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    • 专利摘要:
    method for the production of 2-hydroxy-4- (methylthio) butane nitrile from 3- (methylthio) propanal and hydrogen cyanide. the present invention relates to a method for the production of 2-hydroxy-4- (methylthio) butyronitrile, in which 3-methyl mercapto propionaldehyde is reacted with hydrogen cyanide in the presence of a base as a catalyst in a main reaction zone to form nitrile, and residual amounts of gaseous hydrogen cyanide leaving the main reaction zone are absorbed in an absorption and post-reaction zone that contains a mixture of 3-methyl mercapto propionaldehyde and catalyst, and optionally 2-hydroxy -4- (methylthio) butyronitrile, and are then reacted.
    公开号:BR112013018092B1
    申请号:R112013018092-7
    申请日:2012-02-13
    公开日:2021-04-27
    发明作者:Dieter Buss；Martin Steurenthaler；Michael R. Rinner；Stephan Kretz；Hans Joachim Hasselbach；Caspar-Heinrich Finkeldei；Martin Körfer；Pablo Zacchi
    申请人:Evonik Operations Gmbh；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a catalytic method for the production of 2-hydroxy-4- (methylthio) butyronitrile (MMP-CN) from 3- (methylthio) propanal (= methyl mercapto propionaldehyde, MMP), and hydrogen cyanide (HCN). In particular, the invention describes a process for the synthesis of stable MMP-CN under storage using stoichiometric amounts of prussic acid, in which the product contains super-stoichiometric amounts of prussic acid, with respect to unreacted MMP or MMP in equilibrium with the MMP-CN.
    [0002] 2-hydroxy-4- (methylthio) butyronitrile (MMP-cyanohydrin) is an intermediate for the synthesis of D, L-methionine and the hydroxyl methionine analogue, 2-hydroxy-4-methyl thiobutyric acid (MHA) . Methionine is an essential amino acid that is used, in combination, as a supplement in foodstuffs. MHA is a liquid substitute for methionine that has low bioavailability. Prior Art
    [0003] From MMP, through the reaction with hydrogen cyanide (prussic acid), MMP-cyanhydrin (2-hydroxy-4- (methylthio) butyronitrile) can be produced using appropriate catalysts. Suitable catalysts are, for example, pyridine or triethylamine. By hydrolysis of MMP-cyanhydrin with, for example, mineral acids, MHA is obtained. Methionine is formed by the reaction of MMP-cyanhydrin with ammonium hydrogen carbonate, with the formation of hydantoin, which can be saponified with a base, for example, potassium carbonate or sodium hydroxide. Methionine is released with carbon dioxide or sulfuric acid.
    [0004] It is known, for example, from US 4,960,932, the production of methionine by a four-stage method. In the first step, by adding HCN to MMP in the presence of triethylamine, MMP-cyanhydrin is produced. The amount of HCN used corresponds to 1.05 mol with respect to the amount of MMP used. Then, the MMP-cyanhydrin, in a second stage, is reacted with ammonia, whereby the 2-amino-4-methylthio butyronitrile is formed, which, in a third stage, is then hydrolyzed in the presence of a ketone and an alkali metal hydroxide, forming methyl thiobutyramide, which is finally saponified to form an alkali metal methioninate.
    [0005] In the case of the production of 2-hydroxy-4-methyl thiobutyric acid (MHA), 2-hydroxy-4-methyl thiobutyryl nitrile is obtained by reacting MMP and HCN in a medium containing pyridine or an amine (see US 2,745,745, column 2, lines 52 to 55). Excess HCN is merely removed by distillation, for example, in a vacuum. The resulting 2-hydroxy-4-methyl thiobutyre nitrile is then hydrolyzed with sulfuric acid, whereby the 2-hydroxy-4-methyl thiobutyric acid amide is formed directly, and the 2-hydroxy-4-methyl thiobutyric acid is formed finally formed. A similar method is also described in EP A 330 527 A1 or US 4,912,257.
    [0006] Furthermore, WO 96/40631 A1 describes the production of MMP-cyanhydrin when reacting MMP with hydrogen cyanide in the presence of an appropriate addition reaction catalyst. It has been found that triisopropanolamine, nicotinamide, imidazole, benzimidazole, 2-fluoro pyridine, poly-4-vinyl pyridine, 4-dimethyl aminopyridine, picoline and pyrazine can serve as catalysts for the addition reaction to produce MMP-cyanhydrin. In addition, trialkylamines having three to eighteen carbon atoms in each of the alkyl substituents attached to the nitrogen atom and to the tertiary amines in which at least one of the substituents, other than hydrogen, is attached to the nitrogen atom of according to the above description, they contain an aryl group and can also serve to catalyze the reaction between MMP and hydrogen cyanide to form MMP-cyanhydrin.
    [0007] Preferably, in this case, hydrogen cyanide is used in a molar excess of about 2%, based on MMP.
    [0008] WO 2006/015684 A2 finally presents a method for, in particular, the continuous production of MMP or MMP-cyanhydrin in which each in each case heterogeneous amine catalysts are used for the addition reaction.
    [0009] Furthermore, it is known from US 5,756,803 the reaction of an aldehyde with hydrogen cyanide in the presence of a buffer, whereby the pH of the solution can be adjusted above 4, and the amines are excluded. Generally speaking, as a buffer, mixtures of alkali metal salts of acids and acids, or mixtures of alkali metal acids and hydroxides can be used. The buffer is used in order, first, to prevent the decomposition of the starting materials and the desired product, and secondly to neutralize the acids used to stabilize the hydrogen cyanide. Likewise, here, HCN is added in a molar excess over MMP, and the molar excess is preferably in the range of 2% to 5%. In the reaction of MMP with HCN in the presence of the commonly used bases, although these increase the reaction speed under the specified conditions, they quickly lead to a decomposition of the cyanhydrin formed and to the decomposition of the aldehyde used at the beginning, forming a highly discolored solution.
    [00010] In order to recover the residual amounts of unreacted HCN and MMP contained in the exhaust gas of the reactive absorbent, said unreacted HCN and MMO are removed when using a water remover, in which the removal water passes to the product. The water content in the product is about 48% by weight.
    [00011] The substantial disadvantages of the methods previously described in the literature are that, in order to obtain a high yield of MMP-CN, high molar excesses of HCN have to be used. Excess amounts of HCN are lost in the methods described and constitute a major economic disadvantage. In addition, the catalysts used in the described methods also promote the formation of unwanted by-products from the used aldehydes, which leads to contamination of the product that cannot be tolerated. An approach to solve this problem of the formation of by-products is described in US 5,756,803 with, of course, large amounts of water passing to the product that, firstly, for the production of methionine, need to be removed at least partially and that, in secondly, they promote the decomposition of MMP-cyanohydrin again, which in each case is a non-insignificant disadvantage. Therefore, the product described in US 5,756,803 is not stable under storage and, for storage and, in particular for transportation, it should not be processed in a complex way by removing water through distillation, which is a major disadvantage. method. Purpose of the invention
    [00012] The aim of the present invention is to provide a catalytic method that catalyzes the reaction of aldehyde, in particular MMP with hydrogen cyanide, and prepares a stable cyanhydrin under storage in which the method must at the same time exhibit marked improvements in with respect to yields with respect to used aldehyde and hydrogen cyanide. Description of the invention
    [00013] These and other objectives are achieved by a method for the production of 2-hydroxy-4- (methyl) thiobutyronitrile, in which 3- (methylmercapto) -propionaldehyde is reacted with hydrogen cyanide in the presence of a base as a catalyst in a main reaction zone to form the nitrile and residual amounts of gaseous hydrogen cyanide (HCN), which leave the main reaction zone and are absorbed in an absorption and post-reaction zone that contains a mixture of 3- (methylmercapto) -propionaldehyde and catalyst and optionally 2-hydroxy-4- (methylthio) -butyronitrile, and are further reacted.
    [00014] The residual HCN content reacts, due to absorption or condensation with the aldehyde, to form the cyanhydrin. Due to the effective removal of HCN from the gas phase, it is possible, contrary to the methods known in the literature, to use a molar ratio between hydrogen cyanide and an aldehyde from 0.99 to 1.01, which is a great economic advantage. for the method.
    [00015] The invention relates, in particular, to a method for the reaction of adding hydrogen cyanide to MMP in the presence of a base, in particular an amine, in which the method is arranged in such a way that the residual levels of gaseous hydrogen cyanide are absorbed outside a main reaction zone at temperatures of about 0 ° C to 25 ° C in a liquid mixture of the MMP aldehyde and the MMP reaction product with hydrogen cyanide and catalyst, and then are reacted with the MMP.
    [00016] By means of the method according to the invention, in general, aldehydes containing 1 to 6 carbon atoms which, if desired, are replaced by alkyl, alkoxy or alkylthio, are reacted advantageously with hydrogen cyanide.
    [00017] It is preferable here that the mixture contained in the absorption and post-reaction zone originates at least partially from the main reaction zone. A dilution with foreign materials or foreign solvents is thus prevented, unlike US 5,756,803.
    [00018] The main reaction zone may contain a reactor with agitation or a reactor with recirculation. Both modes lead to fast and good mixing and fast conversion of MMP and HCN.
    [00019] The main reaction zone can also additionally contain a jet pump. This leads to a further intensification of the mixing of the components and can be used concomitantly in a particularly advantageous way to extract the HCN into the main reaction zone.
    [00020] The post reaction can proceed as indicated above between a gas containing HCN and a liquid. It then takes place in an absorption and post-reaction zone that preferably contains a device for putting a gas in contact with a liquid, in particular a column such as, for example, a column with trays, a compacted bed column, a reactor bubble column, a drip column or optionally a reactor that has a mechanically agitated container, or a submerged jet reactor.
    [00021] The absorption zone and the post-reaction zone can also be part of a reactor with recirculation, which performs a great mixing and a quick reaction of the components.
    [00022] In the method according to the invention, substantially gaseous hydrogen cyanide is introduced into the main reaction zone, preferably a gaseous product containing hydrogen cyanide from a hydrogen cyanide production process.
    [00023] The hydrogen cyanide content of the gas mixture used ranges from 1 to 99% by weight, preferably 5 to 75% by weight, and particularly preferably from 6 to 22% by weight. Hydrogen cyanide is produced, in particular, by the Andrussow method as in DE 102007034715A1 or by what is called the German BMA method ("Blausaure aus Methan und Ammonik") 1041476 (reactor), both methods are also described in Ullmann's Encyclopedia of Industrial Chemistry, 1987 VCH-Verlagsgesellschaft mbH, chapter "Cyano Compounds Inorganic", section 1.2.1-1.2.2. The ammonia present is removed in each case of the gas The gas of the product of the Andrussow method (Andrussow gas) contains, after the removal of ammonia, typically about 10% by weight of hydrogen cyanide, on the other hand the gas of the product of the BMA method (gas of BMA) contains about 70% by weight of hydrogen cyanide.
    [00024] Thus, the typical gas compositions of the product of the Andrussow method have more or less the following contents: 10.3% by weight of HCN, 3.7% by weight of H2O, 1.3% by weight of H2, 75.8% by weight of N2, 0.4% by weight of O2, 6.3% by weight of CO, 0.6% by weight of CO2, 0.4% by weight of CH4, 1.3 % by weight of Ar, those of the BMA method of about 68.3% by weight of HCN, 6.7% by weight of H2O, 17.3% by weight of H2, 3.6% by weight of N2, 4% by weight of CH4.
    [00025] The direct use of the product gas has the considerable advantage that no upstream energy-consuming liquefaction of hydrogen cyanide needs to proceed and with coupling corresponding to a plant to produce hydrogen cyanide gas, capital costs are saved considerable steps in the corresponding process steps for the absorption and distillation of HCN. Additional gas fractions in addition to HCN do not surprisingly have a disadvantageous effect on cyanhydrin yield.
    [00026] The residual gas from the production of MMP-cyanhydrin and the production of hydrogen cyanide can then be used together or flared. In the latter case, the resulting energy can be reused to operate both methods, which means more degrees of freedom and a considerable economic advantage.
    [00027] A preferred embodiment of the method according to the invention and a corresponding device are outlined in Fig. 1, which is described in more detail below.
    [00028] When a column with trays or a compacted bed column is used for reactive absorption, the gas flow containing the prussic acid is fed into the lower phase (A) of the column (C) or preferably already in contact with the aldehyde solution through a gas insufflator (B), in which the aldehyde solution is circulated (8) by means of a pump (I). The temperature in the lower phase of the column is adjusted using a heat exchanger (J). The lower phase (A) and the column (C), in particular, serve as the main reaction zone, in which column C can be heated / cooled separately by means of a heat exchanger (K). In this case the temperature of the currents (7) and (8) is selected in such a way that the heat of the reaction can be removed with cooling water that corresponds to the ambient temperature and the reaction between the aldehyde and the HCN in the column part ( C) is 80 to 99.9% complete.
    [00029] The aldehyde can be fed separately or together with the catalyst ((2), (3)). Preferably, the aldehyde or aldehyde / catalyst mixture (2) + (3) is mixed with a subcurrent (6) of the absorption and condensation part (E) of the column which is removed from an intermediate lower phase (D). The catalyst can also be fed, for example, through the passage (4). In this case, the catalyst must, through the passage (13), also reach the part in the upper circuit. The residual amounts of HCN present in the stream (6) are reacted with the aldehyde provided in the residence time vessel (G), the (second) post-reaction zone, completely or virtually complete in cyanhydrin. The current is then cooled to 0 ° C - 25 ° C in the heat exchanger (H) in order to ensure the condensation / absorption of HCN as completely as possible. In particular, the intermediate lower phase (D), the absorption and condensation part (E) and the residence time vessel (G) serve as the absorption and post-reaction zone. Due to the amount of cyanhydrin present in the stream (5), and the cooling that is carried out, the residual gases leaving the top of the column also contain only very low residual amounts of aldehyde, and thus no additional removal for the recovery of the aldehyde from the column. residual gas is required. The cyanhydrin concentration can be adjusted by corresponding measurement of the lower phase of the column (13), preferably in the range of 10% by weight to 70% by weight in the stream (5). The purified gases are advantageously passed to a combustion unit. The product leaving the stream (9) has a molar ratio between hydrogen cyanide and unreacted aldehyde of more than 1, which contributes substantially to stabilizing the product. In addition, the product is clear and only slightly discolored, which highlights the extraordinarily high selectivity of this process procedure.
    [00030] After passing through a post-reactor (L), in which all residual fractions of the present aldehyde are reacted until completion to achieve equilibrium with hydrogen cyanide, the resulting product stream is mixed with an acid. For this purpose, an appropriate mixing element (M) is used. The pH of the product (current (11)) that is adjusted in this case is between 1 and 4, preferably between 2 and 3.
    [00031] If the aldehyde is MMP, as shown in Fig. 1, the MMP starting material stream of the method described in general has a small content of methylmercaptan (MC), the predominant part of which must pass to the current of the exhaust gas (12). This additional MC can also optionally be reacted with acrolein, which can be fed to the method, for example, through the stream (14), to form MMP and in succession with HCN to form MMP-CN and thereby further increase the yield.
    [00032] In the method according to the invention, the catalyst used can consist of amines or solutions of low molecular weight or heterogeneous or solutions of inorganic bases, or mixtures of acids and amines of low molecular weight. These are also necessary in order to adjust the ideal pH range from about 4.5 to 6.0, preferably from 5.0 to 5.5, which is required for the reaction, which is measured when using a type of pH electrode ("Aquatrode Plus with Pt 1000", manufacturer: Metrohm Schweiz AG) directly on cyanhydrin which has a typical water content of 2 to 14% by weight. The measurements are made at a temperature of about 23 ° in a stirred vessel, and the pH measurement is compensated for by the temperature. To follow the reaction conditions close to time, and to eliminate measurement errors, at hourly intervals, in each case the pH is measured 4 times with the formation of the average value, and each measurement takes about 30 seconds. The measurement can, however, also be made directly during the in-line reaction in the reaction system at the temperature that is adjusted there and converted to pH at 23 ° C, which further simplifies the process control.
    [00033] Low molecular weight amines, preferably containing 1 to 36 carbon atoms, have the particular advantage of virtually unlimited miscibility with the reaction medium, which in turn favors a rapid reaction.
    [00034] The low molecular weight amines that are preferred in this case are the Tri- (C1 -C2 alkyl) amines, preferably Triethylamine or Triisopropanol amine, Dialkyl aralkylamines, preferably Dimethyl benzylamine, Dialkyl arylamines, preferably N, N-dimethyl aniline, heterocyclic amines, preferably Nicotinamide, Imidazole, Benzimidazole, 2-Fluoro pyridine, 4-Dimethyl aminopyridine, Picoline or Pyrazine.
    [00035] Alternatively, heterogeneous amines of the general formula
    or polyvinyl pyridine can also be used, where R1 and R2 are hydrogens, alkyl having chain lengths between C1 and C12, aryl or heteroaryl; R1 can be different from R2; X is a number between 0 and 6; and
    [00036] A is a natural or synthetic resin, preferably a polystyrene. These and the advantages associated with them, such as, for example, easier separability, low drag in subsequent reaction stages, are already described in WO 2006/015684.
    [00037] In this case it is preferable that the catalyst according to Formula I is a polymer-bonded base selected from the group of homologous dialkyl aminoalkyl polystyrenes or macroreticular dialkylamino resins.
    [00038] It is particularly preferable that the catalyst according to Formula I is diethyl amino ethyl polystyrene, diethyl amino methyl polystyrene, dimethyl amino methyl polystyrene, a macroreticular diethylaminomethyl resin or dimethyl amino ethyl polystyrene.
    [00039] The inorganic base used may advantageously be an alkali metal hydroxide, preferably NaOH or KOH, an alkali metal cyanide, preferably NaCN or KCN, an alkali metal carbonate, preferably Na2CO3 or K2CO3, or a hydrogen carbonate. alkali metal, preferably NaHCO3 or KHCO3, alone or in a mixed form. These have the advantage of a particularly high catalytic activity which in turn favors a very rapid reaction and also the potential low interference of the resulting low salt fractions in the subsequent method. However, here, extremely good mixing and temperature control must be ensured, so that no significant by-product formation follows.
    [00040] As catalysts, advantageously, mixtures of acids and the aforementioned low-molecular amines can also be used in order to adjust the pH more immediately in the desired range and to be able to stabilize it by the action of buffer. In this case, it is particularly advantageous to use organic acids such as short-chain fatty acids, for example, acetic acid, formic acid, citric acid, and organic sulfonic acids, for example, trifluoro methane sulfonic acid, or use of mineral acids such as, for example, sulfuric acid or phosphoric acid, in combination with low molecular weight amines.
    [00041] According to an additional preferred embodiment of the invention, the temperature in the main reaction zone is selected in such a way that the released reaction heat can be passed to the cooling water according to the ambient temperature, which is another great economic advantage of the method.
    [00042] Correspondingly, the main reaction zone is operated at a temperature of 20 ° C to 80 ° C, preferably from 30 ° C to 70 ° C, and particularly preferably from 35 ° C to 65 ° C. The reaction also proceeds comparatively quickly in this range.
    [00043] In the method according to the invention, it is also preferable that the absorption and post-reaction zone is operated at a temperature of 0 ° C to 30 ° C, and preferably 4 ° C to 15 ° C. This ensures a particularly efficient absorption of hydrogen cyanide and also makes possible a complete reaction of HCN with MMP to form MMP-cyanhydrin.
    [00044] In addition, the use of a second post-reaction zone immediately upstream of the product discharge point for MMP-cyanhydrin is advantageous. This second post-reaction zone is operated at a temperature similar to that of the main reaction zone of 20 ° C to 80 ° C, preferably from 40 ° C to 70 ° C, and particularly preferably from 45 ° C to 65 ° Ç. In this way, a quick and virtually quantitative completion of the HCN and MMP reaction to form the MMP-cyanhydrin immediately upstream of the product discharge is ensured.
    [00045] The method according to the invention is advantageously operated at an absolute pressure of 90 to 500 KPa (0.9 to 5 bar), preferably from 10 to 300 KPa (1.0 to 3 bar), and particularly from preferably from 100 to 15 KPa (1 to 1.5 bar). This has the effect that the rapid degassing of the HCN absorbed from the solution and the corresponding losses are thereby prevented.
    [00046] The method according to the invention, moreover, is characterized by the fact that a molar ratio between prussic acid and 3- (methylthio) propanal can be adjusted from 0.98 to 1.03, preferably from 0, 99 to 1.01. Firstly, losses of prussic acid are thus prevented, especially on an industrial scale, which are a major economic disadvantage. Second, unwanted prussic acid decomposition products such as, for example, polymeric prussic acid or formic acid of the saponification product which has corrosive properties against various metallic materials, are avoided and the corresponding disadvantageous effects at the stages of the method downstream to methionine are thus avoided.
    [00047] In the method according to the invention, preferably a weight ratio between the catalyst and 3- (methylthio) propanal from 0.00005 to 0.002, and particularly preferably from 0.0001 to 0.001 is used. This has the effect of a particularly low by-product formation at the same time as a high reaction rate.
    [00048] The method according to the invention can optionally be carried out batchwise, semi-continuously or continuously, in which the continuous mode is particularly economical to operate on an industrial scale of more than 10,000 tons / a.
    [00049] The MMP-cyanhydrin produced according to the invention has the following typical composition: MMP-CN: 86 - 97% by weight, MMP: 0 - 1% by weight, HCN: 0.05 - 0.5% by weight, H2O: 2 - 14% by weight, Oligomers: 0.01 - 0.1% by weight.
    [00050] MMP-based molar yields are typically 99.50 to 99.99%.
    [00051] The reaction product containing methyl thiopropionaldehyde cyanhydrin (MMP-cyanhydrin) obtained according to the method according to the invention can, particularly advantageously, be used directly to produce methionine and 2-hydroxy-4-methyl acid thiobutyric. For this purpose, it is aminated (aminonitrile route) or reacted with a mixture of ammonia and carbon dioxide (hydantoin route) in order to form methionine or be hydrolyzed directly to form 2-hydroxy-4-methyl acid thiobutyric (methionine hydroxy analogs, MHA). In addition, it has surprisingly been found that the high-boiling MMP oligomers already present in the MMP are mostly reacted in the method according to the invention to form the desired MMP-cyanhydrin. This is shown since, for example, the residue formed in the distillation of the products is markedly less after the reaction than before the reaction to form the MMP-cyanhydrin.
    [00052] The present invention will be described in more detail with reference to the following examples. Analytical methods used:
    [00053] The H2O content in MMP-CN was determined by the titration method with biamperometric indication of the end point (Karl-Fischer titration).
    [00054] For this purpose, 20 to 30 mL of the titration medium (for example, Hydranal Solvent 5, Fluka) was loaded into the titration vessel and titrated to dryness using a titrating agent (for example, Hydranal Titrant 5, Fluka). An amount of about 500 mg was added to the initial charge that had been titrated to exhaustion (disposable plastic syringe) and titrated to the final point with the titrating agent. The exact weight of the sample was determined by differential weighing.
    [00055] The procedure of this standard method is known to those skilled in the art (see, for example, P. A. Bruttel, R. Schlink: Wasserbestimmung durch Karl-Fischer-Titration [Determination of water by Karl-Fischer titration] Metrohm AG).
    [00056] The free prussic acid content of the product was determined by the principle of ion chromatography (IC) when using amperometric cyanide detection on an Ag working electrode, in which sample preparation was continued by separating prussic acid free from the sample matrix by means of preparative column chromatography.
    [00057] The preparative cyanide removal was carried out, for example, at room temperature, in a separation column PRP-X 300, 250 mm long x 4.1 mm internal diameter from Hamilton. The mobile phase consisted of a 5 mmolar sulfuric acid. At a flow rate of 1.0 mL / min, 100 μl of the sample solution (0.1 g of the sample in 10 mL of the mobile phase) was injected. The column eluate from 4 minutes to 8 minutes was collected in a 100 mL measuring flask, made up to the mark with ultrapure water, and 100 μl were injected into the CI to determine cyanide.
    [00058] Similar to the sample solution, a NaCN calibration solution of known content was subjected to preparative separation by means of column chromatography and 100 μl were injected into the CI for the determination of cyanide.
    [00059] The determination of cyanide by ion chromatography was carried out at room temperature, for example, in a column of the Carbo Pac PA1 separation, 250 mm long x 4.0 mm internal diameter from Dionex. The mobile phase consisted of a solution of 1.5 g of sodium chloride and 1 ml of ethylene diamine in 1 liter of a 50 mmolar solution of sodium hydroxide. At a flow rate of 1.0 mL / min, 100 μl of the sample solution or calibration solution was injected. The evaluation was performed by comparing the peak area using the standard external method.
    [00060] The procedure of this standard method is known to those skilled in the art.
    [00061] The MMP-CN and MMP contents of the product were determined by means of isocratic ion exclusion chromatography in a cation exchanger with subsequent UV detection at 205 nm. The determination was carried out, for example, on a separation column PRP X 300, 250 mm long x 4.1 mm internal diameter from Hamilton at a temperature of 25 ° C. The mobile phase consisted of a 5 mmolar sulfuric acid. At a flow rate of 1.0 mL / min, 100 μl of the respective sample solution (0.5 g of the sample for the determination of MMP or 0.06 g of the sample for the determination of MMP-CN in 50 mL of solvent) were injected. Calibration proceeded by injecting the appropriate calibration solutions (0.5 mg MMP in 50 ml solvent, or 50 mg MMP-CN in 50 ml solvent).
    [00062] The solvent consisted of a mixture of 500 μl of 0.5 molar H2SO4 and 5 ml of acetonitrile which was diluted to 50 ml with ultrapure water.
    [00063] The evaluation proceeded by comparing the peak area using the external standard method.
    [00064] The procedure of this standard method is known to those skilled in the art.
    [00065] The components in the starting material containing HCN nitrogen gas (N2), carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), ammonia (NH3), prussic acid (HCN), water (H2O ), argon (Ar) / oxygen (O2) (and / or), hydrogen (H2) (only conditionally) and benzene as an internal standard were determined using gas chromatography. The gas chromatograph 6890 (Agilent, based on HP 6890) was used here. The gas chromatograph for this analysis was equipped with three separation columns: 1. HP-CPWAX 52CB 25 m * 0.32 mm * 0.2 μm (here, NH3, HCN, water and benzene were separated), 2. molecular sieve 30 m * 0.32 mm * 12 μm (here, H2, N2, O2, CO and methane were separated), and 3. Lot 30 m * 0.32 mm * 20 μm (here, CO2 and benzene were separate), two thermal conductivity detectors (TCD), a pressure measurement unit and a mass flow meter (MFM) for helium. Column 1 was connected via a rear injector to the rear detector. Columns 2 and 3 were connected by a front injector to the front detector.
    [00066] The procedure of this standard method is known to those skilled in the art.
    [00067] The methyl mercaptan (MC) and methyl mercapto propionaldehyde (MMP) and acrolein (AC) components of the residual gas leaving the top of the column were determined by gas chromatography. In this case, a 7890A gas chromatograph (Agilent) was used. The gas chromatograph was equipped for this analysis with a separation column (HP-INNOWAX 60 m * 0.32 mm * 0.25 μm) and a rear detector (FID). The procedure of this standard method is known to those skilled in the art. Example 1
    [00068] A configuration as shown in Fig. 1 was used, containing a column of 70 mm in diameter, which was equipped with 2 ordered packages (C) and (E) and which had heights in each case of 2,500 and 1,700 mm. Between the ordered packages, an intermediate lower phase (D) was arranged, from which a current (6) can be drawn to operate an upper circuit. Below the column was the stage at the bottom of the column, which has a volume of 4 liters. The diagram of this device is attached (see figure 1).
    [00069] With the current (1), 8.98 kg / h of gas from the crude product of the production of hydrogen cyanide by the Andrussow method were fed through the gas insufflator (B) in phase A of the bottom of the column that contained , based on weight: HCN: 8.87%, H2O: 3.88%, H2: 1.33%, N2: 76.01%, O2: 1.48%, CO: 5.67%, CO2: 1.13%, CH4: 0.39%. The inlet gas was mixed in the jet pump (B) with a circulating current (8) of 300 kg / h. The temperature of the circulation stream was controlled here in such a way that, at the bottom of the column (A), in a 50% filling state, a temperature of 50 ° C prevailed. The feed stream (7) in the ordered package (C), at 40 kg / h, had a temperature of 35 ° C.
    [00070] Methyl thiopropionaldehyde was introduced into the reactor (G) through the feed (2) in an effluent of 2.966 kg / h. The reactor contained, based on weight:
    [00071] MMP: 96.46%, H2O: 2.77%, MC: 0.2%. Through the feed line (3), at the same time 0.211 kg / h of a mixture of 99% by weight of MMP in the composition described above and 1% by weight of triethanolamine as a catalyst were introduced (G). The entire chain (5) consisting of the starting materials and the circulating chain (6) was 40 kg / h in the supply to the upper ordered package (E) at a temperature of 6 ° C.
    [00072] The HCN / MMP molar ratio of the starting material corresponded to 1. The product left the column bottom phase at 4.20 kg / h and had the following composition, based on weight: MMP-CN: 90, 43%, H2O: 7.82%, MMP: 0.14%, HCN: 0.16%, MC: 0.01%. The exhaust gas left the top of the column at 8.07 kg / h and had the following composition based on weight: HCN: 0.00%, MMP: 0.07%, MC: 0.05%, H2O: 1, 34%, H2: 1.48%, N2: 86.02%, O2: 1.64%, CO: 6.31%, CO2: 1.26%, CH4: 0.44%. The gases were fed into a combustion plant. Example 2
    [00073] The installation of Example 1 was used.
    [00074] With the current (1), 8.94 kg / h of the crude product gas from the production of hydrogen cyanide by the Andrussow method were fed through the gas insufflator (B) in phase A of the bottom of the column that contained , based on weight: HCN: 8.9%, H2O: 3.7%, H2: 1.3%, N2: 76.3%, O2: 1.5%, CO: 5.6%, CO2: 1.1%, CH4: 0.4%. The inlet gas was mixed in the jet pump (B) with a circulating current (8) of 280 kg / h. The temperature of the circulation current was controlled in this case in such a way that, at the bottom of the column (A), in a 50% filling state, a temperature of 49.8 ° C prevailed. The feed stream (7) in the ordered package (C) had a temperature of 35 ° C to 40 kg / h.
    [00075] Methyl thiopropionaldehyde was introduced into the reactor (G) through the load (2) at an effluent of 2,976 kg / h. It contained, based on weight:
    [00076] MMP: 96.9%, H2O: 2.8%, MC: 0.2%. Through line (3), at the same time, 0.2 kg / h of a mixture at 99% by weight of MMP in the composition described above and 1% by weight of the triethanolamine charge as catalyst was introduced into the reactor (G). In addition, 2 kg / h of the lower phase product was introduced through the passage (13) in the reactor (G). The entire chain (5) consisted of starting materials and the circulation chain (6) and the product chain (13) was 42 kg / h in the load for the upper ordered package (E) at a temperature of 5.5 ° Ç.
    [00077] The HCN / MMP molar ratio of the starting material corresponded to 1. The product left the column bottom stage at 4.25 kg / h and had the following composition, based on weight:
    [00078] MMP-CN: 90.06%, H2O: 8.81%, MMP: 0.75%, HCN: 0.21%, MC: 0.01%. The exhaust gas exited the top of the column at 7.88 kg / h and had the following composition based on weight:
    [00079] HCN: 0.00%, MMP: 0.09%, MC: 0.10%, H2O: 0.6%, H2: 1.50%, N2: 86.60%, O2: 1.70 %, CO: 6.40%, CO2: 1.20%, CH4: 0.50%. The gases were fed into a combustion plant.
    权利要求:
    Claims (24)
    [0001]
    1. Method for the production of 2-hydroxy-4- (methylthio) butyronitrile, in which 3-methyl mercapto propionaldehyde is reacted with hydrogen cyanide in the presence of a base as a catalyst in a main reaction zone to form nitrile, the aforementioned method being characterized by the fact that residual amounts of gaseous hydrogen cyanide, which leave the main reaction zone, are absorbed in an absorption and post-reaction zone, which contains a mixture of 3-methyl mercapto propionaldehyde and catalyst, and , optionally, 2-hydroxy-4- (methylthio) butyronitrile, and are then reacted.
    [0002]
    2. Method according to claim 1, characterized by the fact that the mixture contained in the absorption and post-reaction zone originates at least partially from the main reaction zone.
    [0003]
    3. Method according to claim 1, characterized by the fact that the main reaction zone contains a reactor with agitation or a reactor with recirculation.
    [0004]
    4. Method according to claim 3, characterized by the fact that the main reaction zone also contains a jet pump.
    [0005]
    Method according to any one of claims 1 to 4, characterized in that the absorption and post-reaction zone contains a device for bringing a gas into contact with a liquid, preferably a column, in particular a column with trays, a compacted bed column, a bubble column reactor, a drip column or, optionally, a reactor that features a mechanically agitated container, a submerged jet reactor or a jet pump.
    [0006]
    6. Method according to any one of claims 1 to 5, characterized by the fact that the absorption and post-reaction zones are part of a reactor with recirculation.
    [0007]
    Method according to any one of claims 1 to 6, characterized in that the substantially gaseous hydrogen cyanide is introduced into the main reaction zone, preferably a gaseous product containing hydrogen cyanide from a production plant of hydrogen cyanide.
    [0008]
    8. Method according to claim 7, characterized by the fact that the hydrogen cyanide content of the gas used is from 1 to 99% by weight, or from 5 to 75% by weight, or from 6 to 22% in Weight.
    [0009]
    Method according to any one of claims 1 to 8, characterized in that the catalyst used consists of low molecular weight or heterogeneous amines, solutions of inorganic bases, or mixtures of acids and low molecular weight amines.
    [0010]
    10. Method according to claim 9, characterized in that the low molecular weight amines consist of: tri- (C 1 -C 2 alkyl) amines, or triethylamine or tri-isopropanolamine, dialkylalkylamines, or dimethyl benzylamine, dialkylarylamines, or N, N-dimethyl aniline, heterocyclic amines, or nicotinamide, imidazole, benzimidazole, 2-fluoro-pyridine, 4-dimethyl aminopyridine, picoline or pyrazine.
    [0011]
    11. Method according to claim 9, characterized by the fact that heterogeneous amines of the general formula are used:
    [0012]
    12. Method according to claim 11, characterized by the fact that the catalyst, according to Formula I, is a base bound to a polymer selected from the group of homologous dialkylamino alkyl polystyrenes or macroreticular dialkylamino resins.
    [0013]
    13. Method according to claim 12, characterized in that the catalyst, according to Formula I, is: diethylamino ethyl polystyrene, diethylamino methyl polystyrene, dimethylamino methyl polystyrene, macroreticular diethyl aminomethyl resin or dimethylamino ethyl polystyrene.
    [0014]
    14. Method according to claim 9, characterized in that the inorganic base used is: alkali metal hydroxide, or NaOH or KOH, alkali metal cyanide, or NaCN or KCN, alkali metal carbonate, or Na2CO3 or K2CO3, or alkali metal hydrogen carbonate, or NaHCO3 or KHCO3, alone or in mixed form.
    [0015]
    15. Method according to claim 9, characterized by the fact that the acid used in mixtures of low molecular weight acids and amines consists of: organic acids, or short-chain fatty acids, or acetic acid, formic acid, acid citric, or organic sulfonic acids, or trifluoro methane sulfonic acid or mineral acids, or sulfuric acid or phosphoric acid.
    [0016]
    16. Method according to any one of claims 1 to 15, characterized by the fact that a pH of 4.5 to 6.0 is selected, or 5.0 to 5.5, measured when using a pH electrode at 23 ° C and a water content of 2 to 14% by weight in the main reaction zone and in the absorption and post-reaction zone.
    [0017]
    17. Method according to any one of claims 1 to 16, characterized in that the main reaction zone is operated at a temperature of 20 ° C to 80 ° C, or 30 ° C to 70 ° C, or from 35 ° C to 65 ° C.
    [0018]
    18. Method according to any one of claims 1 to 17, characterized in that the absorption and post-reaction zone is operated at a temperature of 0 ° C to 30 ° C, or from 4 ° C to 15 ° Ç.
    [0019]
    19. Method according to any one of claims 1 to 18, characterized in that another post-reaction zone is operated at a temperature of 20 ° C to 80 ° C, or from 40 ° C to 70 ° C , or from 45 ° C to 65 ° C, upstream of the discharge site of the MMP-cyanhydrin product, to complete the reaction of HCN and MMP to form MMP-cyanhydrin.
    [0020]
    20. Method according to any one of claims 1 to 19, characterized by the fact that an absolute pressure of 90 to 500 KPa (0.9 to 5 bar), or 10 to 300 KPa (1.0 to 3 bar), or from 100 to 15 KPa (1 to 1.5 bar).
    [0021]
    21. Method according to any one of claims 1 to 20, characterized in that the molar ratio between prussic acid and 3- (methylthio) propanal is from 0.98 to 1.03, or from 0.99 to 1.01.
    [0022]
    22. Method according to any one of claims 1 to 21, characterized in that a weight ratio between the catalyst and 3- (methylthio) propanal from 0.00005 to 0.002, or from 0.0001 to 0.001 is used .
    [0023]
    23. Method according to any one of claims 1 to 22, characterized in that it is conducted discontinuously, semi-continuously or continuously.
    [0024]
    24. Use of a reaction product, containing MMP-cyanhydrin, produced by the method, as defined in any one of claims 1 to 23, characterized by the fact that it is to produce D, L-methionine or 2-hydroxy-4 acid -thiobutyryl methyl.
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    同族专利:
    公开号 | 公开日
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    法律状态:
    2020-11-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-11-10| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    2020-12-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-27| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    US201161445781P| true| 2011-02-23|2011-02-23|
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