EP2750776A1 - Verfahren zur umsetzung von methylmercaptopropionaldehyd aus roh-acrolein und roh-methylmercaptan - Google Patents
Verfahren zur umsetzung von methylmercaptopropionaldehyd aus roh-acrolein und roh-methylmercaptanInfo
- Publication number
- EP2750776A1 EP2750776A1 EP12750380.3A EP12750380A EP2750776A1 EP 2750776 A1 EP2750776 A1 EP 2750776A1 EP 12750380 A EP12750380 A EP 12750380A EP 2750776 A1 EP2750776 A1 EP 2750776A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rectification column
- range
- reactive rectification
- column
- reactive
- Prior art date
- Legal status (The legal status 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 status listed.)
- Ceased
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
-
- 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
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- the invention relates to a reactive rectification column for the reaction of methylmercaptopropionaldehyde prepared from crude acrolein and crude methylmercaptan to give 2-hydroxy-4-methylmercaptobutyric acid and / or methionine and their use in a process for preparing 2-hydroxy-4-methylmercaptobutyric acid and / or methionine ,
- acrolein For the synthesis of acrolein, several routes are conceivable in principle. In the prior art, the condensation of formaldehyde and acetaldehyde or the dehydration of glycerol is used. Another common process, which dominates on an industrial scale, is the partial oxidation of propene. For the production of acrolein, the reaction is carried out in a conventional process, for example, in a shell-and-tube reactor filled with a catalyst. In the heterogeneously catalyzed
- Oxidation of propene occurs in addition to the target product acrolein different
- Non-condensable gases such as N 2 , excess propene and optionally propane (depending on the quality of propene), CO and C0 2 leave the absorber overhead and can be partially used as an inerting medium in the reaction section.
- the remaining portions of the exhaust gas are fed to a combustion plant.
- the crude acrolein purified from high-boiling compounds and non-condensable gases is obtained from the aqueous acrolein solution under reduced pressure and at elevated temperatures and admixed with suitable stabilizers, for example hydroquinone, in order to counteract polymerization.
- acetaldehyde and water are mentioned as secondary components formed in the production of acrolein, which are contained in the crude acrolein. Distillation of the crude acrolein is possible but would be by distillation purified crude acrolein still contain traces of acetaldehyde. If the crude acrolein is subsequently reacted with methylmercaptan (MC) to give 3-methylmercaptopropionaldehyde (MMP), it is described in the prior art
- secondary components from the crude acrolein are separated off only after its conversion to MMP.
- the volatile acrolein is then converted to a higher boiling component and thus more easily separated from acetaldehyde or generally low boilers and these components do not adversely affect the synthesis of 3-methylmercaptopropionaldehyde from acrolein and methylmercaptan.
- the crude acrolein in addition to the known compounds such as acetaldehyde may also contain traces of allyl alcohol (see Ullmann ' s
- allylic components such as allyl alcohol are principally more toxic than their corresponding saturated alkyl components.
- the products methionine and / or MHA to be produced from acrolein are used as feed additives in modern animal nutrition. The manufacturing process must therefore ensure that all toxic compounds are removed. From a technical point of view, an enrichment of the unsaturated secondary components such as allyl alcohol also interferes with the subsequent process steps. For example, in the process for producing methionine, the product solution after hydrolysis on activated carbon is used as the adsorbent
- the technical object of the invention was therefore to provide a process which enables a separation of unsaturated secondary components, in particular of allyl alcohol, from the production process of methionine and / or MHA.
- Reactive rectification column and its use in the process according to the invention.
- the separation of the unsaturated secondary components, in particular allyl alcohol, is particularly advantageous after the conversion of the acrolein to methionine and / or MHA. It It was found that the alkaline hydrolysis (saponification) of the methionine precursor in the reactive rectification column according to the invention is particularly suitable, the
- Allyl components especially allyl alcohol to remove from the reaction mixture.
- the saponification can be described as a combination of steam distillation and thereby taking place hydrolysis reaction.
- the invention relates to a reactive rectification column (also
- Reactive distillation column or reactive distillation having a weir height of 100 mm and more and a process for the continuous production of a methionine salt using the column according to the invention.
- Weir height 8 100 - 1000 mm, preferably 150 - 700 mm
- Number of bases 15 - 25, especially 18 - 20.
- the cross-sectional area can be calculated using the column diameter 4.
- the gas-flow area is obtained by subtracting from the cross-sectional area the areas of the two drainage segments (2).
- Reactive rectification column for the preparation of a methionine salt, wherein the weir height is 100 mm or more.
- the weir height is in the range of 100 to 1000 mm, preferably in the range of 150 to 700 mm,
- the ground distances are in the range of 500 to 1000 mm
- the ratio of the cross-sectional area to the gas-flow area is in the range of 1.5 to 2
- the number of soils is in the range of 15 to 25, preferably in the range of 18 to 20.
- Reactive rectification column according to 1 or 2, wherein the reactive rectification column is a sieve tray column, slot tray column, valve tray column or
- Bubble tray column is.
- the ratio sum of the area of all holes / gas flow area is in the range of 0.04 to 0.08 and
- the diameter of the individual holes in the sieve bottom is in the range of 5 to 10 mm.
- the cross-sectional area can be calculated using the column diameter 4.
- the area through which gas flows is obtained by subtracting the areas of the two outlet segments 2 from the cross-sectional area.
- Ratio sum of the area of all holes / gas flow area: 0.04 - 0.08 Diameter of the single holes in the sieve bottom 5 - 10 mm.
- FIG. 1 is the top schematic view of a sieve plate and below in a section the side view of a column of a preferred embodiment
- the undesirable allyl components are preferably distilled off overhead in addition to water, ammonia (NH 3 ) and C0 2 .
- NH 3 ammonia
- Embodiment the entire amount of NH 3 or a part thereof is then condensed into the hydantoin synthesis.
- the alkali metal salt preferably the potassium salt of methionine, which is worked up as described in the prior art to methionine, and / or MHA.
- the heating and stripping medium used is preferably water vapor, which is fed under pressure below the lowermost sieve tray. Amount, speed and temperature of the vapor stream are preferably controlled so that a temperature of 180 ° C - 190 ° C is reached in the outlet of the reaction distillation column, while the gas phase leaves the column at a temperature of 160 ° C - 170 ° C at the head.
- the amount of steam is also dependent on the desired
- the tray spacings can be adapted to the different reaction phases in the column.
- the bottom clearances and the weir heights are preferably kept smaller to accelerate the stripping of NH 3 and C0 2 , while in the lower half the bottom clearances and weights are greater to increase the conversion by more residence time complete.
- the weir height in the upper trays of a column in the range of 100 to 200 mm, preferably at 150 mm, at a
- Ground clearance in the range of 800 to 1000 mm, preferably 1000 mm, and the
- the ground clearance is determined from one soil to the lower soil.
- the trays 1 to 4 preferably belong to the upper trays, trays 5 to 1 to the middle trays and the lower trays to the lower trays.
- the trays 1 to 5 preferably belong to the upper trays, trays 6 to 12 to the middle trays and the lower trays to the lower trays.
- the inventive method is particularly suitable for the alkaline hydrolysis of 5- (2-methylmercaptoethyl) -hydantoin to a methionine salt, wherein the 5- (2-methylmercaptoethyl) -hydantoin from 3-methylmercaptopropionaldehyde and hydrogen cyanide (HCN) or a component thereof can be prepared was produced.
- HCN hydrogen cyanide
- only a 5- (2-methylmercaptoethyl) -hydantoin-containing solution is fed to the uppermost bottom of the reactive rectification column while an alkaline cycle solution is fed to an underlying tray, preferably the second tray from above.
- the alkaline circulation solution contains
- Alkali metal carbonate preferably potassium carbonate.
- the invention particularly relates to a
- alkaline hydrolysis is carried out at a temperature in the range of 160 ° C to 190 ° C.
- Reactive rectification column in the range of 160 ° C to 170 ° C.
- alkaline hydrolysis is carried out at a pressure in the range of 8 bar (g) to 10 bar (g).
- Reactive rectification water vapor is used.
- Preferred starting materials for preparing the 5- (2-methylmercaptoethyl) hydantoin are 3-methylmercaptopropionaldehyde, hydrogen cyanide, ammonia and carbon dioxide.
- By-products of this reaction are the components 5- (2-methylmercaptoethyl) hydantoic acid amide, 5- (methylmercaptoethyl) -hydantoic acid, methioninamide and in traces, among other components, 3-methylmercaptopropionaldehyde cyanohydrin. These can be used in alkaline hydrolysis as well as the main product to methionine be implemented. The exception is 3-methylmercaptopropionaldehyde cyanohydrin, which on hydrolysis becomes 4-methylmercapto-2-hydroxybutanoic acid. The exact composition of the product mixture formed in the hydantoin reaction can be elucidated by means of HPLC.
- MMP cyanohydrin can be used in hydantoin production. It is advantageous for complete conversion of MMP to the hydantoin derivative if MMP and NH 3 are used in the reactive absorber in a molar ratio of about 1 to 3, the basic equation of the hydantoin synthesis being as follows (formula I):
- the hydantoin derivative is converted to methionine in the alkaline hydrolysis.
- Methionine means racemic methionine, also referred to as D, L-methionine.
- This step of the process according to the invention is preferably carried out in a sieve plate column which is operated as a reactive distillation.
- the reactive rectification column according to the invention is preferably operated in a coupled reaction distillation reaction absorber system.
- the amount of NH 3 required for this purpose does not have to be provided and metered separately but circulates in the system.
- the concentration of ammonia in the bottom product is less than 120 ppm, more preferably less than 100 ppm, and most preferably less than 80 ppm. Due to this mode of operation, it is advantageously possible to completely dispense with an external NH 3 dosage in the "steady state".
- Hydantoin hydrolysis has surprisingly shown that initially a stable intermediate forms, namely the potassium salt of hydantoic acid, according to the following equation (formula IV).
- the potassium salt formed can react back to the salt of hydantoic acid via the equilibrium reaction, it is of great advantage for as complete a conversion as possible with technically required short reaction times if, in addition to the allyl components, ammonia and CO 2 are also effective from the liquid phase during the reaction be removed.
- a sieve tray column is used.
- the preferred combination of reactive rectification column and a reactive absorber allows the provision of process conditions that makes the production of methionine particularly economically attractive.
- a small part-stream can be selectively removed from the gaseous overhead product and disposed of. In this way, the resulting NH 3 surplus can be discharged from the system in an environmentally friendly manner while avoiding the loss of valuable raw materials.
- the reactive rectification column may be on one or more or all trays
- the samples taken are preferably cooled and analyzed for hydantoin, hydantoic acid, methionine, methionylmethionine by high performance liquid chromatography (HPLC).
- HPLC high performance liquid chromatography
- the NH 3 content can be determined potentiometrically by means of an ion-selective electrode.
- the rain limit is 50% of the specific steam amount mentioned above. Preference is given to amounts of steam in the range of 0.13 t of steam per ton of process solution to 0.4 t of steam per ton of process solution, most preferably in the range of 0.20 t of steam per ton of process solution to 0.25 t of steam per ton of process solution.
- zirconium is used in the reactive distillation and / or in the reactive absorber and / or in the secondary reactor as a material for the product-contacted parts. This can be sustained corrosion damage to the
- claimed process overall very sustainable because it avoids the corrosive discharge of environmentally harmful heavy metals such as chromium and nickel. Furthermore, due to the close association of the process steps, the costs incurred during operation of the column Waste heat to be used in an ideal way for heating the feed streams and in addition to the operation of the evaporation unit.
- the reaction system according to the invention ensures a sufficient residence time of the reactants in the column. At the same time it is advantageous because of the high cost of the material zirconium that the number of soils can be kept small.
- the trays are sieve trays.
- Other common floor constructions eg slotted, valve or bubble-cap floors
- slotted, valve or bubble-cap floors are applicable, but have the disadvantage that their production from the material zirconium is very difficult. It is therefore in this
- the reactive distillation column allows a quantitative
- the mother liquor from the precipitation of the methionine salt is preferably used.
- the mother liquor contains the potassium salts predominantly as KHC0 3 . These are then preferably concentrated to separate C0 2 and water, resulting in a solution with high potassium carbonate content and thus increased basicity, which is advantageous for the hydrolysis reaction.
- the energy required to operate this evaporation step can be particularly suitably from the waste heat of the combination reactive distillation Reactive absorption are related.
- the amount of water required to produce the quantities of steam required to operate the reactive distillation is obtained from the condensate of the evaporation step.
- Reaction solutions are introduced into the reactive rectification column so that only the 5- (2-methylmercaptoethyl) -hydantoin contained solution is fed to the top soil and the alkaline potassium circulating solution is fed to an underlying soil, preferably on the 2nd floor from above , Thus, preferably NH 3 , C0 2 and HCN are stripped from the hydantoin solution and into the
- Hydantoinre is attributed. This minimizes, above all, the loss of HCN according to formula VI and at the same time avoids the formation of potassium formate.
- Potassium formate as a neutral salt is not suitable for supporting the hydrolysis of hydantoin and must therefore be removed from the potassium cycle.
- the associated potassium losses must be compensated by using KOH.
- the sequential feed of hydantoin solution and alkaline potassium cycle solution at the top of the reactive distillation therefore avoids costs for raw materials and disposal.
- the use of a reactive distillation with sieve trays advantageously suppresses the formation of by-products such as methionine dipeptide. Since the simultaneous presence of the starting compound hydantoin and the potassium salt of methionine is necessary for the formation of the methionine dipeptide, to avoid this reaction is an efficient separation of
- Reactant advantageous. This is done in a particularly suitable manner in a equipped with sieve trays reactive distillation, since in this system a
- Soil construction largely prevents backmixing and thereby inhibits the formation of met-dipeptides, and secondly, the intense stripping process increases the basicity in the reaction solution, which is illustrated by the following reaction equation.
- Essential for efficient conversion of the hydantoin to the methionine in the claimed column is the presence of a sufficient amount of non-volatile basic compounds in the reaction matrix.
- These are potassium salts, such as KOH, potassium carbonate, potassium bicarbonate, potassium methioninate, potassium salt of the met dipeptide. Since these potassium salts are very largely recycled, but at the same time in Side reactions also potassium salts of strong acids arise it is important the
- Basizitatsgrad to capture in particular at the exit of the column.
- a sample is taken and subjected to this after cooling to ambient temperature of a classical acid-base titration.
- the pH of the reaction mixture at the outlet of the column is preferably in the range from 4 to 5.
- the basicity values in the reaction matrix at the end of the reaction are preferably in the range from 2.2 to 2.8 mol of base per kg of saponified solution, preferably 2 , 5 moles base / kg saponified solution. lower
- FIG. 2 is used.
- the production of hydantoin takes place.
- the raw materials HCN and MMP are mixed via the feed points S-1 and S-2 in the about 20-fold amount of hydantoin reaction solution, which is circulated by the pump P-1.
- Heat exchanger H-1 is used for heat removal and keeps the reactor contents R-1 preferably at a temperature of 100 ° C - 120 ° C.
- a premix of MMP and HCN or separately prepared MMP cyanohydrin may also be used in the pump P-1
- the liquid hydantoin-containing stream S-6 is passed through a post-reactor R-3 to complete the conversion. At the same time, this prevents the entry of MMP cyanohydrin into the hydrolysis reactor R-2.
- the hydantoin-containing process stream S-6 is preferably preheated to 130 ° C. by means of heat exchanger H-2 before it enters the top bottom of the sieve bottom column R-2. On bottom 1 of the reaction distillation, preferably still existing HCN is expelled. This reduces the hydrolysis of the HCN to form the potassium salt of formic acid, which otherwise takes place in alkaline reaction in the reaction distillation
- the hydrolysis of the hydantoin to methionine begins with the coincidence of the hydantoin-containing process solution and the stream S-8, which originates from the concentrated filtrates of the workup to the methionine salt solid S-9.
- the stream S-8 takes as much heat as possible from the bottom product of the reactive distillation (heat exchanger H-4) and is thus preferably heated to 170 ° C.
- Evaporator unit H-5 is preferably the steam for operating the
- Reactive distillation can be used in the further workup, whereby the entire Production process for methionine according to the claimed method energetically expresses low and therefore economically attractive design.
- a sieve tray column with a diameter of 1 meter and 18 sieve trays as shown in FIG. 2 is used for the continuous production of methionine.
- the arrangement of the sieve trays, their distances and weir heights are shown in the following table:
- the tank R-1 is operated with a hold up of 3 m 3 , the postreactor has a hold up of 1 m 3 .
- a circulation rate of 42 t / h is set via the pump P-1.
- 442 kg / h of HCN (16.92 kmol / h) are fed into S-1 and 16.0 kg / h of MMP (16.24 kmol / h) in S-2.
- S-3 a flow of 6063 kg / h with a NH 3 content of 1 1, 6 wt .-% of condensates from the head of the reactive distillation in the
- the temperature in the outlet of R-1 at 105 ° C is regulated.
- the hydantoin reaction solution (S-6) is passed to complete the reaction via the secondary reactor R-3, heated in the heat exchanger H-2 to 130 ° C and then fed to the top bottom of the sieve tray column.
- On bottom 2 14.14 t / h of heat exchanger H-4 are heated to 170 ° C potassium carbonate-containing process solution (S-8) containing the following components: 66 g / kg Met, 158 g / kg potassium, 48 g / kg Met-Met, 6.5 g / kg MHA, 12.5 g / kg formate, 3.6 moles base / kg to basicity.
- the steam flow required for operation (5470 kg / h) is generated by means of evaporator H-5 (S-7) and fed below the bottom sieve tray. From the overhead stream, a partial stream S-10 (54 kg / h) is diverted and disposed of. The amount of allyl alcohol in S-10 is in the range of 0.5-1.7 kg / h.
- the pressure at the top of the sieve tray column is 8.2 bar (ü) and the temperature at the inlet side of the heat exchanger H-3 is 165 ° C.
- the differential pressure across all sieve trays is 450 mbar.
- the temperature in the bottom of the column is 189 ° C.
- Methionine methionyl methionine examined.
- the NH 3 content is determined by means of a
- ion-selective electrode determined potentiometrically. The concentrations of
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102011081828A DE102011081828A1 (de) | 2011-08-30 | 2011-08-30 | Verfahren zur Umsetzung von Methylmercaptopropionaldehyd aus Roh-Acrolein und Roh-Methylmercaptan |
PCT/EP2012/066376 WO2013030069A1 (de) | 2011-08-30 | 2012-08-23 | Verfahren zur umsetzung von methylmercaptopropionaldehyd aus roh-acrolein und roh-methylmercaptan |
Publications (1)
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EP2750776A1 true EP2750776A1 (de) | 2014-07-09 |
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EP12750380.3A Ceased EP2750776A1 (de) | 2011-08-30 | 2012-08-23 | Verfahren zur umsetzung von methylmercaptopropionaldehyd aus roh-acrolein und roh-methylmercaptan |
Country Status (12)
Country | Link |
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US (1) | US9029597B2 (ja) |
EP (1) | EP2750776A1 (ja) |
JP (1) | JP6092218B2 (ja) |
KR (1) | KR101945072B1 (ja) |
CN (1) | CN103764239B (ja) |
BR (1) | BR112014004538A2 (ja) |
DE (1) | DE102011081828A1 (ja) |
MX (1) | MX2014002249A (ja) |
MY (1) | MY170459A (ja) |
RU (1) | RU2615734C2 (ja) |
SG (1) | SG2014014161A (ja) |
WO (1) | WO2013030069A1 (ja) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010064250A1 (de) | 2010-12-28 | 2012-06-28 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Methylmercaptopropionaldehyd |
WO2012113664A1 (de) | 2011-02-23 | 2012-08-30 | Evonik Degussa Gmbh | Verfahren zur herstellung von 2-hydroxy-4-(methylthio)buttersäurenitril aus 3-(methylthio)propanal und cyanwasserstoff |
EP2750775B1 (de) * | 2011-08-30 | 2020-12-09 | Evonik Operations GmbH | Verfahren zur herstellung eines methioninsalzes |
EP2679579A1 (de) | 2012-06-27 | 2014-01-01 | Evonik Industries AG | Integriertes Verfahren zur Herstellung von Acrolein und 3-Methylmercaptopropionaldehyd |
EP2848607A1 (de) | 2013-09-17 | 2015-03-18 | Evonik Industries AG | Verfahren zur Gewinnung von Methionin |
WO2016046100A1 (en) | 2014-09-24 | 2016-03-31 | Shell Internationale Research Maatschappij B.V. | Process and apparatus for the preparation of alkylene glycol |
CN105061193B (zh) * | 2015-08-10 | 2017-03-22 | 蓝星(北京)技术中心有限公司 | 蛋氨酸生产废水处理中回收有机物的方法 |
CN111491917B (zh) * | 2017-12-19 | 2022-03-22 | 住友化学株式会社 | 甲硫氨酸的制造方法 |
JP7085570B2 (ja) * | 2017-12-28 | 2022-06-16 | 住友化学株式会社 | メチオニンの製造方法 |
EP3656760A1 (de) * | 2018-11-21 | 2020-05-27 | Evonik Operations GmbH | Lagerstabile form von 3-methylthiopropionaldehyd |
US20220219248A1 (en) * | 2019-05-06 | 2022-07-14 | Sabic Global Technologies B.V. | Distillation tray having through holes with different diameters |
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GB1166961A (en) | 1966-04-30 | 1969-10-15 | Sumitomo Chemical Co | Process for Producing beta-Methylmercaptopropionaldehyde |
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DE3335218A1 (de) * | 1983-09-29 | 1985-04-11 | Degussa Ag, 6000 Frankfurt | Verfahren zur hydrolyse von 5-(ss-methylmercaptoethyl) -hydantoin |
SU1360753A1 (ru) * | 1986-07-14 | 1987-12-23 | Киевский Технологический Институт Пищевой Промышленности | Тепломассообменный аппарат |
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2011
- 2011-08-30 DE DE102011081828A patent/DE102011081828A1/de not_active Withdrawn
-
2012
- 2012-08-23 KR KR1020147004805A patent/KR101945072B1/ko active IP Right Grant
- 2012-08-23 MX MX2014002249A patent/MX2014002249A/es unknown
- 2012-08-23 RU RU2014111965A patent/RU2615734C2/ru active
- 2012-08-23 JP JP2014527591A patent/JP6092218B2/ja active Active
- 2012-08-23 CN CN201280042496.8A patent/CN103764239B/zh active Active
- 2012-08-23 BR BR112014004538A patent/BR112014004538A2/pt not_active Application Discontinuation
- 2012-08-23 WO PCT/EP2012/066376 patent/WO2013030069A1/de active Application Filing
- 2012-08-23 SG SG2014014161A patent/SG2014014161A/en unknown
- 2012-08-23 MY MYPI2014000551A patent/MY170459A/en unknown
- 2012-08-23 EP EP12750380.3A patent/EP2750776A1/de not_active Ceased
- 2012-08-29 US US13/597,852 patent/US9029597B2/en active Active
Non-Patent Citations (2)
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Also Published As
Publication number | Publication date |
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JP6092218B2 (ja) | 2017-03-08 |
MY170459A (en) | 2019-08-02 |
CN103764239A (zh) | 2014-04-30 |
MX2014002249A (es) | 2014-04-25 |
SG2014014161A (en) | 2014-10-30 |
CN103764239B (zh) | 2016-05-18 |
WO2013030069A1 (de) | 2013-03-07 |
US9029597B2 (en) | 2015-05-12 |
RU2615734C2 (ru) | 2017-04-10 |
KR20140068030A (ko) | 2014-06-05 |
JP2014529616A (ja) | 2014-11-13 |
KR101945072B1 (ko) | 2019-04-17 |
BR112014004538A2 (pt) | 2017-03-28 |
US20130245318A1 (en) | 2013-09-19 |
DE102011081828A1 (de) | 2013-02-28 |
RU2014111965A (ru) | 2015-11-10 |
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