in water, in particular 10 to 500 mPas, is prepared by dissolving or emulsifying the compounds according formula (1) and (2) in the desired amount.
  • One important aspect of the invention is that the defoaming action and the crystallization can be controlled by changing the ratios of amounts of (1) to (2) in the mixture.
  • Foaming depends greatly on the composition of the process solutions and the other process conditions, such as, for example, pressure and temperature.
  • the mixtures according to the invention already display their defoaming and a crystal growth-promoting action when small amounts are added. Amounts of 10 to 500 ppm, based on the methionine, are already active.
  • the invention also provides a process for the preparation of methionine, in particular with a purity of 80 to 100 wt.%, by reaction of the components 3- methylmercaptopropionaldehyde, hydrogen cyanide, ammonia and carbon dioxide or of those components from which the above-mentioned components can be prepared, optionally in the presence of water, to give 5- (2-methylmercaptoethyl) - hydantoin and conversion thereof into methionine, which is characterized in that, before carbon dioxide is passed in, an aqueous mixture which comprises compounds of the general formula
  • n an integer from 9 to 19, preferably 15, 17 or 19
  • n a distribution in the range from 1 to 10, wherein the maximum is preferably 5 to 8 , in particular 6 to 7 ,
  • the methionine which has precipitated out is dissolved and, in particular using the mother liquor, which preferably comprises the additives (1) and (2) mentioned, is crystallized in the presence of crystalline methionine, optionally with the addition of further amounts of the aqueous mixture.
  • the high stirring energy known from the prior art does not have to be introduced during the precipitation or the crystallization.
  • the process claimed can be carried out continuously or discontinuously.
  • the additive (1) has a defoaming action, while at the same time the presence of (2) has no adverse influence on the defoaming.
  • the recrystallization is preferably carried out by a procedure in which, preferably, methionine suspended in the mother liquor is pumped in circulation at a temperature of 30 to 60 2 C, and a methionine solution which has a concentration of 70 to 150 g/1, in particular 90 to 130 g/1, and has been heated up to 60 to 110 S C, in particular 80 to 100 2 C, is admixed to this suspension.
  • the methionine solution mentioned last optionally comprises a content of 5 to 20 vol.% of mother liquor from the preparation process.
  • Methionine precipitates out in the desired purity by the cooling. Methionine with a purity of 80 to 100 wt.%, in particular 90 to 100 wt.%, which is not to be achieved in one-stage processes, is obtained with this step of recrystallization.
  • the ration of amounts between the suspension pumped in circulation and the solution admixed is in general 1-10:1, in particular 2-6:1, preferably 3-5:1.
  • constituents (1) and (2) can also be added individually. (2) in particular displays its properties in particular during the crystallization.
  • the addition of carbon dioxide is continued at 30 a C until the pH is reduced to 8.0. Foam forms on the reaction mixture at a height of 1 centimeter, while at the same time methionine is precipitated.
  • 60 g methionine are suspended at 40 S C in 300 ml water and 40 g filtrate of the mother liquor from the precipitation with carbon dioxide and the suspension is pumped in circulation.
  • a heat exchanger is connected in series in order to keep the temperature constant.
  • a hot solution at 90 a C of 180 g methionine in 1170 g water and 150 g filtrate of the mother liquor from the precipitation with carbon dioxide is added to this solution with a rate of 1 liter of solution per hour.
  • the SEM photograph with the image number 173029 shows the coarsely crystalline structure of the end product obtained in this way.
  • 0.6 liter of the hot solution is added, 500 ml of the circulating suspension are removed and a further 500 ml of hot solution are added.
  • the suspension is filtered off, the solid is rinsed with 300 ml acetone and dried to constant weight at 60 a C in a vacuum drying cabinet and the bulk density is determined.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Medicinal Preparation (AREA)
  • Fodder In General (AREA)
  • Steroid Compounds (AREA)
  • Degasification And Air Bubble Elimination (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

The invention relates to a process for the preparation of methionine of high bulk density, in which a mixture which comprises a compound which has a foaming action and a compound which influences the crystallization is added to the hydrolysis solution, and to the mixture itself.

Description

Process for the Preparation, of Methionine
The invention relates to a process for the preparation of methionine of high bulk density, in which a mixture which comprises a compound which has a foaming action and a compound which influences crystallization is added to the hydrolysis solution, and to the mixture itself.
It is known that the preparation of amino acids is often associated with difficulties. Handling of solutions or suspensions containing amino acids already leads to severe foaming in laboratory processes, but above all of course in industrial production. This undesirable effect can lead not only to the production proceeding in a very problematic manner and with poor space/time yields, but in individual cases also to failure of an economical production of the amino acid.
JP 09000241 thus describes that the addition of various additives from the family of nitrogen-containing polyoxyalkylenes in the fermentative production of amino acids leads to a reduction in foaming. JP 09000241 relates to the preparation of defoa er mixtures which are composed of fats or oils and the reaction products of fatty acids or derivatives thereof and polyalcohols with alkylene oxides . These mixtures are suitable for use in fermentations . It is known that the yield of lysine and tryptophan production can be increased if silicone are used as foam-destroying additives, instead of sunflower oil. The influence of various silicone oils is investigated by comparison in Khim.-Farm. Zh (1972), 6(5), 27-30.
In the carbonate process known from EP 0 780 370, methionine is obtained on acidification of a solution of potassium methioninate with carbon dioxide in accordance with the equation
2 H3C-S-CH2-CH2-CH( H2)-COOK + 2 C02 + 2H20 2 H3C-S-CH -CH2-CH (NH2 ) -COOH + 2 KHC03
Methionine is in general precipitated out of these solutions in the form of very flat leaflets, separating off of which proceeds only very slowly and therefore uneconomically.
There are therefore attempts to influence the crystallization properties of the methionine by addition of particular auxiliary substances.
It is demonstrated in JP-11-158140 that the use of various auxiliary substances, such as hydroxymethylpropylcellulose, sorbitan monolaurate or polyvinyl alcohols, influences the crystal habit, and the bulk density of the methionine obtained in this way increases.
These compounds are added in an amount of at least 500 ppm during the crystallization, which is carried out continuously and proceeds in two stages under specific stirring conditions. A round-particled methionine is obtained.
No additive or mixture of additives with the aid of which at the same time the foam which forms in the various stages of methionine preparation can be suppressed and the crystal habit of the methionine which has precipitated out, in particular in the carbonate process, can be improved is known from the prior art.
The present invention is based on the object of minimizing the formation of foam in the methionine process and at the same time positively influencing the crystal habit of the methionine which has precipitated out after the recrystallization.
The invention provides an aqueous mixture which comprises compounds of the general formula (additive (1) ) CnH2n+xC=0-0- [CH2-CH2-0 ] m-H ( 1 ) ,
in which the symbols denote:
n: an integer from 9 to 19, preferably 15 to 17,
m: a distribution in the range from 1 to 10, wherein the maximum is preferably 5 to 8, in particular 6 to 7 ,
x: 1, -1, -3, -5, wherein 2n+x is not less than 1,
and additives (2) from the group consisting of modified celluloses, in particular methylcellulose, methylhydroxycellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose and sodium carboxymethylhydroxypropylcellulose in a weight ratio of 1:10 to 10:1, preferably 1:3 to 3:1.
The fatty acid contents in compounds according to formula (1) are preferably of natural origin, and are saturated or unsaturated, depending on the meaning of x.
The mixture is advantageously employed in the form of an aqueous solution or emulsion with a total additive content of 1 to 5 wt.%, in particular 2 to 4 wt.%, based on the total amount.
In order to produce a stable emulsion, it is merely necessary to treat the mixture with a conventional blade stirrer. Since hydroxycelluloses dissolved in water can lead to highly viscous solutions, it is advantageous to use low molecular weight hydroxycelluloses with a viscosity of < 300 mPas (as a 2% solution in water) . The viscosity can furthermore also be adjusted via the degree of dilution. Preferably, an aqueous solution or emulsion of the additives (1) and (2) with a viscosity of between 5 and 5000 mPas, based on a 2% solution of the additives in water, in particular 10 to 500 mPas, is prepared by dissolving or emulsifying the compounds according formula (1) and (2) in the desired amount.
It has been found that the mixture described is suitable for reducing the foaming in process solutions obtained during the preparation of methionine and at the same time effecting the formation of larger crystals during the recrystallization.
One important aspect of the invention is that the defoaming action and the crystallization can be controlled by changing the ratios of amounts of (1) to (2) in the mixture.
Foaming depends greatly on the composition of the process solutions and the other process conditions, such as, for example, pressure and temperature.
The mixtures according to the invention already display their defoaming and a crystal growth-promoting action when small amounts are added. Amounts of 10 to 500 ppm, based on the methionine, are already active.
At the same time, it is to be found that the compounds (1) and (2) employed according to the invention have no adverse influence on the action of the other particular compounds.
On the contrary, it is the case that the interaction of (1) and (2) can lead to an improvement in the crystal structure (see, for example, image no. 1703045) .
The invention also provides a process for the preparation of methionine, in particular with a purity of 80 to 100 wt.%, by reaction of the components 3- methylmercaptopropionaldehyde, hydrogen cyanide, ammonia and carbon dioxide or of those components from which the above-mentioned components can be prepared, optionally in the presence of water, to give 5- (2-methylmercaptoethyl) - hydantoin and conversion thereof into methionine, which is characterized in that, before carbon dioxide is passed in, an aqueous mixture which comprises compounds of the general formula
CnH2n+xC=0-0-[CH2-CH2-0]m-H (1),
in which the symbols denote:
n: an integer from 9 to 19, preferably 15, 17 or 19,
m: a distribution in the range from 1 to 10, wherein the maximum is preferably 5 to 8 , in particular 6 to 7 ,
x: 1, -1, -3, -5, wherein 2n + x is not less than 1,
and additives (2) from the group consisting of modified celluloses, in particular methylcellulose, methylhydroxycellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose and sodium carboxymethylhydroxypropylcellulose, is added to the hydrolysis solution obtained from 5- (2- methylmercaptoethyl) -hydantoin in a weight ratio of 1:10 to 10:1, preferably 1:3 to 3:1, in a total amount of 5 to
5000 ppm, preferably 5 to 500 ppm, based on the methionine (wt.%) contained in the solution, and the methionine which has precipitated out is dissolved and, in particular using the mother liquor, which preferably comprises the additives (1) and (2) mentioned, is crystallized in the presence of crystalline methionine, optionally with the addition of further amounts of the aqueous mixture. According to the invention, the high stirring energy known from the prior art does not have to be introduced during the precipitation or the crystallization. The same applies to the C02 pressures known from the prior art . Only a uniform distribution of the carbon dioxide, which has been introduced, during the precipitation of the methionine into the hydrolysis solution remains essential.
The process claimed can be carried out continuously or discontinuously.
During the precipitation of the methionine, with the addition of carbon dioxide, from the solution obtained as the hydrolysis product, the additive (1) has a defoaming action, while at the same time the presence of (2) has no adverse influence on the defoaming.
The recrystallization is preferably carried out by a procedure in which, preferably, methionine suspended in the mother liquor is pumped in circulation at a temperature of 30 to 602C, and a methionine solution which has a concentration of 70 to 150 g/1, in particular 90 to 130 g/1, and has been heated up to 60 to 110SC, in particular 80 to 1002C, is admixed to this suspension. The methionine solution mentioned last optionally comprises a content of 5 to 20 vol.% of mother liquor from the preparation process.
Methionine precipitates out in the desired purity by the cooling. Methionine with a purity of 80 to 100 wt.%, in particular 90 to 100 wt.%, which is not to be achieved in one-stage processes, is obtained with this step of recrystallization.
The ration of amounts between the suspension pumped in circulation and the solution admixed is in general 1-10:1, in particular 2-6:1, preferably 3-5:1.
The mixture claimed simplifies the process in the respect that during the precipitation of the methionine from the hydrolysis solution and the recrystallization of the methionine which has precipitated out, this same mixture which comprises compound (1) and (2) can be employed.
However, the constituents (1) and (2) can also be added individually. (2) in particular displays its properties in particular during the crystallization.
The invention is illustrated by the following examples.
Example 1
Precipitation with carbon dioxide
A 4% emulsion of hydroxyethylcellulose, which has a viscosity of 200 mPas (V=200) as a 2% solution, in water, and stearic acid ester 1 (n=17; m=7) in a weight ratio of 1:1 are introduced, while stirring, into 1 L of a solution of potassium methioninate and potassium bicarbonate with a methionine concentration of 70 g/1 and a potassium concentration of 150 g/1, such that an emulsion which comprises 50 ppm of additives is formed. Carbon dioxide is fed in at pH = 11 under a pressure of 2 bar in a 2 L autoclave at a stirrer speed of 500 rpm. The addition of carbon dioxide is continued at 30aC until the pH is reduced to 8.0. Foam forms on the reaction mixture at a height of 1 centimeter, while at the same time methionine is precipitated.
Example 2
Recrystallization
60 g methionine are suspended at 40SC in 300 ml water and 40 g filtrate of the mother liquor from the precipitation with carbon dioxide and the suspension is pumped in circulation. A 4% emulsion of hydroxyethylcellulose, which has a viscosity of 200 mPas (V=200) as a 2% solution, in water, and stearic acid ester 1 (n=18; m=7) in a weight ratio of 1:1 are introduced, while stirring, into this suspension such that an emulsion which comprises 50 ppm of additives is formed. A heat exchanger is connected in series in order to keep the temperature constant. A hot solution at 90aC of 180 g methionine in 1170 g water and 150 g filtrate of the mother liquor from the precipitation with carbon dioxide is added to this solution with a rate of 1 liter of solution per hour. The recrystallization of the methionine, which has precipitated out, in the presence of 50 ppm of the additives (total amount) , based on the methionine, leads to crystals with a bulk density of 586 g/1.
The SEM photograph with the image number 173029 shows the coarsely crystalline structure of the end product obtained in this way.
Methionine precipitates out due to the cooling. 0.6 liter of the hot solution is added, 500 ml of the circulating suspension are removed and a further 500 ml of hot solution are added. The suspension is filtered off, the solid is rinsed with 300 ml acetone and dried to constant weight at 60aC in a vacuum drying cabinet and the bulk density is determined.
A 4% emulsion of hydroxyethylcellulose, which has a viscosity of 200 mPas (V=200) as a 2% solution, in water, and stearic acid ester 1 (n=18; m=7) in a weight ratio of 1:1 are introduced, while stirring, into this solution which has been added dropwise, such that an emulsion which comprises 50 ppm of additives is formed.
Example 3
Further Experiments
Further experiments which were carried out in accordance with Examples 1 and 2 are summarized in Table 1. Deviating experimental conditions are to be found underneath the table.
Figure imgf000011_0001
m SEM photographs are attached for documentation of the advantageous results which are achieved with this invention.
It is found that without the addition of additives (1) and (2) , a fine-particled methionine is obtained after the recrystallization (image no. : 170867) .
The use of compound (1) , which in general has a defoaming action, also leads to no substantial coarsening of the crystal structure (image no.: 170875).
The optimum results according to the invention are found only when additives (2) are employed together with (1) (image no. : 173029) .
A comparison with image no. 173045 shows that the sole use of (2) already leads to results which exceed the prior art, but the addition of (1) has the effect of a further improvement .
Table 2
Figure imgf000013_0001

Claims

What is claimed is:
1. Aqueous mixtures which comprise compounds of the general formula
Figure imgf000014_0001
in which the symbols denote:
n: an integer from 9 to 19, preferably 15, 17 or 19,
m: a distribution in the range from 1 to 10, wherein the maximum is preferably 5 to 8, in particular 6 to 7,
x: 1, -1, -3, -5, wherein 2n+x is not less than
1, and additives (2) from the group consisting of modified celluloses, in particular methylcellulose, methylhydroxycellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose and sodium carboxymethylhydroxypropylcellulose in a weight ratio of 1:10 to 10:1, preferably 1:3 to 3:1.
2. Water-containing mixtures according to claim 1, with a total additive content of 1 to 5 wt.%, based on the total amount .
3. Process for the preparation of methionine by reaction of the components 3-methylmercaptopropionaldehyde, hydrogen cyanide, ammonia and carbon dioxide or of those components from which the above-mentioned components can be prepared, optionally in the presence of water, to give 5- (2-methylmercaptoethyl) -hydantoin and conversion thereof into methionine, wherein, before carbon dioxide is passed in, an aqueous mixture which comprises compounds of the general formula
Figure imgf000015_0001
in which the symbols denote:
n: a number from 9 to 19,
m: a distribution in the range from 1 to 10, wherein the maximum is preferably 5 to 8, in particular 6 to 7 ,
x: 1, -1, -3, -5, wherein 2n+x is not less than 1,
and additives (2) from the group consisting of modified celluloses, in particular methylcellulose, methylhydroxycellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose and sodium carboxymethylhydroxypropylcellulose, is added to the hydrolysis solution obtained from 5- (2- methylmercaptoethyl) -hydantoin in a weight ratio of 1:10 to 10:1, preferably 1:3 to 3:1, in a total amount of 5 to 5000 ppm, preferably 10 to 500 ppm, based on the methionine contained in the solution, and the methionine which has precipitated out is dissolved and, in particular using crystalline methionine suspended in the mother liquor, is recrystallized.
4. Process according to claim 3, wherein compounds (1) in which n corresponds to 16, 18 or 20 are employed.
5. Process according to claim 3, wherein compounds (1) in which the maximum of m is 5 to 8 are employed.
6. Process according to claim 5, wherein compounds (1) in which the maximum of m is 6 or 7 are employed.
7. Process according to claim 3, wherein a compound (1) in which n=18 and m=7 is employed.
8. Process according to claim 3, wherein hydroxyethylcellulose is employed as additive (2) .
9. Process according to claim 3 , wherein hydroxyethylcellulose which has a viscosity of 200mPas as a 1% solution is employed as additive (2) .
10. Process according to claim 3, wherein the aqueous mixture comprising (1) and (2) is employed in the form of a pumpable emulsion in water.
11. Process according to claim 3 , wherein the aqueous mixture comprising (1) and (2) is employed in the form of a 2-5% emulsion in water.
12. Process according to claim 3 , wherein the aqueous mixture comprising (1) and (2) is employed in a concentration of 10 to 450 ppm of total additive concentration, based on the methionine concentration.
13. Process according to claim 3 , wherein during the recrystallization, the aqueous mixture is added again in the desired amount.
PCT/EP2002/008742 2001-12-08 2002-08-06 Process for the preparation of methionine WO2003050071A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US10/497,949 US7179938B2 (en) 2001-12-08 2002-08-06 Process for the preparation of methionine
AU2002321293A AU2002321293A1 (en) 2001-12-08 2002-08-06 Process for the preparation of methionine
DE60232268T DE60232268D1 (en) 2001-12-08 2002-08-06 PROCESS FOR THE PREPARATION OF METHIONIN
MXPA04005443A MXPA04005443A (en) 2001-12-08 2002-08-06 Process for the preparation of methionine.
KR1020047008821A KR100874836B1 (en) 2001-12-08 2002-08-06 Method for preparing methionine
AT02754978T ATE430725T1 (en) 2001-12-08 2002-08-06 METHION FOR PRODUCING METHIONINE
CA002469526A CA2469526A1 (en) 2001-12-08 2002-08-06 Process for the preparation of methionine
EP02754978A EP1451139B1 (en) 2001-12-08 2002-08-06 Process for the preparation of methionine
JP2003551098A JP4213038B2 (en) 2001-12-08 2002-08-06 Method for producing methionine
BR0214781-5A BR0214781A (en) 2001-12-08 2002-08-06 Process for the preparation of methionine
IL16238202A IL162382A0 (en) 2001-12-08 2002-08-06 Process for the preparation of methionine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10160358.4 2001-12-08
DE10160358A DE10160358A1 (en) 2001-12-08 2001-12-08 Process for the production of methionine

Publications (2)

Publication Number Publication Date
WO2003050071A1 true WO2003050071A1 (en) 2003-06-19
WO2003050071A8 WO2003050071A8 (en) 2004-04-22

Family

ID=7708513

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/008742 WO2003050071A1 (en) 2001-12-08 2002-08-06 Process for the preparation of methionine

Country Status (16)

Country Link
US (1) US7179938B2 (en)
EP (1) EP1451139B1 (en)
JP (1) JP4213038B2 (en)
KR (1) KR100874836B1 (en)
CN (1) CN1332926C (en)
AT (1) ATE430725T1 (en)
AU (1) AU2002321293A1 (en)
BR (1) BR0214781A (en)
CA (1) CA2469526A1 (en)
DE (2) DE10160358A1 (en)
ES (1) ES2325574T3 (en)
IL (1) IL162382A0 (en)
MX (1) MXPA04005443A (en)
RU (1) RU2294922C2 (en)
WO (1) WO2003050071A1 (en)
ZA (1) ZA200404479B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2641898A1 (en) * 2012-03-20 2013-09-25 Evonik Industries AG Method for manufacturing methionine
EP2848607A1 (en) 2013-09-17 2015-03-18 Evonik Industries AG Method for extracting methionine
CN104744326A (en) * 2015-02-12 2015-07-01 山东新和成氨基酸有限公司 Method for continuously preparing high-bulk density methionine crystals

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2928910B1 (en) * 2008-03-20 2010-03-12 Arkema France IMPROVED PROCESS FOR THE PRODUCTION OF CYANHYDRIC ACID
FR2938535B1 (en) * 2008-11-20 2012-08-17 Arkema France PROCESS FOR PRODUCING METHYLMERCAPTOPROPIONALDEHYDE AND METHIONINE FROM RENEWABLE MATERIALS
JP5930329B2 (en) 2011-02-23 2016-06-08 エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ Preparation of 2-hydroxy-4- (methylthio) butyronitrile from 3- (methylthio) propanal and hydrogen cyanide
DE102011081828A1 (en) 2011-08-30 2013-02-28 Evonik Degussa Gmbh Process for the reaction of methylmercaptopropionaldehyde from crude acrolein and crude methylmercaptan
MX2014002250A (en) 2011-08-30 2014-04-25 Evonik Degussa Gmbh Method for producing a methionine salt.
EP3625211B1 (en) * 2017-05-15 2021-03-17 Evonik Operations GmbH Process for preparing methionine
US20220001304A1 (en) * 2018-09-28 2022-01-06 Doe Global Technologies Llc Hydroxyethyl cellulose derivative foam control agents and methods of processing foodstuffs
EP3986861B1 (en) 2019-06-18 2023-08-02 Evonik Operations GmbH Process for the preparation of d,l-methionine
CN111100051B (en) 2019-12-31 2022-01-28 山东新和成氨基酸有限公司 Additive used in methionine preparation process and methionine preparation method
CN114058094B (en) * 2020-07-31 2023-04-11 中国石油化工股份有限公司 Foaming material composition, foaming material and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1080220A (en) * 1963-12-20 1967-08-23 Exxon Standard Sa Coating composition
US3917683A (en) * 1970-05-08 1975-11-04 Degussa Process for the preparation of DL-methionine
JPH01288267A (en) * 1988-05-16 1989-11-20 Tokuyama Soda Co Ltd Filth treating agent
JPH03266979A (en) * 1990-03-15 1991-11-27 Teijin Ltd Culture of cell
JPH04244056A (en) * 1991-01-31 1992-09-01 Sumitomo Chem Co Ltd Production of methionine
US5681692A (en) * 1996-02-02 1997-10-28 Eastman Kodak Company Nonagglomerating antifoamants
US5990349A (en) * 1995-12-18 1999-11-23 Degussa Aktiengesellschaft Process for the preparation of D,L-methionine or the salt thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR910004482B1 (en) * 1989-02-15 1991-06-29 선종건 Oral pharmaceutical compositions
JP4482973B2 (en) * 1998-09-11 2010-06-16 住友化学株式会社 Method for producing methionine
DE19846825A1 (en) * 1998-10-10 2000-04-13 Degussa Free-flowing moldings containing methionine and process for their production
JP2001072656A (en) * 1999-07-02 2001-03-21 Nippon Soda Co Ltd Control over physical property of methionine crystal powder

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1080220A (en) * 1963-12-20 1967-08-23 Exxon Standard Sa Coating composition
US3917683A (en) * 1970-05-08 1975-11-04 Degussa Process for the preparation of DL-methionine
JPH01288267A (en) * 1988-05-16 1989-11-20 Tokuyama Soda Co Ltd Filth treating agent
JPH03266979A (en) * 1990-03-15 1991-11-27 Teijin Ltd Culture of cell
JPH04244056A (en) * 1991-01-31 1992-09-01 Sumitomo Chem Co Ltd Production of methionine
US5990349A (en) * 1995-12-18 1999-11-23 Degussa Aktiengesellschaft Process for the preparation of D,L-methionine or the salt thereof
US5681692A (en) * 1996-02-02 1997-10-28 Eastman Kodak Company Nonagglomerating antifoamants

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 1990-004588, XP002223484 *
DATABASE WPI Derwent World Patents Index; AN 1992-019318 [03], XP002223482 *
DATABASE WPI Derwent World Patents Index; AN 1992-337741 [41], XP002223483 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2641898A1 (en) * 2012-03-20 2013-09-25 Evonik Industries AG Method for manufacturing methionine
WO2013139562A1 (en) * 2012-03-20 2013-09-26 Evonik Industries Ag Process for the preparation of methionine
US9156782B2 (en) 2012-03-20 2015-10-13 Evonik Industries Ag Process for the preparation of methionine
US9464045B2 (en) 2012-03-20 2016-10-11 Evonik Degussa Gmbh Process for the preparation of methionine
EP3187489A1 (en) * 2012-03-20 2017-07-05 Evonik Degussa GmbH Process for the preparation of methionine
RU2640656C2 (en) * 2012-03-20 2018-01-11 Эвоник Дегусса Гмбх Method of producing methionine
EP2848607A1 (en) 2013-09-17 2015-03-18 Evonik Industries AG Method for extracting methionine
WO2015039935A1 (en) * 2013-09-17 2015-03-26 Evonik Industries Ag Process for obtaining methionine
US9617209B2 (en) 2013-09-17 2017-04-11 Evonik Degussa Gmbh Process for obtaining methionine
CN104744326A (en) * 2015-02-12 2015-07-01 山东新和成氨基酸有限公司 Method for continuously preparing high-bulk density methionine crystals

Also Published As

Publication number Publication date
ES2325574T3 (en) 2009-09-09
CA2469526A1 (en) 2003-06-19
JP4213038B2 (en) 2009-01-21
JP2005511733A (en) 2005-04-28
RU2004121138A (en) 2006-01-10
ZA200404479B (en) 2006-02-22
WO2003050071A8 (en) 2004-04-22
AU2002321293A1 (en) 2003-06-23
US7179938B2 (en) 2007-02-20
IL162382A0 (en) 2005-11-20
BR0214781A (en) 2004-11-09
DE10160358A1 (en) 2003-06-18
KR20040061024A (en) 2004-07-06
DE60232268D1 (en) 2009-06-18
US20050131111A1 (en) 2005-06-16
EP1451139B1 (en) 2009-05-06
CN1332926C (en) 2007-08-22
RU2294922C2 (en) 2007-03-10
EP1451139A1 (en) 2004-09-01
CN1599712A (en) 2005-03-23
ATE430725T1 (en) 2009-05-15
MXPA04005443A (en) 2006-02-24
KR100874836B1 (en) 2008-12-19

Similar Documents

Publication Publication Date Title
US7179938B2 (en) Process for the preparation of methionine
CN104203912B (en) The preparation method of methionine
US4310690A (en) Preparation of the calcium salt of α-hydroxy-gamma-methylmercaptobutyric acid
RU2679309C2 (en) Method of obtaining methionine
JP7388647B2 (en) Additives used in the methionine production process and methionine production method
CN111484426A (en) Method for synthesizing aminoacetonitrile hydrochloride from hydrocyanic acid
WO2022144292A1 (en) Process for the diastereomerically pure preparation of dl/ld-methionylmethionine
US3980653A (en) Process for the production of 3,6-bis-(2-methylmercaptoethyl)-2,5-piperazinedione
JPH0794401B2 (en) Method for separating n-perfluorooctanoic acid
EP3986861B1 (en) Process for the preparation of d,l-methionine
RU2078083C1 (en) Method of preparing alkaline, earth-alkaline or transient metal ascorbates
CN115636772B (en) Preparation method of high-purity creatine monohydrate
CN114702410B (en) Preparation method of guanidinoacetic acid
CA1121351A (en) Preparation process of benzothiazol-sulfenamides
JPS60123473A (en) Manufacture of cyclic urea of imidazolidine structure and use for sizing fiber product particularly
EP2091868B1 (en) Method of preparing potassium hydroxide dihydrate
RU2402241C1 (en) Method for production of magnesium lactate dietary supplement
CN116102475A (en) Methionine composition and preparation method thereof
JPH06228081A (en) Production of sodium salt of nitro-containing aromatic sulfinic acid
JPH05178801A (en) Method for crystallizing l-phenylalanine
CN110963979A (en) Synthesis method of oxathioethers
CN116496245A (en) Process for preparing R-alpha-lipoic acid and related intermediates thereof
FR2706453A1 (en) Process for the preparation of concentrated aqueous solutions of sulphuric salts of dialkylaminoalkyl acrylates and methacrylates
JPH0579673B2 (en)
JPH04368357A (en) Production of secondary amide type n-long chain acylaminocarboxylic acid or aminoalkanesulfonic acid

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i

Free format text: IN PCT GAZETTE 25/2003 ADD "DECLARATION UNDER RULE 4.17: - AS TO APPLICANT?S ENTITLEMENT TO APPLY FOR AND BE GRANTED A PATENT (RULE 4.17(II)). - OF INVENTORSHIP (RULE 4.17(IV)) FOR US ONLY."

WWE Wipo information: entry into national phase

Ref document number: 2002754978

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: PA/a/2004/005443

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2004/04479

Country of ref document: ZA

Ref document number: 162382

Country of ref document: IL

Ref document number: 20028243897

Country of ref document: CN

Ref document number: 2469526

Country of ref document: CA

Ref document number: 10497949

Country of ref document: US

Ref document number: 200404479

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: 2003551098

Country of ref document: JP

Ref document number: 1020047008821

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2004121138

Country of ref document: RU

WWP Wipo information: published in national office

Ref document number: 2002754978

Country of ref document: EP