TW495500B - Continuous hydrolysis process for preparing 2-hydroxy-4- methylthiobutanoic acid or salts thereof - Google Patents

Abstract

A continuous process for the preparation of 2-hydroxy-4-methylthiobutanoic acid or a salt thereof which includes introducing an aqueous mineral acid into a nitrile hydrolysis reactor including a continuous stirred tank reactor and introducing 2-hydroxy-4-methylthiobutanenitrile into the nitrile hydrolysis reactor. 2-hydroxy-4-methylthiobutanenitrile is continually hydrolyzed within the nitrile hydrolysis reactor to produce a nitrile hydrolysis reactor product stream containing 2-hydroxy-4-methylthiobutanamide. The nitrile hydrolysis reactor product stream is continuously introduced into an amide hydrolysis flow reactor. 2-hydroxy-4-methylthiobutanamide is continually hydrolyzed within the amide hydrolysis flow reactor to produce an aqueous hydrolyzate product containing 2-hydroxy-4-methylthiobutanoic acid. 2-hydroxy-4-methylthiobutanoic acid is recovered from the aqueous hydrolyzate product.

Description

495500 A7 ----- B7 V. Description of the invention (i) Formal examination of the relevant application This application is part of the US Patent Application No. 08 / 477,768 (i 99 5, 6 7 ^ application). case. BACKGROUND OF THE INVENTION The present invention relates to the preparation of 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, and more particularly to an improved method for preparing an aqueous product containing 2-hydroxy-4-methylthiobutanoic acid. -Methyl I-butadiene 'is usually called several amino analogs of methionine and is also 2-hydroxy-4-methylthiobutyric acid or only ... ^ 8, is an essential amino acid methionine I analog .曱 Thiamine analogs such as 1 ^ 1 ^] 8 are effective in supplying methionine for nutritional purposes, especially as a supplement to poultry feed. In order to effectively produce HMBA-containing feed supplements, hydrolysis must be sufficiently complete. HMBAs have been manufactured by various methods, which include 2-hydroxy-4-methylthiobutyronitrile (also known as ΗM BN or 2-hydroxy-4_methylthiobutyronitrile, hereinafter referred to as, HMBN, or ,, nitrile π) Foot hydrolysis. HMBA has been prepared as a racemic d, L-mixture, hydrolyzed ΗΜΝΒΝ by mineral acid, precipitated acid residue by addition of alkaline earth hydroxide or carbonate, and for example described in Blake et al., U.S. Patent No. 2,745,745 By evaporation crystallization, the salt of HMB A was recovered from the aqueous phase. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) British patent brother No. 915,19j $ has described a method for preparing HMBA4 bow salt, in which the reactor used for continuous mixing is diluted H2S〇 "# liquid hydrolyzes HMBN to HMB A, and Η Μ BA is separated from the reaction solution by ether extraction. Due to the use of a continuous reverse mixing reaction system, the method of the British patent cannot achieve the complete conversion of HMBN or amidine intermediates Μ Μ BA. When a liquid Η Μ BA product is to be produced, the presence of a significant amount of unreacted substances is undesirable. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 A7 _ _ B7 V. Description of the invention (2) Recently, 'HMBN has been commercially hydrolyzed by sulfuric acid to form a high-quality hydrolysate containing HMBA. The HMBA is extracted from the hydrolysate and borrowed from Ruest et al., US Patent No. 4,524,077. Recovered ^^ 6 VIII made 11 ^^ person. In this method 'HMBN and sulfuric acid with a strength between about 50% and about 70% by weight (based on the basis of no organic matter) in about 2 5 it Between about 6 and 5 Under mixing. To control the reaction rate, it is better to add Η Μ BN to the acid within a period of about 30 to about 60 minutes. Under better conditions, about ½ / 2 hours and about 1 / 1/2 The substantial conversion of this nitrile into 2-mercapto-4-methylthiobutamidamine occurred within a period of 4 hours and is hereinafter referred to as " fluorenamine "). Thereafter, it was at about 70 ° C and 20 ° C. At temperatures between 0 and 5%, amidine was converted to HMBA by additional hydrolysis. The final hydrolysis of amidine to acid is performed in H2S04 with an initial strength between about 30% and about 50% by weight (based on this organic matter). To provide better acid strength, the aqueous phase is diluted by adding water before heating the reaction mixture. Under the conditions of fairly dilute acid strength and increased temperature, amidine is converted to acid within a period of about 1 1/2 hours to 3 hours. In performing the hydrolysis, about 1 mole of sulfuric acid was used per mole of HMBN feed, with a 0 to 10% excess (preferably 0 to 5%) of acid, providing satisfactory results. R u e s t et al described the batch process and Chen Yuan batch process. It was better to ensure that the hydrolysis reaction proceeded qualitatively to completion. If a continuous reaction system is used, the description of Ruest et al. Should be designed and operated to ensure a substantially complete transformation. For example, continuous operation can be performed in a plug flow tube reactor or a cascade tank system. A single inverse mixing reactor, as described by Ruest et al., Provides a sufficient conversion only for dwell times that are generally considered unacceptable for commercial manufacturing.

Hernandez et al., US Patent No. 4,912,257 describes that HMBA applies the Chinese National Standard (CNS) A4 specification (210X297 mm) by this paper size (please read the precautions on the back before filling this page. • Staff of the Central Bureau of Standards, Ministry of Economic Affairs Printed by the Consumer Cooperative 495500 A7 B7 V. Description of the invention (3) HMBN is produced by a single step of sulfuric acid hydrolysis. Η Μ BN is fed into an acidification vessel, where it is mixed with 98%. H2S〇4 to The acid / nitrile mole ratio is mixed between 0.5 and 2 to form a reaction mixture containing 20-50% by weight. H 2 S 0 4. When the reaction mixture is manufactured in batches, the mixture is added in a continuous addition loop. Stir and cool to 50 ° C for 30-60 minutes. The reaction mixture is then fed into the hydrolysis reactor and heated at a temperature between 60 ° C and 140 ° C for 5 minutes to 6 hours while applying Micro-vacuum to the reactor. It is said that the method described by Hernandez et al. Produced HMBA by hydrolyzing acidified HMBN solution in a single step, unlike the two-step hydrolysis method known in the art. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs System (read first Please fill in this page before filling in this page.) In order to provide high-quality hydrolysate with the maximum amount of HMB A and the minimum amount of nitrile and amidine components, HMBN and 2-hydroxy-4-methanbutamine must be highly converted into amidine. Μ BA. Batch manufacturing of HMB A provides high conversion. However, the conventional batch method of manufacturing HMB A has several disadvantages. The manufacturing power of the batch method is limited by the batch reversal time. In addition, because each The reaction conditions can be changed during batch manufacturing, so the quality of HMBA hydrolysate will vary from batch to batch. Filling and emptying of batch reactors and non-steady state conditions cause vapor emission, which must be processed before release. Previous techniques The equipment required for the method is expensive. Mix H 2 S04 with water in an acid dilution barrel to form a dilute sulfuric acid feed. A heat exchanger is required to remove the heat of dilution generated in the barrel. The barrel, heat exchanger, pump, and The recycling loop must be of anti-corrosive composition. SUMMARY OF THE INVENTION Among the several objects of the present invention, to provide an improved HMB A preparation method; to provide such a method that can be operated in a continuous manner; to provide such a method that can be operated with high productivity; When compared with the conventional method, it can effectively reduce the main paper size. Applicable to China National Standard (CNS) A4 specification (210X 297 mm) 495500 A7-* --- B7 V. Description of the invention () (Please read the back first Please pay attention to this page before filling in this page) 2. This method of 隹 濩 cost; provide a method to control the reaction conditions when changing compared with the conventional batch hydrolysis system ^, provide the method of batch and conventional, This method of reducing the gas emission when comparing gram and gram; provides the method to eliminate the separated 1 acid dilution < required method, especially provides a method which can be operated with concentrated H2S04 feed stream without previous dilution; provides substantially effective A method to completely convert HMBN to HMBA; and a method to provide a consistent quality HMBA for use in preparing animal feed supplements. These and other objects are obtained by a method of preparing HMBA or a salt thereof, including adding mineral acid to a nitrile hydrolysis reactor containing a continuous stirred tank reactor, and adding 2-hydroxy-4-methylthiobutyronitrile to a nitrile hydrolysis reaction. Device. In the nitrile hydrolysis reactor, 2-hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed to produce a nitrile hydrolysis reactor product stream containing 2-hydroxy-4-methylthiobutamine. The nitrile hydrolysis reactor product stream is continuously introduced into the amine hydrolysis flow reactor. In the hydrazine hydrolysis flow reactor, hydrolyzation of 2- and 4-benzyl-4-methylthiobutyric acid amine to produce an aqueous hydrolysate containing το formed by 2-methyl-4-methylthiobutyric acid. From the completed aqueous hydrolysate, 2-kidoxy-4-methylthiobutanoic acid was recovered. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed in another specific embodiment of the present invention, in which 2-hydroxymethylthiobutyronitrile and concentrated osmium 2 S 〇 4 have a weight ratio of about 70% and a weight ratio of about 99%. The strength between the two, and the method of simultaneously adding water to a container, and hydrolyzing 2-hydroxy-4-methylthiobutyronitrile therein to produce 2-hydroxy-4-methylthiobutyric acid or a salt thereof. Hydrolysis of 2-hydroxy-4-methylthiobutyronitrile in a container yields an aqueous hydrolysis mixture containing 2-hydroxy-4-methylthiobutamide. The hydrolysis of 2-hydroxy-4-methylthiobutanamine produces a completed aqueous hydrolysis product containing 2-hydroxy-4-methylthiobutanoic acid. 2-Hydroxy-4-methylthiobutanoic acid was recovered from the completed aqueous hydrolysate. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A7 B7 V. Description of the invention (5) Another specific embodiment of the present invention is intended for use in Apparatus for preparing HMBA. This unit includes the first continuous stirred tank reactor for the continuous hydrolysis of 2-hydroxy-4-methylthiobutyronitrile in the presence of mineral acid to produce an aqueous hydrolysis mixture containing 2-hydroxy-4-methylthiobutamine. The unit also includes a hydrazine hydrolysis flow reactor for the continuous hydrolysis of 2-hydroxy-4-methylthiobutane amine and H2S04 to produce a completed aqueous hydrolysate containing 2-hydroxy-4- thiosulfate. In addition, a specific embodiment of the present invention is directed to a method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, which includes introducing 2-hydroxy-4-methylthiobutyronitrile and an aqueous mineral acid into an aqueous hydrolysate, which contains 2 -Hydroxy-4-methylthiobutamide, mineral acid and unreacted 2-hydroxy-4-methylthiobutyronitrile. 2-Hydroxy-4-butyrothiobutyronitrile in an aqueous hydrolysis mixture is hydrolyzed in a continuous nitrile hydrolysis reactor containing a backmixing reaction zone and a circulation zone in a fluid flow communicating with the reverse mixing reaction zone. The loop area contains loop lines. The aqueous hydrolysis mixture is continuously circulated in the circulating flow withdrawn from the remixing reaction zone, and then returned to the backmixing reaction zone through the circulation zone. When the circulating flow withdrawn from the backmixing reaction zone contains unreacted 2-hydroxy-4 -Methiobutyronitrile. A portion of the aqueous hydrolysis mixture is removed from the forward flow port in the circulation zone, forming a nitrile hydrolysis reactor product stream. The nitrile hydrolysis reactor product stream is transferred to the amidine hydrolysis stream reactor. The nitrile hydrolysis reactor product stream is a reaction stream that is diluted with water downstream of the forward flow port to complete the reaction stream. Hydrolyzation of 2-methyl-4-methylthiobutyramine in the completed reaction stream in a hydrazine hydrolysis flow reactor produces a completed aqueous hydrolysate containing 2-hydroxy-4-methylthiobutyric acid. The sum of the residence time of the circulating stream in the circulation zone upstream of the forward flow port and the residence time of the product stream of the nitrile hydrolysis reactor downstream of the forward flow port before dilution, before the product stream of the nitrile hydrolysis reactor is diluted, It is sufficient to substantially distinguish the remaining 2-hydroxy-4-methylthiobutyronitrile. This paper size applies to China National Standard (CNS) Α4 size (210X297 mm) (Please read the precautions on the back before filling out this page) • I · 495500 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (<) 6 Brief description of the drawing Figure 1 is a schematic flow chart of the method of the present invention 'illustrates the continuous manufacturing of HMBA from HMBN, water and mineral acid; Figure 2 is the type illustrated in Figure 1 when modified to ensure Schematic flow chart of a preferred method in which residual HMBN can be substantially distinguished; Figure 3 is a schematic flow chart of the method of the present invention, in which the 2-hydroxy-4-methylthiobutanamine leaving the nitrile hydrolysis reactor is continuously The stirred tank reactor and the continuously operated ammonium hydrolysis flow reactor are converted to HMB A; Figure 4 is a diagram illustrating a preferred method of the type shown in Figure 3 when modified to ensure that residual HMBN can be substantially distinguished Figure 5 is a diagrammatic illustration of a continuous stirred tank reactor suitable for converting HMBN to 2-hydroxy-4-butathioamide when a concentrated sulfuric acid stream is introduced into the reactor. Figure 6 is a diagram As shown in Figure 5, it is suitable to convert HMBN to amidine. Schematic illustration of a continuous stirred tank reactor that can distinguish HMBN before dilution; Figure 7 is a schematic flow chart of a laboratory-scale continuous hydrolysis process, in which 2-hydroxy-4 -methanine leaves the first cycle reactor Amidine is converted to HMBA in the second cycle reactor and plug-flow reactor with continuous operation; Figure 8 shows the amidine concentration, nitrile concentration, and the Gardner color of the hydrolysate fed to the first reactor are acid. A graph of the function of the molar ratio of nitrile to nitrile and the temperature in the plug flow reactor (based on laboratory scale experiments); and Figure 9 is a diagrammatic flow chart of a laboratory scale continuous hydrolysis process, in which 2 leaving the first reactor -Hydroxy-4-methylthiobutamide is introduced into a plug flow reactor and hydrolyzed to produce ΜBA. This paper size applies to China National Standard (CNS) A4 specifications (210 x 297 male shame) (Please read the precautions on the back before filling out this page), -'tv 495500 A7 B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (7) Element code description 10 represents a continuous churning tank reactor (CSTR); 12 represents a back mixing reaction zone; 14 represents a circulation line;] 6 represents an SS amine hydrolysis flow reactor; 1 8 represents a pipeline; 2 0 represents a pipeline; 2 2 represents a pump; 2 4 represents an external heat exchanger; 2 6 represents a forward flow port; 2 8 represents a transfer line; 30 represents a dilution point; 3 2 represents an on-line mixer; 3 4 represents a preheater; 36 represents a CSTR; 38 represents a water heater; 40 represents a cooler; 42 represents a hydrolysate balance tank; 4 4 represents a pipeline; 4 6 Represents a recycling reactor; 4 8 represents a chestnut; 50 represents a recycling reactor; 5 2 represents a pump; 5 4 represents a coil; (Please read the notes on the back before filling out this page) •• I binding ' This paper size applies to Chinese National Standard (CNS) A4 Specifications (210X 297mm) 495500 Α7 Β7 V. Description of the invention ()-8 5 6 represents a certain temperature oven; 5 8 represents a coil; 60 represents a small mixing circle; 6 2 represents a pump; and 6 4 Represents a hot bath. The details of the light-weight embodiment are printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Continuous hydrolysis in acid to form 2 • min · 4_methylpyramine (hereinafter referred to as " nitrile hydrolysis "), and continuous hydrolysis to form 111 ^ .: 6 eight (hereinafter referred to as " hydrazine hydrolysis ") '. This method uses a first continuous stirred tank reactor (hereinafter referred to as ncs τ r,), a nitrile hydrolysis and ammonium hydrolysis flow reactor, preferably a plug flow reactor (also referred to as `` PFR ''), It is used for the subsequent hydrolysis of amidine. The nitrile water liberation heat is large, so it is most effectively carried out under the CSTR reverse mixing heat transfer and temperature control. The amidine water liberation heat is less, but it must be almost completely to achieve the required Product quality and yield. PFR has been found to be very suitable for amine hydrolysis because it can be configured to operate without substantial backmixing, but provides sufficient dwell time for the reaction without undue pressure drop. For example, it has been found Industrial scale pipeline reaction It can be operated at an excess Reynolds number of about 5000 without excessive pressure drop throughout the reactor, resulting in a hydrolysate containing less than about 0.1% amidine and less than about 0.1% nitrile based on Η Μ BA. In particular, the present invention is directed to a device comprising a nitrile hydrolysis reactor containing a CSTR for receiving an aqueous mineral acid and a ΜM BN feed stream. For the purposes of the present invention, the aqueous mineral acid is water and up to 99% by weight mineral acid The composition of hydrous mineral acid is generally sulfuric acid or hydrochloric acid. Sulfuric acid is particularly preferred. When Μ Μ Β Ν reacts with water in CSTR to form -11-This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297). 495500 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (9) Aqueous hydrolysis mixture containing 2-hydroxy-4-methylthiobutamide. The amidine is typically hydrolyzed to some in a nitrile hydrolysis reactor. To the extent that the ammonium salt and BA BA are formed in the hydrolysis mixture. The aqueous hydrolysis mixture is continuously removed from the CSTR, cooled and returned to the CSTR. A portion of the circulating aqueous hydrolysis mixture is removed from the 'flow port' to form nitrile water. Reactor product stream. This stream is diluted to form a complete reaction stream before being introduced into the flow reactor for completion of amidine hydrolysis. Because ammonium is hydrolyzed to some extent in nitrile hydrolysis preparations, it is generally preferred to dilute the nitrile hydrolysis reactor product. A solution that can practically provide water for ammonium hydrolysis and prevent liquid phase separation. Dilution also prevents the precipitation of ammonium bisulfate when sulfuric acid is used. However, it has been found when the dilution point is close to the point of the aqueous hydrolysis solution withdrawn from the CSTR. The residual% can be introduced into the elementary reaction stream. Because the nitrile hydrolysis rate can be reduced by adding dilution water, the residual wax can be increased in the product. It has also been found that residual nitrile can provide excessive but important flow before dilution. The dwell time of the system allows the nitrile hydrolysis reaction to be completed qualitatively and reduced to a very low content. More specifically, 'it has been found that the residual nitrile is substantially distinguishable by providing a residence time of the nitrile hydrolysis flow system of at least about 20 seconds, and depending on the degree of anti-mixing, preferably about 30 seconds and about 5 Between minutes, for example, by the sum of the residence time between the point withdrawn from the csTR and the forward flow port plus the residence time of the nitrile hydrolysis reactor product stream between the forward flow port and the dilution point. For the purposes of the present invention, residual nitriles can be substantially distinguished when no more than about 0.05% by weight nitrile is left in the completed reaction stream. It has also been found that concentrated Ηθ04, water, and HMBN can be simultaneously and directly introduced into the first CSTR to produce a more dilute effective sulfuric acid strength in the CSTR that is suitable for ΗΜΒΝ hydrolysis. Μ Μ Β Ν, water and concentrated H 2 S〇4 can be simultaneously fed to the first -12-This paper size applies to China National Standard (CNS) Α4 size (210X 297 mm) (Please read the precautions on the back first (Fill in this page again) 、 Printed by 495500 A7 _____B7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1A)

Within 1U C / TR without hindering HMBN hydrolysis, despite the different densities and viscosities of sulfuric acid and HBMN and release of high dilution heat when dilute hso and worship with water. ¥ 〇4 Dilute the reaction in the same way as the separate acid used in the conventional method (required, reduce costs and maintain the hydrolysis system. The water and acid required for the hydrolysis reaction can be mixed with any practical concentrated h2S04 diluted acid and water Introduced to achieve the concentration required for the first hydrolysis and the proportion of mineral acid. In the specific embodiment of the invention illustrated in Figure 3, the nitrile hydrolysis reactor product stream removed from the wax hydrolysis reactor is diluted with water A hydrazone hydrolysis stream is formed, which is fed to the second cstr before moving to the hydrazine hydrolysis flow reactor. Alternatively, the nitrile hydrolysis · reactor product stream and water stream can be straightened. Borrowed in the second hydrazine—step hydrolysis will The substantial part of the amine ^ = HMBA forms the elementary reaction stream. The completed reaction stream is then hydrolyzed in a hydrazine hydrolysis flow reactor located below the second csTr to form a completed aqueous hydrolysate containing 11% 8 A. Alternatively The second CSTR can be supplemented with a bypass tube to cause the completed reaction stream to be continuously fed directly into the amidine hydrolysis flow reactor and hydrolyzed to form a hydrolysate. The method of the present invention has been found to be capable of producing more than one consecutive CSTRs with high productivity. Operate in a reactor with flow. Therefore, the main cost of implementing this method, when compared to batch methods deemed necessary in the prior art, is to greatly reduce and provide sufficient conversion with high productivity. This continuous hydrolysis method has been found It can provide high-quality hydrolysate that efficiently converts hmbn to HMBA, producing very low amounts of HMBN and 2-hydroxy-4-methanbutamine. To produce high-quality feed supplements containing HMB A, the method of the present invention It can be operated with high productivity to produce a completed aqueous hydrolysate, which is at least about 06% by weight 1 ^] \ 48, at least about 18% by weight, according to the national standard (CNs) Α4 specification according to the salt, at least about this paper size (210X297 mm) (Please read the notes on the back before filling this page) Order, '495500 A7 B7 V. Description of the invention (u) 20% by weight water, south to about 0.05% by weight amidine and up to Approx. 005 weight. / 0 month cream. The HMBA in the completed aqueous hydrolysate contains HMBA monomers and dimers and other oligomers. When the mineral acid used for hydrolysis is Ηβ04, the aqueous hydrolysis is completed Product contains at least about 36 weight % Η μ BA, at least about 30% by weight as a salt such as ammonium bisulfate or ammonium sulfate, at least about 25% by weight water, up to about 0.05% by weight amidine and rhenium to about 005% by weight nitrile. When used in When hydrochloric acid is used in the hydrolysis, the completed aqueous hydrolysate contains at least about 50% by weight 11 "[38, at least about 18% by weight I / O gasification, at least about 20% by weight water, and up to about 0.05% by weight % Ammonium and hydrazone to about 0.05% by weight nitrile. In a particularly preferred embodiment of the invention, starting with Ha S 0) and resulting in a better hydrolysate composition can be consistently produced throughout all process operations In the steady state, a substantially complete transformation is achieved. According to the method of the present invention, a relatively pure aqueous hydrolysate can also be prepared by using a lower ratio of acid to nitrile for hydrolysis. Such an aqueous hydrolysate contains at least about 30% by weight 2-isopropyl-4-methylthiobutanoic acid, at least about 20% by weight ammonium salts such as ammonium sulfate or ammonium bisulfate, at least about 25% by weight water, up to about 5% by weight of amidine and hydrazone to about 0.1% by weight of nitrile, and having a color not exceeding about 丨 0 (based on the Gardner scale). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) In general, before establishing a stable situation, for example, at the beginning, the hydrolysate produced can contain specific quality Η Μ BA products required Higher ammonium amines and nitriles. It has been found that this compositional fluctuation can be prevented by operating at a higher molar ratio of mineral acid to nitrile in the beginning of the reaction to quickly establish a stable situation. Assume that all mineral acids and HMBN Introduced the first CSTR reactor, but separated the mineral acid flow-partly introduced directly into the amine hydrolysis flow reactor. Therefore, the molar ratio of mineral acid to nitrile is based on the accumulation of mineral acid and nitrile in the process. Rate. Applicable to China National Standard (CNS) A4 specification (210X297 mm) at higher mineral paper size. B7 V. Description of the invention (12) Red to ride ratio is lack of operation + Guishi, # Rate in the reactor So that the second measure is to control the flow of money to the sum of the nitrile and amidine in the amidine hydrolysis flow reactor. The anti-molar ratio is about I. and about 2 .... of; =: = Hour, ah , Better than about U and about 15 gates to establish stability After reaching a stable state, H2S ◦ ^ 1.15 and about L25 4 + Ruyi Er ear is better than about 0. ό and about 1.5 'Car father good place in about 0.99 set, ， Between 1 and 2 I, and more preferably between about 0.9 5 and about 1.05. When hydrolyzed with H c 丨% 咛 疋 resentment <HC1 to Molar ratio of nitrile 21.0 to about U It is better to be between S05 and K3, more preferably; "1, · 15 and 1.2". The above-mentioned preferred ratio of acid to nitrile is the most suitable for the high-energy housing method. For the most effective control, the rate of mineral acid is preferably at least more than equal to 5% of the rate of the sum of nitrile and amidine. Reducing the ratio of acid to nitrile can reduce the color of the finished aqueous hydrolysate and reduce the operating costs, as described herein The lower acid to nitrile ratio operation, if you want low # use, low productivity can be better when the production of water-soluble hydrolyzed products. Central Bureau of Standards of the Ministry of Economic Affairs, Consumer Cooperatives, printed Figure 1, 2-hydroxy-4 _ Thiobutamide is continuously produced by hydrolyzing HMBN in CSTR 10. At the beginning of this process, a mineral acid feed stream is introduced into reactor 10 and back mixed therein. The reaction zone 2 is mixed. Then HMBN is introduced into the mineral acid stream, where it reacts with water in the aqueous hydrolysis mixture to form ammonium amine. When Μ BN and mineral acid stream are continuously fed into the aqueous hydrolysis mixture in the reactor In the middle period, continuous nitrile hydrolysis occurs. The ore is preferably h2S04 with a strength between about 50% by weight and about 70% by weight, preferably between about 60% by weight and about 70% by weight. H, s〇4 as a catalyst 'and no consumption in the nitrile hydrolysis reaction. However, with ammonium water -15-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 5500 Α7 Β7 V. Description of the invention (13) The decomposition reaction (which usually occurs to some extent in the nitrile hydrolysis reactor) consumes this acid, resulting in the formation of NH4HS04 when H2S04 is used in the nitrile hydrolysis reaction. The reaction is carried out at a temperature between about 4 ° C. and about 70 °, preferably between about 60 ° and about 65.0, and at a total pressure between about 0 and about 15 psig. The aqueous hydrolysis mixture contains In the reactor 10, the dwell time is between about 20 minutes and about 60 minutes, preferably between about 25 minutes and about 45 minutes. The calculation of the dwell time within cs TR 100 is made by CSTR The volume of the aqueous hydrolysis mixture in 10 and circulation line 14 is divided by the volumetric flow rate of the nitrile hydrolysis reactor product stream moving through the forward flow port 26 to the downstream. The aqueous hydrolysis mixture manufactured in CSTR 10 contains up to about 6 % By weight Η Μ BA, up to about 12% by weight, ammonium salt, at least about 6% by weight water, at least about 30% by weight amidine and up to about 2% by weight nitrile. When using H 2 S〇4 The aqueous hydrolysis mixture produced in CSTR 10 contains up to about 16% by weight ΗΜΒΑ, up to about 12% by weight ammonium salt, such as NH4HS04 or (NH4) 2 S 〇4, at least about 6% by weight, at least About 35% by weight ammonium amine and up to about 2% by weight nitrile, preferably between about 5 and about 12% by weight Η Μ BA, between about 4 and about 9% by weight Ammonium salt, between about 10 and about 15% by weight water, between about 35 and about 50% by weight amidine and up to about 2% by weight nitrile, and more preferably, containing about 5 Μ BA between about 11% by weight, ammonium salt between about 4 and about 8% by weight, water between about 11 and about 13% by weight, between about 40 and about 50 Acid amines between about 1% by weight and nitriles up to about 1% by weight. When HC 1 is selected as the mineral acid for the nitrile hydrolysis reaction, the acid preferably has a content between about 30% by weight and about 40% by weight. Strength, more preferably between about 35% by weight and about 37% by weight. HC 1 acts as a catalyst and is not consumed in the nitrile hydrolysis reaction. However, HC 1 is generally used in nitrile hydrolysis reactors. Occurred to some degree -16-This paper size applies to China National Standard (CNS) Α4 size (210 × 297 mm) (Please read the precautions on the back before filling this page) Order printed by the Central Consumer Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A 7 B7 ------------------------ 5. Description of the invention (14) Consumption of amine fermentation hydrolysis Stingy NH4C1 is formed in the alkaline hydrolysis mixture. After the finished aqueous hydrolysate is obtained, any NH4C1 solids are soluble. This reaction is at a temperature between about 25 ° C and about 60 ° C, preferably about 45 ° C and Between about 5 5 ° C, and under total pressure between about 2 and about 15 psig. • The aqueous hydrolysis mixture is contained in the reactor 10, and the residence time is about 25 minutes and about 60. It is preferably between about 40 minutes and about 50 minutes. When HC 1 is used, the aqueous hydrolysis mixture produced in CSTR 10 contains up to about 10% by weight BA BA, up to about 5% by weight NH 4 C 1 and at least about 20% by weight water / 0%, At least about 40% by weight amidine and up to about 2% by weight nitrile, preferably between about 2 and about 10% by weight of MGBA, between about 0.5 and about 5% by weight of NH4C1, about 20 and about 30% by weight of water, about 40% and about 60% by weight of fermented amines, and about 0.5% by weight of wax, and more preferably, HMBA of about 5 and about 9% by weight, NH4C1 between about 0.5 and about 4% by weight, water between about 25 and about 30% by weight, fermented amine between about 45 and about 60% by weight, and up to about 0.1% by weight % Wax. In an alternative embodiment of the present invention, the mineral acid stream is separated such that a portion is fed to CSTR 10 and the rest passes upstream of line 18 at the inlet of on-line mixer 32 as shown in Figures 1, 2 and 4 Feed, or via line 20 to be fed to a continuous amidine hydrolysis reactor, as shown in Figure 3

~ He amine hydrolyzed mixture of C S T R 3 6. Feeding to ^ s TR 1 0 _ "^^ Bismuth to Nitrile Molar ratio is between about 0.6 and about 1.5, preferably between about 0.8 and about 〖1 1 z &lt; between. The ratio of total molar acid to nitrile is between about 0.7 and about 1.5, preferably between about 0.9 and about 1.2, and more preferably between about 0.95 and about 1.0. between. The ratio of total molic acid to nitrile for the purpose of this cigarette is x for any mineral acid feed stream &quot; ^ and divided by -17-This paper size applies to China National Standard (CNS) A4 (210X 297) Gongchu) &quot;-

I (Please read the precautions on the back before filling out this page} Order '495500 A7 B7 V. Description of the invention (15) Nitrile feed to nitrile hydrolysis reactor. When you want low cost, low productivity to produce the finished hydrolysate A lower molar ratio of acid to nitrile is preferred. In these cases, the molar ratio of acid to nitrile fed to cstr 〇 is between about 0.5 and about 0.95, and preferably about 0. 8 And about 0.9 5. The ratio of total molate to nitrile is between about 0.6 and about 0.95 ', preferably between about 0.8 5 and about 0.95. In Figure 1, continuous The nitrile hydrolysis reactor also includes a circulation zone in the fluid flow with the back-mixing reaction zone 12. The circulation zone includes a circulation line 4 through which the aqueous hydrolysis mixture withdrawn from the back-mixing reaction zone 12 is pumped. 2 2 continuous circulation. The external heat exchanger 24 is preferably included in the circulation line to remove the exothermic reaction heat by transferring to the coolant. After passing through the pump 22 and the heat exchanger 24, the aqueous hydrolysis mixture returns to Mix the reaction zone 1 2. In the circulation zone, remove a part of the aqueous hydrolysis mixture from the forward flow port 2 6 to form a nitrile hydrolysis The product stream of the reactor is moved to the ammonium hydrolysis flow reactor 16. The temperature of the aqueous hydrolysis mixture circulating in the entire circulation zone is at least 3, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) Fill out this page again) Better than 40. (3 and about 60. (: Between. When using Η2 S04, the temperature is at least about 50. (3, better than about 55 ° C and about 6CTC) Between (in the entire circulation zone), and when using HC 1 ', the temperature in the entire circulation zone is at least about 30 ° C, preferably between about 40C and about 50C. The reactor 10 can be provided with jackets, providing Additional cooling capacity, and if required at the beginning, the contents of the heating reactor are also provided. The liquid content in the reactor is maintained by the content controller. Although the liquid content can also be controlled from the gravity overflow of the reactor If you use positive content control, it is easier to design the hydrolysis system, and the content controller is also good. Because the size of the water-based paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 A7 V. Description of invention (M ) The solution mixture is sticky. The use of the controller makes it possible to change the working capacity and dwell time of the reactor according to the operator's choice, for example, to adapt to changes in the throughput of the material. In a particularly preferred embodiment of the present invention, a flow regime of at least about 2G seconds The dwell time is provided to effectively complete the nitrile hydrolysis before the reaction solution is diluted for ammonium hydrolysis. Figure 2 illustrates this configuration. The hydrolyzed mixture leaving the back-mixing reaction zone 12 is preferably not from the pumping side of the pump 22 Remove, and instead transport through the circulation line 14 through the circulation line 14 to the forward flow port 26 located on the circulation line via the pump 22, to provide a sufficient downstream distance of the pump foot, to provide a flow reaction system, preferably one of which is consumed Residual nitrile plug flow section. Advantageously, the forward flow port 26 is so selected to provide a residence time of at least about 3 seconds, typically between about 3 seconds and about 1 $ second, and preferably between about 5 seconds and about 10 seconds. Flow above the flow port 2 6 of the circulation system 1 4 to promote the reaction of the residual nitrile. Since the substantial volume of the aqueous hydrolysis mixture is circulated through the heat exchanger 24 to remove the reaction heat, the flow system in the circulation line is maintained in a system that is easily disturbed, so that the circulation between the point of withdrawal from CSTR 10 and the flow port 26 The part of the system 14 is substantially used as a plug flow reactor. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) Part of the circulating aqueous hydrolysis mixture such as the nitrile hydrolysis reactor product stream is removed from the forward flow port 2 6 and the remaining circulating stream Flow back to CSTR 10. To ensure the most effective reduction of residual nitrile, provide at least about 30 seconds, preferably between about 30 seconds and about 5 minutes, more preferably between about 30 seconds and about 3 minutes, more The dwell time of the flow system between about 2 minutes and about 3 minutes is used to complete the nitrile hydrolysis reaction in the flow system nitrile disappearance reaction zone, which is part of the circulation line between the exit of CSTR 10 and the forward flow port 26 Product transfer line with nitrile hydrolysis reactor 2 8 Dilution point 3 〇 This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 495500 Printed by A7 B7, Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 17) It is composed upstream, so, as mentioned above, between the point of withdrawal from the CSTR 10 and the flow port 26, it is advantageous to provide a residence time between about 3 seconds and about 15 seconds, and the conveyor line 2 8 is better Structured to improve Provide a residence time between about 10 seconds and about 5 minutes, more preferably between about 30 seconds and about 5 minutes, and most preferably between about 1 minute and about 3 minutes. To provide the required residence time Without excessive flow speed and pressure drop, the conveyor line 28 can be configured for thin layer flow, but for any flow conditions, the conveyor line provides at least one equivalent back-mixed reaction zone. The conveyor line 28 can also be structured Type for disturbing flow. Preferably, the speed is such that at least about two equal back-mixed reaction zones are provided in the aforementioned nitrile disappearance reaction zone, and more preferably between about 3 and about 5 back-mixed reactions in sequence The equivalent area of the zone. In a specific embodiment of the special, the residual HMBN at the dilution point 30 in the product stream of the nitrile hydrolysis reactor is not higher than the sum based on the sum of HMBA and amidine contained in the product stream of the nitrile hydrolysis reactor. About 0.01% by weight. The transport line 28 is preferably configured as a vertical lower duct, so that nitrogen or other gases taken away by the aqueous hydrolysate mixture in CSTR 10 can be liberated from the downward flowing liquid and released through the lower duct. Top of conveyor line 2 8. Although horizontal structure is available However, any gas in the horizontal line can be liberated and accumulated from the forward flow, reducing the effective liquid volume in the pipeline. When the nitrile hydrolysis reactor product stream is transported downstream of the forward flow port 26, it is in the on-line mixer 3 2 is mixed with any separated part of the water flow and mineral acid flow to form a complete reaction flow. The product stream of the nitrile hydrolysis reactor is mixed with the water flow and any acid flow to ensure that the homogeneous liquid mixture is led to the ammonium hydrolysis flow reactor 16. Any water stream is then diluted in the mineral acid in the completed reaction stream, which provides the consumed reaction water in the acid-amine hydrolysis, and reduces the viscosity of the completed reaction stream. When using sulfuric acid, the paper size applies the Chinese National Standard (CNS) A4 Specifications (210X 297mm) (Please read the notes on the back before filling out this page) Order-1¾ 495500 A7 _B7 V. Description of the invention (18) The dilution of the product flow of the nitrile hydrolysis reactor can avoid the hydrolysis of the ammonium amine Liquid phase separation or sinking of NH4HS04 in reactor 16. When hcI is used for hydrolysis, NQ / 1 will typically precipitate. The water stream is typically provided to provide a ΗθΟ * strength in the completed reaction stream between about 30% and about 50% by weight based on the absence of organic matter, preferably between about 35% and about 45% by weight, and more It is preferably introduced at a rate of about 43% by weight. If H C 1 is used at a weight ratio of about 30% to about 38%, no additional water is required. The strength of HC 1 in the completed reaction stream is between about 30% and about 40% by weight based on organic-free matter, preferably between about 35% and about 38% by weight, and more preferably about 36%. weight ratio. The water stream can be heated 'before being mixed with the nitrile hydrolysis reactor product stream to form a completed reaction stream, or the completed reaction stream can be heated before being fed to the amidine hydrolysis flow reactor 16 to provide the required reactor operating temperature. Typically, the water stream is heated to between about 60 ° C and about 100 ° C, preferably about 70 ° C. 〇 and about 90. (: Between, and more preferably between about 75 ° C and about 80t. If the water is not preheated or the temperature of the reaction stream is too low, this stream can be brought to the required temperature in the preheater 34. The residence time of the completed reaction stream between the dilution point 30 and the entrance to the amidine hydrolysis stream reactor is not important. The complete reaction stream is thoroughly mixed in this zone before entering the amidine hydrolysis flow reactor 16. Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the notes on the back before filling this page). In the amidine hydrolytic flow reactor, some residual HMBN is hydrolyzed to form another fermented amine, which is then hydrolyzed to HMBA. Preferably, the ratio of water to hydrazine fed to the amidine hydrolysis flow reactor is between about 5 and about 1.00. The flow rate to complete the reaction stream is preferably operated to maintain the amidine hydrolysis flow reactor. A suitable speed to maintain disturbances and reduce anti-mixing of the shaft. As indicated above, the dwell time specified in the amidine hydrolytic flow reactor has been adapted to the Chinese national standard (CNS) A4 specification Ul0X297. 19 ^ 5500 A7 five Description of the invention (It is found that by increasing the mineral acid / nitrile mole ratio in the feed, the conversion can be substantially increased. Experiments have shown in some cases that when the H2S04 / nitrile mole ratio is L0, it is stable at the beginning ^ 2 hours State, but when the molar ratio of 304 / nitrile is u, a stable state can be obtained almost immediately. The rapid establishment of a stable state enables consistent production of high-quality hydrolysate, which leaves the hydrazine hydrolysis flow reactor. Contains up to about 0.05% by weight ammonium amine and up to about 0.05% by weight nitrile. However, the consumption of excess mineral acid, if the steady state is established, the increased mineral acid / nitrile is maintained during the routine% production operation. Ear ratio can be prevented. Therefore, it is better to use Ηβο, / nitrile molar ratio between about ι · 〇 and about 15 only from the beginning to the establishment of a stable state in the hydrazine hydrolysis flow reactor. Better than = 1.15 and about 1.25 to avoid the production of substandard hydrolysates during the start. When the molar excess added to the amidine hydrolysis flow reactor 16 is between about 0 and about 50%, Between about 15 and about 25%, stoichiometrically reacted with the introduction of amidine hydrolytic flow Such a mole ratio can be obtained with the equivalent amine of the device. After the steady state is established, the I% / lamer ratio can be adjusted again and maintained at a more efficient mole ratio of about 0.99. Between about 1.2 and about 0.9, preferably between about 0.95 and about 105. The rate at which water is fed into the mixer 32 can be increased to avoid when using a molar ratio of 0.004 / nitrile below 10 The organic and aqueous phases are separated in the liquid phase. When H c is used for hydrolysis, in the steady state, the molar ratio of HC1 to nitrile is between about 10 and about 15, preferably about 1.05 and about 1.3. It is more preferably between about 丨 and about 12. When the molar excess of HC1 added to the amine hydrolysis flow reactor 16 is between about 0 and about 50%, preferably between about 5 and about 30% It is more preferably between about 10% and about 20%, which is more than the stoichiometric amount of amidine introduced into the amidine hydrolysis flow reactor. 22 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 public meals (please read the notes on the back before filling out this page) D,,-* 0 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A7 B7 V. Description of the invention () v 20; available Kind molar ratio. It has been found that at the beginning, the amidine hydrolysis flow reactor is operated with a high mineral acid / nitrile mole ratio, and the amidine conversion in the amidine hydrolysis flow reactor 16 is improved to a, which darkens the color of the hydrolysate. Despite the stringency of the increased I reaction conditions provided by the high acid / nitrile ratio, it was unexpectedly found that the acid / nitrile mole ratio did not significantly affect the color of the hydrolysate. Moreover, the high acid-to-nitrile molar ratio also allows the amidine hydrolysis flow reactor to operate at lower temperatures during stable operation, thus producing a colored hydrolysate. Printed by the Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs (please read the notes on the back before filling out this page) The hydrolysate leaving the amine hydrolysis flow reactor 16; when measured with a Garner colorimeter, it has about 5 to about The light color between 1 and 0, preferably between about 5 and about 7, is adversely affected by the temperature and residence time of the amidine hydrolysis flow reactor 16 which is excessive in the amidine hydrolysis flow reactor 16. The amidine hydrolysis flow reactor is operated between about 70 ° C and about 120 ° C. When the amidine hydrolytic flow reactor is operated under adiabatic conditions, when the reaction product absorbs adiabatic reaction heat, the temperature rises along the flow path to reach a point (hot spot) on the flow path, and at that point the temperature reaches the platform, and if The situation is not so completely adiabatic, beyond which it can drop slightly. The maximum temperature in the amidine hydrolysis flow reactor is better than about 90 ° and about 20 °. 〇, more preferably between about 90 ° C and about 105 ° C. The completion reaction / watt residence time in the amidine hydrolysis flow reactor is between about 30 minutes and about 1000 minutes, preferably between about 50 minutes and about 70 minutes. When the amidine hydrolysis flow reactor is operated at a temperature higher than that, a darker hydrolysate can be produced. However, the temperature of the amidine hydrolysis flow reactor below 90 ° C can cause incomplete hydrolysis of amidine unless a higher acid to nitrile mole ratio is used. If the residence time exceeds about 20 minutes, the hydrolyzed product can also be deepened. When using acid / moon cream between about 1.1 and about 1.5 in the beginning, Morse ratio This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) B7 21 5. Please read the description of the invention first Please fill in this page again on the back of the page and normal operation when the ammonium hydrolysis flow reactor 16 is between about 70 and about 95, preferably between about 80 ° C and about 90 ° C. , Can produce light-colored hydrolysis products. When operating under adiabatic conditions, the temperature of the ammonium hydrolysis flow reactor 1 can be reduced by reducing the temperature of the water stream entering the mixer 32. If I complete the reaction stream before introducing it to the amidine hydrolysis flow reactor, introduce it into the preheater (Figure 0, which can reduce the heat applied to the preheater and reduce the operation of the amidine hydrolysis flow reactor. Alternatively, when When the amidine hydrolysis flow reactor is operated at isothermal temperature, cooling and / or heating may be provided to control the temperature of the amidine hydrolysis flow reactor. When the first 03 but 1136 is also 717 shown in FIG. 3, in the amidine hydrolysis flow reactor Before 16, the operating temperature of the right first CSTR is too high, which can produce dark-colored hydrolysate. When using the above acid / nitrile mole ratio and between about 70 and about 95. It is better than When the second cstr is operated at an intermediate temperature between about 8 ° C and about 9 ° C, a light-colored hydrolysate is produced. The flow reactor most suitable and used in the amidine hydrolysis method of the present invention is a plug flow reactor, It is configured to provide a Picrete number of at least 50 and operate at a PFR operating temperature of at least 90 ° C. The Picrete number is a measure of backmixing of axes within pFR, as defined by:

P e = u L / D Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics where .u-speed, L = length, and D = axis dispersion coefficient. The Pickeret number of pFR is inversely proportional to the inverse mixing of the axis. When the Pickeret number is at least 50, preferably between about 50 and about 2000 or more, and the residence time is between about 40 and about 100 minutes, preferably about 50 and about 6 Between 0 minutes, the shaft anti-mixing is effectively reduced. -The PFR 16 of the present invention may be a pipe pFR or a filling pillar P F R filled with a filling material. The hydrazine hydrolysis reaction is non-zero, but it has been found that the kinetics of the reaction is 210X2 "· 495500 A7 B7. V. The description of the invention (22) is advantageous, and the high conversion can be understood within the above-mentioned rather modest residence time. There is no substantial pressure drop. More specifically, it has been found that the nitrile has been substantially converted to amidine, and the concentration of wax in the stream entering the plug flow reactor is not higher than about 2% by weight, The reaction flows in a perturbed flow range regime, such as a pipeline reactor operating at a speed below a Reynolds number of at least about 3 0 0, preferably at least about 5 0 0; the nitrile concentrations can each be reduced to More than about 0.2% by weight. If the nitrile / fluorenamine ratio of the completed reaction stream entering the reactor is not higher than about 1% by weight in the reaction stream entering the PFR, the concentrations of fluorenamine and nitrile in the reaction product may be different. Reduced to no more than about 0.1% by weight (based on Η BA). For a reasonably dwell time required to achieve this conversion, the PFR reactor can operate at a perturbed speed without excessive pressure drop. Moreover, it has been found The required transformation can be moderately manipulated The operating temperature is between 90 ° C and 105 ° C. It does not require a high-pressure reactor and it can produce light-colored products. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please Read the notes on the back before filling this page.) Alternatively, you can use the packed column PFR for the final hydrolysis reaction. By using well-structured packing, the packed column reactor can be operated at a significantly lower speed than the pipeline reactor. There is no significant anti-mixing due to wall action or channel flow. This filling promotes perturbation and radial mixing, and reduces anti-axis mixing, reaction flow dead spots and channel flow, so that all fluid elements reside at about the same Passes PFR within time. Therefore, a packed column reactor can have a substantially larger diameter and a tighter configuration than a pipe reactor. It is particularly advantageous when the reactants or products are of high viscosity. However, For the purpose of the present invention, it has been found that a pipe reactor, that is, an extended tubular reactor that is substantially free of internal fillings or other internal flow obstacles is preferred. Although in a pipe reactor, per unit length Affected by a slightly higher degree of axis -25-This paper size applies to Chinese National Standard (CNS) A4 (210X29 * 7 mm) 495500 Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, India A7 B7 V. Description of the invention (r ) W port, but the kinetics of the hydrolysis of nitrile and amidine has been found to be able to be converted almost quantitatively with the above-mentioned modest residence time and low pressure drop. Because it is suitable for the reactor of the present invention, even high speed It suffers a low pressure drop, so the tube reactor can be configured, that is, with a high L / D (length-to-diameter) ratio, at a very similar Picrete number, typically with an excess of 200, and easily The excess is 2000. In addition, the pipeline reactor used in the method of the present invention can be configured into a relatively convenient and material, such as a carbon steel pipe lined with Teflon. For packing column reactors, foreign structural materials are needed. Pipeline reactors also provide higher flexibility because they can operate with a much higher gas-to-air ratio than packed strings, the latter of which has a sharply reduced conversion to a defined valve speed. The valve speed in the packed string reaches between thin layer and disturbed flow. The amine fermentation hydrolysis reactor 6 is insulated to compensate for heat loss to the atmosphere. The heat of reaction generated during the hydrolysis of amidine is sufficient for autothermal operation under adiabatic conditions. Advantageously, the 'halogenation reaction stream can enter the ammonium hydrolysis flow reactor at a temperature below the reaction temperature of the ammonium hydrolysis. During autothermal operation, the reaction heat generated by the amidine hydrolysis increases the temperature in the amidine hydrolysis flow reactor and reduces the possibility of hot spots forming in it. The temperature profile in the amidine hydrolysis flow reactor can be measured through several temperature sensors Ti (Figures 1-4) along the length of the reactor. The water feed temperature can be adjusted to achieve the required temperature profile in the ammonium hydrolysis flow reactor. Before entering the mixer 32, the water heater is used to increase or decrease the heat supplied to the water feed stream to form Complete the reaction stream. In addition, the temperature of the completed reaction stream leaving the mixer 32 can be increased by using a preheater 34, which increases the operating temperature of the ammonium hydrolysis flow reactor. Although the residual nitrile is hydrolyzed in the inlet part of the ammonium hydrolysis flow reactor, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). ： 495500 A7 B7 V. Description of the invention (24 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ¾ But nitrile water ^ in CSTR 1G and disappearance of nitrile The reaction zone includes decantation on the forward zone and the product flow of the nitrile hydrolysis reactor The front flow port has 26 dilution points, and the flow zone is fully carried out until the solid mass in the flow-resolving reactor has been completed, such as' I amine water, &lt; such as &lt; Hydrolysis I reaction heat, which may cause Hotspots in the reactor. Although the hotspot temperature is as high as &quot; substitute to about i20t: tolerable in the amidine hydrolysis flow reactor, the hydrolysate can be significantly deeper in these cases. In essence The nitrile in the product stream of the nitrile hydrolysis reactor is reduced so that the ammonium hydrolysis flow reactor is operated at a lower temperature to provide a light-colored, complete aqueous hydrolysate. The amidine hydrolysis flow reactor is between about 0 and about 15 psig. Pressure between The pressure control valve at the outlet of the amidine hydrolysis flow reactor provides a reaction up to i 5 psig to avoid boiling in the reactor system when the amidine hydrolysis flow reactor is operated above 105. Ground, the amidine hydrolysis sample can be drawn from the sample valve s (Figure 4) and analyzed by gas chromatography to determine the side profile of the amidine hydrolysis composition along the length of the amidine hydrolysis flow reactor. Once a steady state condition is established, each From 8 to i 2 hours, the hydrolysate sample can be removed from the outlet of the amidine hydrolytic flow reactor and quantitatively analyzed to monitor the product quality. The aqueous hydrolysate leaving the amidine hydrolytic flow reactor 16 is completed and stored in the hydrolysate equilibrium tank 4 2 flowed through the cooler before. The nitrile hydrolysis reactor, the amidine hydrolysis reactor and the hydrolysate balance tank used in the present invention, by using ordinary exhaust manifolds covered with nitrogen and controlled by a pressure controller on the same top Depressing operation, when the pressure exceeds about 15 '... coincidentally, exhaust the pressure to the header of the sintering furnace to relieve the pressure. The exhaust can remove volatile organic sulfur compounds such as methyl sulfur, methyl disulfide,- 27 This paper size applies to China National Standard (CNS) A4 (210X 297 mm) f Please read the notes on the back before filling out this page) ··· · Bookmark Printed by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 495500 A7 B7 V. Description of the invention (25) and methyl mercaptan 'It is a by-product of the reaction. Vapor emission is less than 0.5 scf per 1000 pounds. The HMBA product is usually less than 0.3 scf ° 2 scf per 1000 pounds of HMBA product, and even lower jade is easier to achieve, especially when only a single CSTR is used. HMBA, or a salt or derivative thereof, can be recovered from the aqueous hydrolysate for recovery of the aqueous hydrolysate used in the manufacture of animal feed supplements. For example, HMB A in the hydrolysate can be recovered for use in liquid animal feed supplements, comprising between about 80% and about 98% by weight of the total weight ratio, preferably about 80% and about 95% by weight. HMB A between weight ratio, and water between about 2% and about 20% by weight, preferably between about 5% and about 20% by weight, and having a color not higher than about 8 (when When measured on the Garner scale), measured with a Cannon-Fenske viscometer at a kinematic viscosity at 25 ° C above about 500 centistokes, preferably 90 centimeters bubble, and its After being subjected to an accelerated colorimeter, it exhibits non-exothermic or endothermic thermochemical effects at any temperature less than about 50 ° C. HMBA can be recovered from the completed aqueous hydrolysate, by neutralization with NH4〇Η as described in Heriiandez equal to US Patent No. 4,9 12,25 7 (incorporated herein by reference), or by means such as Ruest Equivalent to the extraction method described in US Patent No. 4,524,077 (which is incorporated herein by reference). WO 96/01808, W〇96 / 01809, and WO 96/05 173, which are incorporated herein by reference, describe the preparation of HMBA ammonium salt, nitrile hydrolysis of sulfuric acid to prepare HMBA, and thin film evaporation and solvent recovery to recover hmbA Method. More specifically, WO 96/0 1808 describes the preparation of an aqueous hydrolysate completed by neutralization. The organic phase containing Hmb a and the aqueous ammonium salt phase are formed by extraction with a salt and a solvent. The application states that the organic phase is then treated with ammonia to form a second paper with HMBA ammonium salt. This paper is suitable for household use (CNS) ~ specifications (2lQx 297). !! (Please read the notes on the back before filling this page)

Printed by 1T Central Standards Bureau of the Ministry of Economic Affairs—Industrial and Consumer Cooperatives 495500 A7 B7 V. Description of the invention (26) Water phase and organic solvent phase. The ammonium salt of HMB A is recovered from the second water phase. It is said that the ammonia is recovered by treating the ammonium salt solution with NaOH to form NaC1 * Na2S04, which is easier to handle. W0 96/01809 describes the formation of concentrated HMBA2. The aqueous sulfuric acid hydrolysate completed by extraction with an organic solvent forms an organic phase containing HMBA and an aqueous phase and evaporates the organic phase containing HMBA. Provides a concentrated 98% HMBA with less than 4% by weight of water. . WO 96/05 173 describes the recovery of HMBA, and the practically anhydrous, HMB A-containing salt residue is obtained by evaporation of the aqueous sulfuric acid hydrolyzed product. The residue is treated with an organic solvent to form a suspension, and the solid is separated from the suspension to form rhenium. The solution of μ BA 'was removed from the solution containing HMB A to obtain the hmBA residue, and water was added to the BA BA residue to form a Μ BA solution. Previous techniques include various other methods for recovering HMBA or HMBA salt products, including at least a few that are already commercially available. Any method can be selected by those skilled in the art to recover the HMBA product from the hydrolysate, and according to the present invention there is a natural benefit from the initial preparation of the aqueous hydrolysate. The hydrolysate produced according to the present invention is highly suitable for any method of operation for recovering the product acid or salt. The salt of HMBA can also be prepared from the completed aqueous hydrolysate. Cummins are equal to US Patent No. 4,310,69, Nufer US Patent No. 3,272,860, and Blake et al., US Patent Nos. 2,938,053 and 2,745,745. This article is for reference. Cummins describes the preparation of the calcium salt of HMBA, by mixing an HMBA-containing aqueous hydrolysate with a mixture of NaCl and Ca salt, and reacting this mixture with Nao, the resulting solution is reacted with a slurry of Ca (OH) 2 to form # 5 salt of HMBA, and then separate the salt of HMBA. Blake et al. Described the formation of ammonium and calcium salts of HMBA, by adding Ca (〇H) 2 to neutralize h2S〇4 &amp; (NH4) 2S〇4 in HMBA-containing aqueous hydrolysate, filtering this paper is applicable to China Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page), 11 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A7 B7 V. Description of the invention (27) Mixture, except CaS04, the filtrate is reacted with Ca (OH) 2 slurry, the mixture is filtered to remove CaS04, and the filtrate is dried to recover the composition containing HMBA salt, ammonium salt of HMBA and a small amount of CaS04 and water. Blake et al also described the preparation of calcium salt of HMBA, by reacting CaC03 with HMBA-containing aqueous hydrolysate, h2S04 and (1 ^^ 14) 2304 to form ammonium salt of HMBA and CaS04, separating CaS04, and separating the remaining liquid with Ca (OH) 2 &amp; should form HMBA calcium salt and NH4OH, heat the mixture to decompose NH4OH and drive out NH3, filter the resulting mixture to remove CaS04 & Ca (〇H) 2, evaporate water from the mixture to form HMBA # 5 salt Thick slurry. Filter the slurry and dry the filter cake to obtain the calcium salt of HMBA. Nufer described the formation of HMBA calcium salt. The HMBA was mixed with the monoalkyl ether of ethylene glycol, the mixture was reacted with Ca 0 -glycol ether slurry, the resulting slurry was filtered, and the filter cake was dried to recover the calcium salt of HMBA. Other methods for forming HMBA salts or derivatives are well known and include methods for preparing HMBA salts, by direct reaction with metal oxides or other bases, and as described in U.S. Patent Nos. 4,855,495, 4,579,962 and 4,335,357 (Incorporated herein for reference) Isolation or partial isolation of HMBA. Fig. 3 illustrates a specific embodiment of the present invention, in which the amidine hydrolysis reaction is performed upstream of the amidine hydrolysis flow reactor 16 and the second Cs T R 3 6 of the amidine hydrolysis flow reactor. The second CSTR enables easy handling of viscose amidines, thoroughly mixes the amidine hydrolysis mixture with dilution water and any separate parts of the mineral acid stream in the second CSTR 'and controls the temperature of the completed reaction stream when the latter introduces amidine hydrolysis When the reactor is flowed, a relatively low-viscosity complete reaction stream is created. The nitrile hydrolysis reaction takes place in CSTR 10, and any separate part of the product stream, water feed stream and mineral acid stream leaving the nitrile hydrolysis reactor of c STR 10 will be introduced via pipeline 20. The second paper size applies to China National Standard (CNS) A4 specification (210X 297) (Please read the notes on the back before filling out this page) Order 495500 Printed on the A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (28) ^ CSTR 36. Hydrolysis of amidine in a substantial portion thereof to HMBA. For the purpose of the present invention, when more than 50% by weight, preferably between about 50% and about 80% by weight, of the amidine is hydrolyzed to HMBA, a substantial portion of the amidine is hydrolyzed. The residence time of the amidine hydrolysis mixture contained in the second CSTR 36 is between about 30 minutes and about 60 minutes, preferably between about 40 minutes and about 60 minutes. The dwell time in the second CStr 36 is calculated by dividing the liquid volume of the second CSTR by the volume flow rate of the completed reaction stream leaving the second CSTR. The liquid content in the second cstr can be controlled by gravity overflow to the ammonium hydrolysis flow reactor 6 or better by positive content control as described above. '' Amidine hydrolysis reaction in a second CSTR at a temperature between about 70 ° C and about 120 ° C, preferably between about 90 ° C and about 105 ° C, and between about 0 and about 15 psig Begin under total pressure. The increase in conversion to BM B A is generally achieved by increasing the temperature to about 90 ° C and about 110. (: The second CSTR is operated in between. The second CSTR 36 is typically supplied with a reaction stream heating jacket to maintain the operating temperature. If the temperature sensor T 丨 (Figure 3) detects a hot spot in the hydrolyzed flow reactor, then The operating temperature of the second CSTR can be lowered. The amidine hydrolysis reaction is substantially performed in the second CSTR to generate a complete reaction stream, which is introduced into the amidine hydrolysis flow reactor. 6. The complete reaction stream contains at least about 30% by weight HMB A , At least about 17% by weight ammonium salt, at least about 15% by weight water, up to about 10% by weight amidine and up to about 1% by weight nitrile. Preferably, the completed reaction stream contains about 30 and about 5 Between 0% by weight BA Μ BA, between about 17 and about 30% by weight ammonium salt, between about 15 and about 30% by weight water, between about 1 and about 6% by weight fluoramine and up to About 0.1% by weight of nitrile. When using H2S04, the complete reaction stream contains at least about 31% by weight of BABA, and at least about 20% by weight of ammonium salt. If this paper is scaled to the Chinese National Standard (CNS) Α4 specification (210X297 mm) ί Please read the precautions on the back before filling out this page} Set the staff consumption of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A7 B7____ printed by the company V. Description of the invention (29) NH4HS04 or (NH4) 2S04, at least about 20% by weight 0 / 〇 water, up to about 5% by weight amidine and up to about 1% by weight nitrile, and more than Preferably between about 32 and about 42% by weight Η BA, between about 20 and about 30% by weight salt, between about 22 and about 30% by weight water, about 2 and about 4% by weight % Fluorene and up to about 0.1% by weight nitrile. When using HC 1, the completed reaction stream contains at least about 45% by weight Η Μ BA, at least about 17% by weight N H4 C 1, at least about 15 Weight percent water, up to about 8 weight percent amidine and up to about 1 weight percent nitrile, and preferably between about 45 and about 50 weight percent HMB A, between about 17 and about 19 weight percent NH4C1 , Between about 18 and about 22% by weight of water, between about 2 and about 6% by weight of amidine and up to about 0.1% by weight of nitrile 'amidine is hydrolyzed as described above for iamine The hydrolysis flow reactor is completed. Figure 4 is a better and modified method of the method shown in Figure 3. The residence time of the product of the nitrile hydrolysis reactor flowing between the outlet of the hydrolysis reactor and the second CSTR is extended, as described above. Related to Figure 2 The nitrile is eliminated. When the nitrile hydrolysis reactor product stream is diluted with any separate portion of water and / or mineral acid to form the ammonium hydrolysate stream, it is fed to the second CSTR. The ammonium hydrolysate occurs in the second CSTR to produce and is delivered to The complete reaction stream of the ammonium hydrolysis flow reactor is shown in Figs. 5 and 6. The preferred embodiment of the present invention can be used. $ Τ r 10 The method shown in Fig. 1 is used to accept concentrated H.2S. 〇4, ΗΜΒΝ and water, material. The BMNB and the water feed stream are fed directly to the CSTR. Concentrated or, circulated, mixed with the circulating stream, or fed directly to CSTR. The concentrated Η 2 s〇4 stream can be directly fed to the CSTR, but it is preferably fed to the heat exchanger (, circulation, and downstream of the spring via a pipeline), so that the concentrated Η2 S〇4 stream is returned to cs TR 1 〇 Thoroughly mix with the aqueous hydrolysis mixture. When all flow back, feed to cstr, -32-) A4 size (210X29 ^^ --- (Please read the precautions on the back before filling this page) Order * 495500 A7 B7 30 V. Description of the invention (When the nitrile hydrolysis reactor occurs, Η44 is diluted in the reactor. In any case, it is not necessary to separate the acid dilution system, and to avoid the related installation and maintenance. Introduce the aqueous hydrolysis mixture The concentrated HJCU has a strength between about 70% by weight and about 99% by weight I, preferably between about 90% by weight and about 98% by weight. The aqueous hydrolysis mixture in CSTR 10 has about 50% by weight The strength between the weight ratio and the weight ratio is preferably between about 60% by weight and about 70% by weight. "H2S 0 # (based on no organic matter). The aqueous hydrolysis mixture is continuous at a high ring rate. The heat of reaction is removed by pumping through the outer heat exchanger 24. The pump 22 applies the aqueous hydrolysis mixture to the CSTR 10 and the external heat exchanger 24, which is transported to the cooler to remove the exothermic heat of the reaction. When concentrated H2S04 is directly fed to the reactor 10, the heat exchanger also removes H2S〇4 The heat generated by the dilution. The method of the present invention provides an improved method for preparing HMBA. With this method, the productivity can be achieved, because it can be continuously operated and provides a greater throughput of materials than the conventional batch method. This method significantly reduces the Major and maintenance costs related to batch reactions, such as by eliminating the need for separate HdO4 dilution when Η2 S Ο 4 is introduced into the reactor without pre-dilution. This method also provides improved control when compared to conventional batch hydrolysis systems Reaction conditions. This improved controlled hydrolysis reaction enables uniformly-oriented hydrolysates of uniform quality. The exhaust emission of this method is significantly reduced when compared with conventional batch systems, due to the elimination of tank filling and emptying, and non-standard Operation under steady-state conditions. The following examples provide preferred embodiments and uses of the present invention, but are not intended to limit the present invention, except in the scope of additional patent applications. Other statements in 1 ------ 1T ----- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495500 Α7 Β7 V. Description of Invention (31 ) Example 1 A laboratory-scale apparatus as shown in FIG. 7 was used to demonstrate the continuous hydrolysis process. Nitrile (2-mercapto-4 -methylthiobutane) and 65% aqueous H 2 s0 4 were each 1 ％. Pumped continuously at a rate of 1 g / min and 1.1 67 g / min into a thoroughly stirred recirculation reactor 46 with a liquid volume of 4 2. ^ ml. The reaction temperature was controlled to 65T via a cooling jacket provided on the recirculation reactor, which removed the heat released by the nitrile hydrolysis reaction. Pump 48 recycles the aqueous hydrolysis mixture in the reactor loop. Based on the total feed rate, the residence time of reactor 46 was 25.4 minutes. Samples are periodically removed at the reactor outlet 'in a steady state. All sampling ports are named S in Figure 7. The sample was analyzed by gas chromatography and the hydrolysate leaving the reactor was decided. The gas chromatography results showed that in practice all the nitrile feedstocks were hydrolyzed and converted to amidine, and about 15% of the amidine formed was then hydrolyzed in this reactor to form ΜMBA, the final hydrolysis product. The Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs printed the hydrazine-rich hydrolysate leaving the recycle reactor 4 6 to be continuously fed to the first-recycle reactor 50 'which is similar to the first recycle reactor * 6, But with liquid gift 1 1 9.3 ml. A water feed of 57 g / min was also introduced into a second thoroughly dropped reactor, which provided a dwell time of 52.6 minutes. The temperature of this reactor ring was maintained at 0 2 via the heating fluid jacket provided on the recirculation reaction ring. 〇. Line 52 recycles the hydrolysate in the reactor loop. A sample from the reactor 50 was analyzed by gas chromatography, which showed that about 94.5% of the feed amine was hydrolyzed to 水解 ΜΒΑ. The contents from the second recycling reactor 50 continuously enter the final completion reaction device, which is composed of a group of four Teflon tube coils 54. The paper size of the finished reactor is set to the Chinese National Standard (CNS) Α4 size (210 X 29 * 7 male thin) 495500 A7 D-7 32 V. Description of the invention (in a constant temperature oven 5 6 to prevent shanghai students,冃 Net,,. ',,, and children are around, so to maintain the entire reactor, table ring 5 4 to 1 0 2 C. 屮 pen, wnr ... and this temple 洫 疋 PFR has a total liquid volume of 9 The dwell time of 1 ml, 'ying 4 knives is designed to ensure the complete hydrolysis of amidine. In this case, the hydrolysis of amine is completed at the exit of the third coil 58. It is obtained from the exit of pfr (the hydrolysis product contains 35% HMBA 'The remaining substances are water and by-products NH4HS〇4. The color of the hydrolysate is 6-7 based on the Garner color scale. Examples 2-9 4 See the same continuous laboratory-scale equipment used in Example 1 for measuring gastric residence time And the effect of reaction temperature on the conversion. The acid to nitrile feed ratio of each sample was maintained at about 1.0 Molar stoichiometric ratio. At the outlet of each recycle reactor and the end of each PFR coil, it was removed at steady conditions Samples (referred to as π RECIRC and S respectively in Table 8 below), gas chromatography The composition of the hydrolysis mixture leaving the reactor or coil was determined by method analysis. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 8 below. The remaining products include water and nh4hso4. The results are based on various feeds The speed (丨 〇1_2 33 g / min, nitrile feed) and temperature (60-65 ° C for nitrile hydrolysis and 90-12 ° for amidine hydrolysis) indicate that increasing the residence time and reaction temperature, improving the conversion of the two hydrolysis reactions, however , Increasing the temperature also results in an increase in the color of the product. Example 2 Nitrile was fed to the first recycle reactor at 1.01 g / min, together with 115 g / min 6 4 · 7% H 2 S〇4 'to obtain 0.99 acid / Nitrile mole ratio. The water feed was also introduced into the second recycle reactor at 0.055 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 1 below. Table 1 -35 This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page) Ordered by the Central Consumers Bureau of the Ministry of Economic Affairs to print 495500 A7 B7 V. Description of the invention (33

RECIRC-I RECIRC-II S1 S2 S3 Temperature (° C) 64 Dwell time (minutes) 25 103 53 104 11 104 11 104 11 Hydrolysis mixture composition (% by weight) Nitrile 0.11 Trace trace Trace trace HMBA 8.3 34 33 35 Phenylamine 38 2.7 0.70 0.12 0.03 Color of hydrolysate: 6-7 Based on the Garner color scale. Please read the winter% on the back before filling in this page. Example of printing by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Feed to the first recycle reactor, together with 1.16 g / min 6 4.7% H 2 SO 4, to obtain a 0.99 acid / nitrile mole ratio. The water feed was also introduced into the second recycle reactor at 0.54 g / min. The composition, temperature and residence time of the hydrolyzed mixture in each reactor or coil are shown in Table 2 below. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 495500 A7 B7 34 V. Description of the invention (Table 2 RECIRC-I RECIRC-II S1 S2 S3 Temperature (° C) 62 Dwell time (minutes) 25 98 53 102 11 102 11 102 11 Hydrolysis mixture composition (% by weight) Nitrile 0.22 0.05 0,05 Trace 0.035 HMBA 7.8 33 38 38 38 Phenylamine 35 3.5 0.81 0.18 0.09 Please read the winter notes on the back before filling in the hydrolysate on this page Color: 5-6 Based on the temperature of the Garner color scale (° C) 65 Dwell time (minutes) 18 105 36 105 7.7 105 7.7 105 7.7 Composition of hydrolyzed mixture (wt%) printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Nitrile 0.36 0.06 0.05 Trace Trace HMBA 6.7 34 36 37 38 Pyramine 39 3.1 0.79 0.28 Trace Hydrolysate Color: 6-7 Based on Garner Color Specimen Paper Size Applicable to Chinese National Standard (CNS) A4 Specification (210X 291 2 3 4 public %) 37-1 Example 4 2 Nitrile was fed to the first recycle reactor at 1.43 g / min, together with 1.65 g / min 3 4.7% H 2 S04, to obtain 0.9 9 acid / nitrile mol The water feed was also introduced into the second recycle reactor at 0.7 6 g / min. The composition, temperature and dwell time of the hydrolysis mixture in each reactor or coil are shown in Table 3. Table 3 4 RECIRC-I RECIRC-II SI S2 S3 495500 A7 B7 V. Description of the invention (35) Example 5 (Please read first Note on the back, please fill in this page again.) Nitrile was fed to the first recycle reactor at 1.45 g / min. Together with 1.69 g / min, 6 4.7% H2S04, 1.0 acid / nitrile mole ratio was obtained. Each reactor The composition, temperature and dwell time of the hydrolysis mixture in the coil are shown in Table 4. Table 4 RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° c) 65 90 90 90 90 90 Dwell time (minutes) 18 37 7.7 7.7 7.7 7.3 Hydrolysis mixture composition (weight ° / 〇) nitrile 0.37 trace trace trace trace trace HMBA 6.1 32 36 37 36 37 amidine 40 5.8 2.1 0.99 0.60 0.40 color of hydrolysate: 4 based on Garner color scale example 6 Nitrile was fed to the first recycle reactor at 2.0 g / min, together with 2.33 g / min 65% H2SO4 to obtain a 1.0 acid / nitrile molar ratio. The water feed was also introduced into the second recycle reactor at 1.09 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 5 below. Printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -38-This paper size applies to the Chinese National Standard (CNS) A4 (210X 297 mm) 495500 A7 B7 V. Description of the invention (36 Table 5 RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° C) 65 Dwell time (minutes) 13 105 26 105 5.4 105 5.4 105 5.4 105 5.2 Hydrolysis mixture composition (% by weight) Nitrile 0.45 0.09 Trace 0.04 Trace 0.06 HMBA 5.3 34 36 36 36 37 37 Amidine 40 〇 〇0.84 0.28 0.12 0.07 Please read the 5th item before filling in this page Hydrolysate color: 6-7 based on the example of the Garner color scale 7 Nitrile was fed to the first recycling reaction at 1.4 2 g / min The reactor, together with 1.65 g / min and 65% H 2 S04, yielded an acid / nitrile molar ratio of 1.0. The water feed was also introduced into the second recycle reactor at 0.7 95 g / min. Each The composition, temperature and residence time of the hydrolysis mixture in the reactor or coil are shown in Table 6. Table 6 RECIRC-I RECIRC-II SI S2 S3 Temperature fC) 60 Residence time (min) 18 120 36 120 7.5 120 7.5 120 7.5 Economic Composition of the hydrolyzed mixture printed by the Consumer Standards Cooperative of the Ministry of Standards of the Ministry (wt%) Nitrile 0. 23 0.05 Trace Trace Trace HMBA 5.2 36 35 36 36 Phenamine 39 1.5 Trace Trace Trace Hydrolysate Color: 17 Based on Garner Color Specimen Paper Size Applicable to Chinese National Standard (CNS) A4 Specification (210X297 mm) 5. Description of the invention 37 A7 B7 Example 8 Nitrile was fed to the first recycle reactor at 1.43 g / min, together with 166 g / min acid / nitrile mole ratio. The water feed was also introduced into the second recycle reactor at 0.078 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 7 below. Table 7 RECIRC-I RECIRC-II Sl Magic S4

Composition of hydrolysis mixture (weight 0 / 〇)

NA NA NA

NA NA NA (Please read the notes on the back before filling in this page) · Packing. Hydrolysate color: 6 Based on the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs of the Garner Color Standard Du Printing Example 9 Nitrile feed at 1.04 g / min To the first recycle reactor, together with 65% H2SO4, a 0.96 acid / nitrile mole ratio was obtained. The water feed was also introduced into the second recycle reactor at 0.57 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 8 below. This paper size applies Chinese National Standard (CNS) A4 Regulation (210X 297 mm) 38495500 A7 B7 V. Description of Invention (

(Please read the precautions on the back before filling out this page) Example of printing cracks in the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 1 〇-2 〇 The effect of measuring the molar ratio of acetic acid / nitrile feed on the reaction conversion, and the proportion and Coupling effect on reaction temperature. In these examples, the nitrile feed rate is substantially sufficient, and the water feed rate is adjusted to various 65% H2SO4 feeds to adjust to ensure the same water content of the final hydrolysate in each operation. At the reactor outlet and the coil &lt; end of the PFR, the sample is removed in a steady state and analyzed by gas chromatography to determine the composition of the hydrolysate leaving the reactor or coil. The composition, temperature and residence time of the hydrolysate in each reactor or coil are shown below. Other hydrolysates include water and NH4HS04. Based on the analysis of the variable range, that is, the acid / nitrile molar ratio is from 0.6 to 1.2, and the ammonium hydrolysis temperature is derived from 90-12 (rc, as shown in Figure 8 for the fixed foothold (or nitrile feed rate) tested The optimal conditions range. Any combination of temperature and acid / nitrile molar ratio within the range of 90 ″ 1 0 1 C and 1.0 ～ 1.2 acid / nitrile ratio, resulting in a satisfactory product Contains up to 5% by weight of ammonium amine, 0.5 to 5% by weight of nitrile and has a color between 5 and 7 (based on Ghana's paper size, applicable Chinese National Standard (CNS) A4 size (210X 297 (Mm) 5500 A7 B7 V. Description of the invention (39 mil color scale). Example 1 0 Nitrile was fed to the first ring reactor at 1.02 g / min, together with IQ] g / min 64.75% H2S〇4. 0.88 acid / nitrile molar ratio. The feed water was also introduced into the second recycling reactor at 053 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 9 below. Table 9 RECIRC -I RECIRC-II S1 S2 S3 / S4 Temperature (° c) 65 105 105 105 105 Dwell time C minutes) 27 53 11 11 11 Hydrolysis mixture composition (% by weight) Nitrile 0.80 0.31 0.35 0.40 NA HMBA 8.3 35 41 49 NA Pyramine 41 3.7 1.7 0.96 NA * Hydrolysate color: 6-7 based on the Garner color scale (please read the notes on the back before filling this page) Example 1 printed by the Consumers' Cooperative of Huangzhong County Bureau of Standards 1 Nitrile was fed to the first recycling reactor at 0.99 g / min, and 0.70 g / min 65% H2S04 was obtained to obtain a 0.62 acid / nitrile molar ratio. The water feed was also introduced into the second recycling reactor at 0.94 g / min. The composition, temperature, and residence time of the hydrolyzed mixture in each reactor or coil are not in the following table 10. 42-This paper size applies Chinese national standards ( CNS) A4 specification (210X 297 mm) t 495500 A7 B7 V. Description of invention (4 ()) Table 1 0 RECIRC-I RECIRC-II SI S2 S3 S4 Temperature (° c) 65 90 90 90 90 90 Please stay time (Points) 32 53 11 11 11 11 Read the composition of the hydrolysis mixture (% by weight) 5 Nitrile 5.2 2.2 2.4 2.5 2.5 2.5 ί HMBA 7.9 25 27 29 30 30 Items Reamine 45 9.5 7.4 5.9 5.2 4.6 Color: 5 based on the Garner color scale example 1 2 nitrile to 1. 0.1 g / min was fed to the first recycle reactor, along with 1.3 g / min 64.7 5% H 2 SOd · ^ 1.19 acid / nitrile molar ratio. The water feed was also introduced into the second recycle reactor at 0.53 g / min. The composition, temperature and residence time of the hydrolyzed mixture in each reactor or coil are shown in Table 11 below. Table 1 1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° C) 65 90 90 90 90 90 Dwell time (minutes) 23 50 10 10 10 10 (/)) Nitrile Trace Trace Trace Trace Trace Trace HMBA 7.7 31 35 34 35 35 Amine 〇〇jj 2.8 0.72 0.17 0.03 Trace Hydrolysate Color: 5 Based on Garner Color Specimen Paper Size Applicable to China Standard (CNS) A4 specification (210X 297 mm) 495500 A7 B7 V. Description of the invention (41 Example 1 3 Nitrile was fed to the first recycle reactor at 1.0 1 g / min, together with 0.70 g / min 6 5 ° / 0 Η 2 S 〇 4 to obtain a 0.66 acid / nitrile molar ratio. The water feed was also introduced into the first recycle reactor at 0.90 g / min. The composition of the hydrolysis mixture in each reactor or coil and The temperature and dwell time are shown in Table 1 below. Table 1 2 RECIRC-I RECIRC-II S1

Composition of hydrolysis mixture (wt%) Nitrile ΗΜΒΑ 醯 amine 6.0 7.7 44 2.6 27 5.4 2.7 32 4.0 2.2 29 1.4 2.7 34 1.8 2.3 31 1.4 Color of hydrolysate: 10 based on Garner color scale (please read the precautions on the back before filling in this Page) Example printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1 4 Nitrile was fed to the first recycle reactor at 1.0 g / min. Together with 37 g / min 64.75% H2S04, 1.19 acid / nitrile Morby. The water feed was also introduced into the second recycle reactor at 513 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 13 below. -44-This paper size applies Chinese National Standard (CNS) A4 specification (21〇 &lt; 297 mm) 495500 A7 B7 42 V. Description of the invention (Table 1 3 RECIRC-I RECIRC-Π S1 S2 S3 S4 Temperature (° C) 65 Dwell time (minutes) 23 120 50 120 10 120 10 120 10 120 10 Hydrolysis mixture composition (% by weight) Nitrile trace trace trace trace trace trace HMBA 8.5 34 34 35 35 34 31 0.44 Traces Traces Traces Please read I on the back of the page and fill in this page Hydrolysate Color: 12+ Based on the example of the Garner color scale 1 5 Nitrile was fed to the first recycle reactor at 1.0 g / min Together with 1.05 g / min 6 4.7 5% H 2 S04, 0.9 1 acid / nitrile molar ratio was obtained. The water feed was also introduced into the second recycle reactor at 0.6 7 g / min. Each reactor or The composition, temperature and dwell time of the hydrolyzed mixture in the coil are shown in Table 14 below. Table 14 RECIRC-I RECIRC-II SI S2 S3 S4 Temperature (° C) 65 Dwell time (minutes) 27 105 53 105 105 11 11 105 1 -5 11 11 Composition of hydrolyzed mixture printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (wt%) Nitrile 0.39 0.11 0.11 0.11 0.10 0.09 HMBA 8.9 34 34 37 38 38 Pyramine 37 4.0 1.5 0.71 0.32 0.20 Color of hydrolysate: 6 Based on the size of the Garner specimen Specimen size Applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -45 Which 500 A7 B7 V. Description of the Invention (43 Example 16 Nitrile was fed to the first recycle reactor at 1.02 g / min, together with 0.77 g / min 64.75%; 2804 gave a 0.6 acid / nitrile mole ratio. Water feed It was also introduced into the second recycle reactor at 093 g / min. The composition, temperature and residence time of the hydrolyzed mixture in each reactor or coil are shown in Table 15 below. Table 1 5 RECIRC-I RECIRC-II SI S2 S4 Temperature (° C) Dwell time (minutes) 65 32 120 52 120 11 120 11 S3 120 11 120 11 (Please read the precautions on the back before filling this page)

Composition of hydrolysis mixture (% by weight) Nitrile 5.7 2.5 2.7 2.6 HMBA 8.5 29 33 34 mm 45 6.2 4.3 2.6 2.6 35 2 0 2.5 35 1.5 Order hydrolysate color: 6 based on the example of the Garner color scale 1 7 Nitrile at 1.02 g / min The mixture was fed to the first recycle reactor and together with 0.69 g / min 65% ββ4, a 0.59 acid / nitrile mole ratio was obtained. The water feed was also introduced into the Brother-I recycle reactor at 0.90 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 16 below. Consumption of the Central Bureau of Standards of the Ministry of Economic Affairs 衽 Printed paper sizes are applicable to Chinese national standards (CNs) A4 specifications (210X 297 mm 495500 A7 B7 V. Description of invention (44 Table 1 6 RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° C) 65 Dwell time (minutes) 32 90 53 90 11 90 11 90 11 90 10 Hydrolysis mixture composition (weight ° / 〇) Nitrile 6.0 3.4 3.2 3.2 3.3 3.3 HMBA 8.2 25 27 28 29 30 Amines 44 12 8.0 7.5 6.6 5.7 Please read the following items before filling in this page Color of hydrolysate: 5 Based on the example of Garner color scale 1 8 Nitrile was fed to the first recycle reactor at 1.02 g / min, together with 1.38 g / min 65 % H2S〇Jf 1. 18 acid / nitrile molar ratio. The water feed was also introduced into the second recycling reactor at 0.54 g / min. The composition and temperature of the hydrolysis mixture in each reactor or coil and the residence time are shown below Table 1 7. Table 1 7 RECIRC-I RECIRC-II SI S2 S3 S4 Temperature 〇C) 65 Dwell time (minutes) 23 90 50 90 10 90 10 90 10 90 10 Hydrolyzed mixture printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Composition (wt%) Nitrile Trace Trace Trace Trace Trace Trace HMBA 7.2 31 35 35 35 36 Pyramine 34 2.9 0.75 0.24 Trace and trace hydrolysate Color: 5 Based on Garner color specimen Paper size Applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) Α7 Β7 i 、 Invention Explanation (45) Example 1 9 Nitrile was fed to the first recycle reactor at 1.03 g / min, together with 1.39 g / min 65% H 2 S04 to obtain a 1. 17 acid / nitrile mole ratio. Water feed The material is also introduced into the second recycling reactor at 0.52 g / min. The composition, temperature, and residence time of the hydrolysis mixture in each reactor or coil are shown in the following table 18. Table 1 8 (Please read the notes on the back first Please fill in this page again.) ·························································································································································································· 18 Based on Garner color scale 1 D RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature Cc), 65 120 120 120 120 120 Time (minutes) 23 50 10 10 10 10 Composition of hydrolysis mixture (wt%) Central Bureau of Standards, Ministry of Economic Affairs Printed by Consumer Consumption Cooperative Example 2 Nitrile was fed to the first recycle reactor at 1.02 g / min, together with 1 .05 g / min 65% ΗΘ〇4 to obtain a 0.90 acid / nitrile mole ratio. The water feed was also introduced into the first re-shield ring reactor at 0.63 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 19 below. This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 0 × 297), 495500 A7 B7 V. Description of invention (46) Table 1 9 RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° c) 65 105 105 105 105 105 Dwell time (minutes) 27 53 11 11 11 11 Mixture composition (% by weight) Nitrile 0.38 0.06 0.09 0.06 0.09 0.09 HMBA 8.9 28 39 31 41 38 Amine 40 2.5 0.97 0.31 0.18 0.10 Hydrolysate Color: 7 based on Ghana Color Code (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 495500 A7 B7 5. Description of Invention (47) 15.2 points. The amidine hydrolysis is completed in the final PFR coil. Example 2 2 The equipment used in the continuous hydrolysis process shown in Figure 3 consists of 2 CSTRsA and a packed column PFR. The first CSTR is dedicated to nitrile hydrolysis and the second CSTR and PFR are used for amidine hydrolysis. pfr is an 8-inch diameter carbon steel pipe lined with Teflon filled with Kirk (& 0 ()] 1) 8] ^ \ ^ iron. PFr is manufactured by Koch Engmeering. The SMVP filling has a valve speed of 0.95 mm / .sec. 1.05 lbs / hr of nitrile and 2 1 lbs / hr of 65% H 2 S 0 4 were continuously fed to the first 20 gallon CSTR, of which 13 gallons of liquid was controlled by the reactor outlet of the Ministry of Economy Central Standard Printed by the Bureau ’s Consumer Cooperative (read the precautions on the back before filling this page). The active controller is maintained. The reactor was maintained at 65 ° C outside the cooler outside the product recycle loop. The residence time based on the total feed rate and reactor liquid volume was 38 minutes. Exported hydrolysate samples were analyzed based on gas chromatography and found to contain less than 0.1% nitrile, 3 4.9% amidine and 11.2%% Μ B A. The outlet stream was directed into a second 30 gallon C S T R with a liquid volume of 2 7.7 gallons. The 80 ° C hot water stream was also fed to the second cS T R at a rate of 6 0.5 pounds per hour. The reactor temperature was 105 ° C, and the residence time was 91 minutes. The hydrolysate from the reactor contained 1.9% amidine, indicating that more than 90% of the incoming amidine was converted to ΗΜ B A in this vessel. The second c STR exit stream then enters the packed column reactor with structured packing and a total liquid volume of 25 gallons. From various samples obtained along the length of the column reactor, the amidine hydrolysis reaction was found in the reactor. 70% of the strengths have been completed. The temperature profile of the adiabatic column reactor ranges from 丨 〇〇 ～ 丨 〇2 ° C, the residence time in PFR is 529 minutes, and the final product contains less than 0.1% nitrile, less than 0.1% g Reoamine, and 48% Η Μ BA. The main by-product of this hydrolysis method, this paper size is applicable to the Chinese National Standard (CNS) a4 specification (210X29 * 7 mm) 495500 A7 B7 48 5. Description of the invention (&gt; ^ 11411304 can be separated from the product by conventional methods. (Please read the precautions on the back before filling this page) Example 23 The equipment in Example 2 was used for the following hydrolysis method, except that the second CSTR was connected to the bypass tube so that the column reactor was filled with ammonium hydrolysis reaction. The main reactor. The feed rate to the first CSTR was as described in Example 22. However, the temperature in the first CSTR was 60 ° C. Analysis of the exit sample showed that the intermediate hydrolysis mixture contained 0.2% nitrile, 3 9.4% ammonium amine and 9.5% Μ Μ BA. The lower CSTR operating temperature results in slightly higher nitrile concentrations, but lower Η Μ BA concentrations. The intermediate hydrolysis mixture is placed in a static mixer on the line with hot water flow (6 0.5 lb / hr) mixed stone. The Yuancheng reaction stream enters the PFR and maintains a steady state. The temperature profile is from 80 ° C at the inlet to 105 ° C, the highest temperature in the middle, and decreases to the outlet of the packed column. 1 0 2 C. Although the column wall is exposed to heat It is insulated, but it also suffers from some heat loss. The retention time in the column reactor is 5 2 · 9 minutes. The final hydrolysate at the outlet of the column reactor contains 0.1% nitrile, 〇.丨% ammonium amine and 40.8% HMBA, the rest are by-products NH4HS〇4 and water. Example 2 4 The equipment printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs was used for the following hydrolysis except for concentrated h2S 〇4 is directly fed to the first CSTR (Figure 5) without being pre-diluted with water to 65% H2S04. The water stream is also fed to the reactor. Therefore, the heat of dilution of the acid and the heat of hydrolysis pass through the circulating cooler Removed. The second C s TR was bypassed. Nitrile (72 lb / hr), 96% H2SO4 (56.2 lb / hr) and dilution water (26.7 lb / hr) were simultaneously fed to the first cstr, where Hydrolysis of nitrile occurs. The volume of the operating liquid is 10 gallons, which is based on the sum of the three feed rates. 51-495500 A7 B7 V. Description of the invention (49) Dwell time of 4 2.5 minutes. The reaction temperature is controlled at 5 5 ° C Gas chromatography of the aqueous hydrolysis mixture showed that it contained 0.5% nitrile, 4 0.6% amidine and 5.7% Η BA. Water The hydrolysis mixture was mixed with 4 1.3 lbs / hr of hot water in a static mixer on-line. The reaction flow was completed to enter the packed column reactor as described in Example 23, except that the adiabatic reaction temperature in the column reactor was slightly The higher outside may be due to the additional heat released by the higher content of unreacted nitrile leaving the CSTR operating at the lower temperature. The sample drawn from the column reactor was measured at a height of 70% from the inlet of the bottom of the column, and the hydrolysis of amidine was completed. Example 2 5-3 8 Samples of hydrolysis mixture taken at the exit of each CSTR, PFR addition (SI), PFR outlet (S6) and 4 sampling ports (S 2 to S 5) along the length of PFR are shown in Figure 3 . The sample was removed at steady state and analyzed by gas chromatography to determine the composition of the hydrolyzed mixture when leaving C S T R s and when flowing through P F R. The composition, temperature, and residence time of the hydrolyzed mixture in each CSRT and PFR of each segment are shown below. The rest of the hydrolysis mixture includes water and NH4HSO. Example There is no indication of a device containing CSTR-II data, where a bypass tube is placed on the second CSTR to cause the dilute aqueous hydrolysis mixture to flow directly from the in-line mixer to PF R. Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) This data proves that the conversion is affected by the temperature in the plug flow reactor, the acid / nitrile ratio, and the degree of shaft reverse mixing. Backmixing is in turn the number of speeds at which the reaction mixture flows through the reactor. In the example where the effect of anti-mixing is transformed, the reactor is operated at less than 1.0 mm / sec of its valve speed, resulting in a lower average driving force, i.e. the ammonium concentration of this non-zero reaction along the reactor Length integration. In some cases, operations below the valve speed can be compensated for using relatively high temperatures and / or acid / wax ratios. Further discussion on the relationship between speed and shaft anti-mixing and the effect of the result on the conversion -52-This paper size applies the Chinese National Standard (CNS) A4 specification (210X29 * 7mm) 495500 A7 B7 V. Description of the invention (50 described in the example The end of 3 8. Example 2 5 Nitrile was fed at 105.000 lbs / hr to No. 037111, together with 12.095 lbs / hr 65% H2S〇d ^ .〇3 Molar ratio. Water feed was also The second CSTR was introduced at 6050 lbs / hr. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 20 below. Volume (plus 13 CSTR-I CSTR-II 27.7 S1 Table 20 S2 S3 S4 S5 S6 17.5 (Total PFR) (Please read the precautions on the back before filling in this page) Temperature Γ〇103 103 102 Moon paste 0.02 0.02 0.01 0.01 0.01 ΗΜΑ 12 41 34 39 39 Amines 34 2.0 0.5 0.27 0.04 Central Bureau of Standards, Ministry of Economic Affairs Printed by Consumer Consumption Cooperative Example 2 6 Nitrile was fed to the first at 105.00 lbs / hr (8:11, together with 125.095 lbs. Hrs 6 5% H 2 S 〇 4 to obtain 1.0 0 acid / nitrile molar ratio. Water The feed was also introduced into the second CSTR at 6050 hours. For the composition and position of the hydrolyzed mixture for each sample The temperature is shown in the following table 21. -53 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 495500 A7 B7 51 V. Description of the invention (

CSTR-I CSTR-II S1 Table 2 1 S2 S3 S4 S5 S6 Volume (gallon 13 temperature (° C) 13 27.7 17.5 (total PFR) 65 105 101 102 102 102 102 101 101 PFR speed = 10 mm / sec nitrile. 0.01 mark HMBA 11 36 Phenamine 35 1.9 Composition of hydrolysis mixture (% by weight) Trace trace Trace trace Trace 0.01 37 29 26 30 31 47 1.1 0.21 0.05 0.05 0.05 0.05 Hydrolysate color: 6-7 based on Garner color scale Please read the notes before filling in this page

Printed by the Consumer Standards Cooperative of the Central Bureau of Standards, Ministry of IT and Economy 2 7 Nitrile was fed to the first CSTR at 105.0 0 lbs / hour, together with 145.14 lbs / hour 65.5% H 2 S〇4 1.2 1 acid / nitrile mole ratio. The water feed was also introduced into the second CSTR at 5 7.4 lbs / hour. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 22 below. Table 22 CSTR-I CSTR-II SI S2 S3 S4 S5 S6 1 I Volume (Gal 13) 27.7 17.5 (Total PFR) Temperature (° C) 65 93 90 93 92 92 92 91 1 PFR speed = 10 mm / sec composition of hydrolysis mixture (% by weight) nitrile trace trace trace trace trace trace ΗΜΒΑ 11 33 34 35 36 36 amine 31 1.8 1.3 0.14 0.02 0.01 Traces Traces 38 33 0.01 0.01 Color of hydrolysate: 9-10 based on Garner color scale Example 2 8 Nitrile was fed to the first CSTR at 7 2.0 0 lbs / hour, together with 8 2.9 4 lbs / hour -54-Paper Zhang scale is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 A7 B7 V. Description of the invention (52) 6 5% H2SOdl 1.0 acid / nitrile mole ratio. The water feed was also introduced into the inline mixer at 41.30 lbs / hour. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 23 below. Table 23 _CSTR-I_S1_S2_S3_S4_S5_S6 Volume (gallon 10 19.9 (total PFR)) Temperature (° C) 65 80 96 97 97 97 97 97 _PFR speed = 0.69 mm / sec_; _ Hydrolysis mixture composition (% by weight) Nitrile 0.13 0.03 0.02 0.01 0.01 0.01 0.02 HMBA 14 22 28 24 27 25 44 Pyramine 40_1_9_33_L6_1 / 7_L4_1.2 Hydrolysate Color: 3 Based on the Garner Color Scale Example 2 9 Nitrile was fed to the first CSTR at 7 2.0 0 lbs / hour, together with 8 2.9 4 lbs 6 5% H2SO4 to obtain 1.0 acid / nitrile mole ratio. The water feed was also introduced into the on-line mixer at 4 1.30 lbs / hour. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 24 below. Table 24 _CSTR-I_S1_S2_S3_S4_S5_S6 Volume (Gallon 10 19.9 (Total PFR) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)) Temperature (° C) 60 81 103 103 101 101 100 PFR speed = 0.69 mm / sec Composition of hydrolysis mixture (% by weight) Month 0.19 0.01 Trace Trace Trace Trace Trace HMBA 8.8 20 38 37 39 47 54 Amidine 38 22 1.4 0.59 -55-0.34 0.33 0.06 Paper Zhang scale is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 Five inventions description (53 Hydrolysate color: 6-7 based on the Garner Color Standard Example 3 0 Nitrile is fed to 15th A CSTR, together with 17,279 pounds / hour 65% H2S0jl.〇4 acid / nitrile molar ratio. The water feed was also introduced into the Cyi CSTR at 86 400 / J. For each sample, the composition and position of the hydrolysis mixture The temperatures are shown in Table 25 below. Table 25 ____ CSTR-I CSTR-U SI S2 S3 S4 S5% volume (gallon 10 277 25.0 (total PFR) ^) temperature (° C) 65 1〇4 100 102 102 102 102 101 __ PFR speed = 14 mm / s (Please read the precautions on the back before filling this page)

Composition of the hydrolyzed mixture printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (wt%) Nitrile 0.26 0.03 0.01 Trace Trace Trace Trace Trace HMBA 8.1 35 37 39 37 37 39 38 38 3.0 1.5 0.21 0.03 0.02 0.02 0.02 __ Hydrolysate color: 10-11 based on the Garner color scale 'Example 3 1 Nitrile was fed to the first CSTR at 150.0 lbs / hr, along with 1 72_ .7 9 lbs / hr 65% Η 2 S. 4 gives 1.0 2 acid / nitrile mole ratio. The water feed was also introduced into the -CSTR at 86.4 lb / hr. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 26 below. Table 26 — CSTR-]: CSTR-II S1 S2 S3 S4 S5 S6 Volume (plus 10) 27.7 25.0 (Total PFR) Temperature fc) 65 102 100 103 103 104 103 102 PFR speed = 14mm / s order t -56 This paper size applies Chinese National Standard (CNS) A4 specification (210X 297mm) 495500 A7 B7 ^ Description of the invention (54 Yueqing 0.13 〇. 〇1 HMBA 7.0 36 Fermented amine 40 3.2 Decomposition mixture composition (%) 〇-〇3 0.03 0.02 0.02 0.02 37 39 39 40 41 2.4 0.84 0.23 0.18 0.16 Hydrolysate color: 8-9 based on Garner color scale 0.01 40 0.13 Example 3 2 Nitrile was fed to the first 033 but 11 at 105.0 lbs / hr, together with 12.05 Torr / hr 65.5% Torr 2 S04 to give a 1.02 acid / nitrile mole ratio. Water feed The material was also introduced into the first CSTR at 60.5 pounds per hour. The composition of the hydrolyzed mixture for each sample and the temperature at each location are shown in Table 27 below. Table 27_CSTR-I CSTR-II SI S2 S3 S4 Volume (gallon 27.7 I7.5 (Total PFR) (Please read the precautions on the back before filling this page) 1 · Install S5 S6 temperature fc)

1〇1 103 1〇3 PFR speed 2 10mm / s Hydrolysis mixture composition (weight 0 / n) 0.36 0.03 0.01 0.01 0.01 9.1 38 38 40 40 39 2.7 1.8 0.32 0.08 Trace 41 __-〇. Still hydrolysate color: 10-11 base; ^ Garner color scale &quot;-Example 'nitrile was fed to the first CSTR at 72.00 lbs / hour, together with 8 2.94 at 6 5% 1123〇4 A 1.0 acid / nitrile mole ratio was obtained. The water feed was also introduced into the inline mixer at 41.3%. For each sample, the composition of the hydrolysis mixture and the respective t temperatures are not lower than those in Table 28 below. '〆

CSTR-I S1

.Piece of paper I Original meaning applies to Chinese National Standard (CNS) 8 4 specifications (210/495500 7 Β V. Description of invention (55) Volume (gallon) Temperature (° C) 10 60 19 · 9 (Total PFR) 84 103 105 105 PFR speed = 0.69 mm / s 105 103 Hydrolysis mixture composition (wt%) Month f 0.41 0.02 0.01 0.01 0.01 0.01 0.01 0.01 HMBA 9.5 23 26 23 23 23 47 Phenamine 43 17 2.3 0.63 0.62 0.61 0.72 Hydrolysate color: 5- 6 Based on the Garner color scale example 3 April green was fed to the first CSTR at 9 0.6 0 lbs / hour, together with 103.80 lbs / hour 65% H 2 S 〇 4 to obtain a 1.03 acid / nitrile mole ratio. The water feed was also introduced into the on-line mixer at 5 1.90 pounds per hour. The composition of the hydrolyzed mixture for each sample and the temperature at each location are shown in Table 29 below. Table 29 CSTR -1 SI S2 S3 S4 S5 S6 Volume (Gallon 12.6 25.0 (Total PFR)) Temperature (° C) 59 82 104 105 105 105 104 PFR speed = 0.86 mm / sec Hydrolysis mixture composition (wt%) Monthly meeting 0.39 0.03 0.01 0.01 0.01 0.01 0.01 HMBA 9.1 23 33 30 31 31 38 Phenamine 41 18 2.0 0.92 0.79 0.71 0.76 Hydrolysate : 8-9 Based on the example of the Garner color scale. 3 5 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Together with 1 2 4.80 lbs / hr and 65% H 2 S04, a 1.2 acid / nitrile mole ratio was obtained. The water feed was also introduced into the on-line mixer at 4 9.40 lbs / hr. For the hydrolysis mixture of each sample The composition and the temperature of each position are shown in the following table 30. -58-This paper size applies the Chinese National Standard (CNS) A4 specification (21 OX 297 mm) 495500 A7 B7 V. Description of the invention (56) Table 3 0 _CSTR-I S1_S2_S3_S4_S5_S6 Volume (gallon 12.6 25.0 (total PFR)) Temperature Γ〇45 86 107 107 107 107 105, _PFR speed = 0.86 mm / s_ Composition of hydrolysis mixture (wt%) Month 0.07 0.01 Trace trace Trace trace HMBA 8.1 23 35 33 39 37 37 Phenylamine 36_12_1.0 Traces Traces Traces_0.01 _ Hydrolysate Color: 1 M2 based on the Garner Color Scale_ Example 3 6 Nitrile was fed to the first CSTR at 90.60 lbs / hour Together with 124.80 lbs / hr of 65% H2SO4, a 1.20 acid / nitrile molar ratio was obtained. The water feed was also introduced into the inline mixer at 4 9.40 lbs / hr. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 31 below. Table 3 1 _CSTR-I_S1_S2_S3_S4_S5_S6 Volume (gallon 12.6 25.0 (total PFR)) Temperature (° C) 58 82 105 103 103 103 103 _PFR speed = 0.86 mm / s_ Composition of hydrolysis mixture (wt%) Nitrile trace trace trace Traces Traces Traces Traces Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) HMBA 8.3 20 38 37 38 38 39 Coolamine 31 18 0.96 Traces Traces Trace hydrolysate color: 1 M2 based on the Garner color scale example 3 7 Nitrile was fed to the first CSTR at 9 0.6 0 lbs / hour, together with 10 3.80 lbs / hour 65% H 2 S〇4 1.0 acid / nitrile mole ratio. The water feed is also 5 1.90 lbs / min. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) 495500 A7 B7 V. Description of the invention (57)-In-line mixer. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 32 below. Table 32 _CSTR-I S1_S2_S3_S4_S5_S6 Volume (gallon 12.6 25.0 (total PFR)) Temperature (° C) 59 88 109 109 109 109 109 107 _PFR speed = 0.86 mm / s_ Composition of the hydrolysis mixture (% by weight) Nitrile 0.09 0.01 Q.01 Trace Trace 0.01 HMBA 8.8 26 38 69 38 40 41 Phenylamine 37_13_0.30 0.02 0.01 0.01 Trace Hydrolysate Color: 1M2 based on the Garner Color Scale (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 495500 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (1) Example 3 8 Nitrile at 1 05 · 00 lbs / hour Feeding to the first CS TR together with 1 20.95 pounds / hour 65% Η 2 S 0 4 gives a 1.0 acid / nitrile mole ratio. The water feed was also introduced into the inline mixer at 60.50 pounds / hour. The composition of the hydrolysis mixture and the temperature of each position for each sample are shown in Table 33 below. Table 3 3-~~-CSTR-I S1 S2 S3 S4 S5 S6 Volume (Gallon) 14.6 25.0 (Total PFR) Temperature (° c) 60 80 103 104 105 104 102 PFR Speed = 1.0 mm / s Hydrolyzed mixture The composition will be 0.2% 0.02 0.01 0.01 0.01 0.01 0.01 HMBA 9.5 24 39 45 45 42 41 39 21 2.5 0.19 0.20 0.28 0.11 -____ Hydrolysate Color: 8-9 Based on the Garner color scale as described above, in the filling Some of the conversions obtained in the pipette PFR were insufficient to meet the target residual amine concentrations in the product hydrolysate. These lower conversions can be attributed to the low reaction temperature or acid / nitrile ratio of the car parent, excessive axial backmixing, or some combination of these factors. Based on studies performed to operate the reactor at a speed sufficient to provide a pic Crete number higher than about 50, the determination of the residual amidine concentration in the hydrolysate can consistently reduce at least the steady state operation above. The preferred range of the reaction temperature and the acid / nitrile ratio in question is about 0.03%. However, when the Pickcrete number is below 50, lower conversions are generally found, unless increased by temperature and / or acid / month f ratios to compensate. In order to study the effect of velocity on anti-mixing in packed column PFR, the pulse of salt was injected at the bottom of the column (with tap water flowing upward) to change the velocity. (Notes on the back then fill out this page)

1T-Am 495500 A7 V. Description of the invention (B7 59 = Tracer for dwell time distribution test. Insert a conductivity probe at the outlet of the reactor to measure the conductivity of the outlet flow, and obtain the tracer response data from it. Expressed as salt (NaCi) concentration versus time. According to customary methods, do calculations based on response data to determine the average dwell time (the first moment of distribution), the degree of variation (the first knife, the moment of cloth), the Picrit criterion, And continuous equivalent stirred tanks of the reactor / Noritake reactor's flow rate (qpm), average residence time (㊀), etc., because of the input k degrees (σ2), Pickeret number (Pe), and equivalent The number (j) of the stirred tank reactors is described in Table 34. ajpun 0.95 0.47 0.90 The entire table 34 θ__ σ2 P e 丄 29.5 0.0393 50.9 25.5 66.3 0.0681 29.4 14.7 25.1 0.0749 26.7 13.4 The mouth left on the bottom of the reactor. Adjust this factor (please read the precautions on the back before filling this page). Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, J = 20.5 and pe = 41. These data prove the filling tube used in these tests. The critical speed threshold is in the range of 0.5 qpm. Based on the calculation of the kinetics of the amidine hydrolysis reaction, the relationship between the number of equivalent stirred tank reactors and the remaining amidine concentration is calculated. The equivalent agitated reactor and : (A) the ratio of the required reactor length to the specified degree of conversion) to (the required length for the same degree of conversion under perfect plug flow conditions) (L / Lp); and (b) Correlation between (residue concentration of ammonium amine for a specified reactor length) and ratio (c / cP) of (residual enzyme amine concentration for a reactor of the same length under tedious plug flow conditions). These calculations are described in Table 35. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 A7 B7 V. Description of the invention (60) Table 3 5 JL L / L ^ C / Cl Pyramine%) 15 1.236 2.66 0 · 〇 5 8 1% 20 1.177 2.25 0.0491 25 1.14 1 2.00 0.0436 3 0 1.178 1.83 0.03 99 40 1.088 1.62 〇 · 〇353 CO 1.000 1.00 0.0218 Example of cooperation between employees of the Central Standards Bureau of the Ministry of Economic Affairs and social printing 3 9-5 5 A sample of the hydrolyzed mixture was removed in Stables® and analyzed by gas chromatography. When leaving the CSTR, enter the PFR and then leave the pFR * as shown in Figure 2 of Example 39_48 and as shown in Figure 49-5 The composition of the hydrolyzed mixture shown. The data demonstrate that the conversion of HMBN to amidine was improved by increasing the residence time by about 3 minutes in the zone between the exit of the C S T R and the dilution point in the reaction flow to pFR. Examples 44 and Η are directly comparable to Examples 45, 46, and 53 because they operate at the same flow rate and show the same peak temperature in p F R. Examples 3 9-4 8 demonstrate when the peak temperature of the flow reactor is from 105 or 106. (: The color of the hydrolysate is improved when it is lowered to 101 or 102C. Example 3 9 Such as '96% H 2 S04 and water was fed to cs τ R (as shown in Figure 2) to obtain the acid / mol. Ratio to form an aqueous hydrolysis mixture. 60 t in CsTR: 37 minutes after standing below, the 'hydrolysis mixture contains 0.03% nitrile and 39% ammonium amine by weight. It is in the forward direction of the forward flow port. The forward flow between the flow port and the dilution point is the Chinese National Standard for Paper (CNS) Α4 ^^ ΤΤΪ0 × 297 公 ίΤ (Please read the precautions on the back before filling this page) Order 495500 A7 B7 V. Description of the invention (61 shall The residence time of the aqueous hydrolysis mixture ^ in the zone is 4 seconds and 3 minutes, respectively. After dilution, the reaction stream is fed into the bamboo shoots to PFR, which is 8 b 10 6 under adiabatic conditions. (: Operation and residence time is 70 points. The water-soluble hydrolysate containing U. sylvestris is 0. 0 1% ammonium amine and less; 0. 0 1% such as a few percent &lt; the color of the water-based hydrolysate is based on the Garner color scale 8. 5 〇 Example 4 0 month, 96% Η 2 S 〇 4 and fire; Jia 々 Ligong p. 2 4 夂 water into the CSTR (as shown in Figure 2) to get 1 () acid A Mo An aqueous hydrolysis mixture is formed. The hydrolyzed milk compound contains 0.01% nitrile and 38% ammonium amine by weight in the CSTR after 37 minutes of TC residence. It flows forward in the I #% area of the forward flow port. The residence time of the aqueous hydrolysis mixture in the forward-flow reaction zone between the mouth and the dilution point were 4 seconds and 3 minutes, respectively. After dilution, the completed reaction stream was fed to PFR, which was operated at 81 ° under adiabatic conditions. And the residence time is 70 minutes. The finished aqueous hydrolysate is Qi% g &amp; amine and less than 0.01% nitrile. The color of the redundant aqueous hydrolysate is based on the Garner color scale of 8.5 ° Example 4 1 Central standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperative (please read the precautions on the back before filling this page) 96% H2S〇4 and water is fed to the CSTR (as shown in Figure 2) to obtain the acid / nitrile mole ratio of 〇〇, which forms hydrolysis Mixture. After staying at CSTR $ 6 (rc for 37 minutes, the hydrolyzed mixture contains 0.08% nitrile and 38% amidine by weight. It is in the forward flow ^ upstream of the core-circulation zone and between the forward flow port and the dilution point. The residence time of the aqueous hydrolysis mixture in the forward flow reaction zone was 4 seconds and 3 minutes after dilution. It should be fed to p FR, which operates under adiabatic conditions for 80 minutes and stays for 70 minutes. The completed aqueous hydrolysis yields less than 0.00% amidine and nitrile. The color of the completed aqueous hydrolysis product Based on the Garner color scale, it is 8.5. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 Α7 Β7 62 5. Description of the invention (Example 4 2 (Please read the precautions on the back before Fill in this page) Nitrile 96% H2SO4 and water were fed to the CSTR (as shown in Figure 2) to obtain a molar ratio of acid / nitrile to form an aqueous hydrolysis mixture. After standing at CSTR600C for 30 minutes, the hydrolysis mixture contained 0.08% nitrile and 38% amidine by weight. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the forward flow port and the upper dilution are 4 seconds and 3 minutes, respectively. After dilution, Fancheng reaction stream was fed to p F R, which was operated under adiabatic conditions, with a residence time of 70 minutes. The finished aqueous hydrolysate contains less than 0.001% amidine and wax. The color of the redundant aqueous hydrolysate was 7.5 based on the Garner package. Example 4 3 Wax wax, 96% H2SO4, and water were fed to a CSTR (shown in Figure 2) to obtain an 1.0 acid / pubic mole ratio 'to form an aqueous hydrolysis mixture. In C s τ r, 60. (: After 37 minutes in Shimojota, there is no analysis of the hydrolysis mixture. Retention of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the Xiangbei / Wadong port and the dilution point The time is 4 seconds and 3 minutes respectively. After dilution, the reaction stream is fed to PFR ', which is operated at 79-104 ° C under adiabatic conditions, with a residence time of 70 minutes. Fancheng's aqueous hydrolysate contains 0 · 〇1% ammonium amine and less than 0.01% nitrile. The color of the finished hydrolyzed hydrolysate is based on the Garner color scale of 8 5. Example 4 4 Monthly cream printed by employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, 96% H 2 S04 and water were fed to cSTR (as shown in Figure 2) to obtain a 1.0 acid / monthly mole ratio 'to form an aqueous hydrolysis mixture. After standing at CS τ r, 60 ° C for 37 minutes,' no Analyze the hydrolysis mixture. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the tile moving port and the dilution point are 4 seconds and 3 minutes, respectively. Dilution After that, complete the reaction flow feed to-65-this paper is suitable for (cNS) A4 size (mm '495500 A7 B7 'Explanation of the Invention (63 PFR printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs' It is adiabatic' 79_1104 It is operated with a dwell time of 70 minutes. Complete &lt; Aqueous hydrolysate contains less than 0.01% amine And nitrile. The color of the finished aqueous hydrolysate 1 was 8.5 based on the Garner color scale. Example 4 5 gamble, 96% H 2 S04 and water were fed to c S τ R (as shown in Figure 2) to give 1.0 acid / Month Mohr ratio 'forms an aqueous hydrolysis mixture. After staying for 37 minutes at C s τ r, 60 ° C, the' hydrolysis mixture contains 004% nitrile and 40% amide by weight. It flows forward The residence time of the aqueous hydrolysis mixture in the upstream region of the mouth and in the forward flow reaction zone between the forward flow port and the dilution point is 4 seconds and 3 minutes, respectively. After dilution, the reaction stream is fed to p FR , Its adiabatic, 7 7 _ 丨 〇2. 0 operation 'dwell time is 70 minutes. The completed aqueous hydrolysate contains 0.00 %% ammonium amine and less than 0.0 1% wax. Aqueous aqueous hydrolysis product The color is based on the Garner color scale as 8.5. Example 4: June cream, 96% H2SO4, and water were fed to the CSTR (as shown in Figure 2). Molar ratio of 1.0 mol / month forms an aqueous hydrolysis mixture. After staying at CSTR, 60 ° C for 37 minutes, the hydrolysis mixture contains 0.03% wax and 40% ammonium by weight. At the forward flow port The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone and in the forward-flow reaction zone between the forward flow π and the dilution point are 4 seconds and 3 minutes, respectively. After dilution, the reaction stream is fed to PFR, which Operating under adiabatic temperature, 7 7-10 ° C, the dwell time is 70 minutes. The redundant aqueous hydrolysate contains 0.001% amidine and less than 0.01% nitrile. The color of the finished water-based hydrolysate is 7.5 ° based on the Garner color scale. Example 4 7 This paper ruler ”applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling in this page)

, 1T will 495500 A7 _____B7 V. Description of the invention (64) Nitrile, 96% H 2 S 〇 4 and water are fed to c STR (as shown in Figure 2) to get 1.0 acid / moire green mole ratio 'to form aqueous hydrolysis mixture. After staying for 37 minutes at C s τ R and 60 ° C, the 'hydrolysis mixture contains 0.06% nitrile and 37% amidine by weight. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the forward flow port and the dilution point were 4 seconds and 3 minutes, respectively. After dilution, the reaction mixture was fed to p F R, which was operated at 7 5-101 ° C under adiabatic conditions and the residence time was 70 minutes. The finished aqueous hydrolysate contains 0.1% amidine and less than 0.01% nitrile. The color of the finished aqueous hydrolysate is 6.5 based on the Garner Color Scale. Example 4 8 Nitrile, 96% H2SO4, and water were fed to a CSTR (as shown in Figure 2) to obtain a 1 () acid / nitrile mole ratio to form an aqueous hydrolysis mixture. After C s T R, 60 dwells for 37 minutes, the hydrolyzed mixture contains 41% acetonitrile with a weight ratio of less than 0.9%. The residence times of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the forward flow port and the dilution point were 4 seconds and 3 minutes, respectively. After dilution, the reaction stream was fed to PFR, which was operated under adiabatic conditions at 75-100, with a residence time of 70 minutes. The finished aqueous hydrolysate contained 0.01% amidine 2 and less than 0.01% nitrile. The color of the finished aqueous hydrolysate was 6.5 based on Ghana. Printed by employees of the Central Standards Bureau of the Ministry of Economic Affairs, printed by the society (please read the precautions on the back before filling this page) -Am Example 4 9 Nitrile, 96% H2S04 and water are fed to the CSTR (as shown in Figure i) ) Moironitrile is obtained to form an aqueous hydrolysis mixture. It resides in C s T R, 69 ff, ^ t A 2 C for 46 minutes. The 'hydrolysis mixture contains 43% ammonium amine and 0.2% nitrile. Water-based Yongru,, _ &gt; Kun compound is in the upstream of the circulation zone of Xiangxiang flow port and between the forward flow port and, | 1,000 points. The paper size applies Chinese National Standard (CNS) A4 specifications (210X297 Mm) ^ 500〇A7

65 V. Description of the invention The residence time of the aqueous hydrolysis mixture in the tile reaction zone is 1 second and less than 1 minute. After dilution, the reaction stream is fed to p FR, which is 80- 1 04 ° C operation, dwell time is 88 minutes. The completed aqueous hydrolysate contains 0.02% nitrile and less than 0.0 1% amidine. The color of the completed aqueous hydrolysate is ^ on the Garner color scale. 8. Examples 5 0 Nitrile, 96% H2SO4 and water were fed to the CSTR (as shown in Figure i) to obtain an acidic nitrile mol ratio of iO acid to form an aqueous hydrolysis mixture. At C s TR, 6 η v "r: U After 49 minutes, the hydrolysis mixture contained 40% ammonium and 0.04% nitrile. The aqueous hydrolysis mixture reacted in the forward flow of the forward flow port &lt; upstream of the circulation zone and between the forward flow port and the dilution point. The residence time of the aqueous hydrolysis mixture in the zone is 1 type 2 less than 1 minute. After dilution, the reaction stream is fed to the p FR, which is operated at an adiabatic 82-104 °, and the residence time is 92 minutes. Complete aqueous hydrolysis : 0.03% nitrile and 0.01 1% amidine. The color I of the finished aqueous hydrolyzate is nal. The color scale is 8.5. Example 5 1 Nitrile, 96% H2SO4, and water were fed to the CSTR (as shown in Figure 丨) to obtain a molar ratio of 10 acid / nitrile to form an aqueous hydrolysis mixture. After 37 minutes in cs TR and 6 L, the hydrolysis mixture remained 35% ammonium amine and 03% nitrile. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow port and the dilution point ^ 2 The residence time of the aqueous hydrolysis mixture in the forward flow reaction zone are 1 =. Less than 1 minute. After dilution, the reaction stream is fed to ρ FR, which is performed in S2-1〇rC operation and residence time 70 minutes. Aqueous water completed :: 丄 0 · 0 2 % Nitrile and 0.0 1% ammonium amine. The color of the finished aqueous hydrolysate is applicable to the national standard (&amp; S) A4 in terms of strength (please read the precautions on the back before filling this page). Printed by the Consumers 'Cooperatives of the quasi bureau-68 495500 Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (66) I ~-The color scale of Nal is 8. Example 5 2 Nitrile, 96% H2S〇4 And water is fed to the CSTR (as shown in Figure i)! 〇Acid / nitrile ratio, forming an aqueous hydrolysis mixture. After tr, 61.0, the two-peak kun compound contains 43% ammonium amine and 0.05% nitrile. Aqueous hydrolyzed mixture: the material is moved to the upper part of the soil along the upstream and forward. The residence time of the aqueous hydrolysis mixture in the forward flow reaction zone between the flow port and the dilution point are… and less than 1 minute. After dilution, the reaction stream is fed to PFR, which is adiabatic '7 8-1 G 3 C operation and dwell time is 7 Q minutes. The finished aqueous hydrolysate contained 0.02% amidine, and the nitrile was not determined. The color of the finished aqueous hydrolysate is 5 based on the Garner color scale. Example 5 3 Nitrile, 96% H 2 S0 4 and water were fed to c S T R (as shown in FIG. 1) to obtain a molar ratio of acid / nitrile to form an aqueous hydrolysis mixture. After 6 丨 it stayed in c s τ R for 37 minutes, the hydrolysis mixture contained 40% amidine and 0.04% nitrile. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the tendon flow port and in the forward flow reaction zone between the forward flow port and the dilution point were 丨 seconds and less than 1 minute, respectively. After dilution, the reaction stream was fed to p F R, which was operated at 7 7-102 ° C under adiabatic conditions with a residence time of 70 minutes. The finished aqueous hydrolysate contains 0.01% St amine and 0.05% nitrile. The color of the finished aqueous hydrolysate is 6 based on the Garner color scale. Example 5 4 Nitrile, 96% H2SO4, and water were fed to a CSTR (as shown in Figure 1) to obtain a 10 acid / nitrile mole ratio to form an aqueous hydrolysis mixture. In CSTR, 6 4 t: Resident 3 7 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). ·) Binding 495500 A7 B7 Fifth invention description (67 After printing by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, the hydrolysis mixture contains 41% ammonium amine and 0.02% nitrile. The aqueous hydrolysis mixture is located upstream of the circulation zone towards Qiliukou and in The residence time of the aqueous hydrolysis mixture between the forward flow port and the dilution point in the Ru / Wan reaction zone is 1 second and less than 1 minute. After dilution, the reaction stream is fed to PFR, which is adiabatic, 7 9-1 03 ° C operation, and dwell time is 70 minutes. The completed aqueous hydrolysate contains 0.01% ammonium amine and 0.03% nitrile. The color of the completed aqueous hydrolysate is not determined. Example 5 5 Nitrile , 96% H 2 S 〇 4 and water were fed to c STR (as shown in Figure 1) to obtain the acid / nitrile molar ratio to form an aqueous hydrolysis mixture. After CsTr, 6 (49 minutes in TC, hydrolyzed The mixture contains 40% ammonium amine and 0.04% nitrile. The aqueous hydrolysis mixture is in the circulation zone of the forward flow port. The residence time of the aqueous hydrolysis mixture in the forward flow reaction zone between the forward flow port and the dilution point is 丨 seconds and less than 1 minute. After dilution, the reaction flow is fed to the PFR, which is adiabatic Operating under 79_ 1 03 ° C and dwell time 70 minutes. The completed aqueous hydrolysate contains 0.00% ammonium amine and 0.04% nitrile. The color of the completed aqueous hydrolysate is based on the Garner color scale of 9. Example 5 6 Based on experiments The batch hydrolysis data in the chamber was simulated by computer to simulate the performance of continuous hydrolysis system. 96% HC1 and nitrile were continuously fed to CSTR, and the acid / nitrile molar ratio of 1:15 was formed to form an aqueous hydrolysis mixture. In the CSTR, 50% was resident. After 60 minutes, the hydrolysis mixture contained 46% ammonium and 0.1% nitrile. The product stream of the nitrile hydrolysis reactor leaving CSTR was sent to the amidine hydrolysis cascade reactor. It was agitated to enhance fluid mixing and suspend the NH4C1 solids in In various compartments. Chinese national standards (CNS Γα4 size ♦ m · pack ------ 1T ----- Am are applied around the paper size of the reaction table) (Please read the precautions on the back before filling this page ) 495500 A7 B7 V. Description of Invention (68 Economy The jacket of the printed shell of the Consumer Standards Cooperative of the Central Bureau of Standards may provide a reactor temperature of 80 t by passing the product stream through an external feed preheater. The residence time of this stream in the amidine hydrolysis reactor is 4 Hourly redundant aqueous hydrolysis product contains 0.04% ammonium amine and 0.004% nitrile. Example 5 7 Based on laboratory batch hydrolysis data, the performance of a continuous hydrolysis system is simulated by computer. 36% HC1 and nitrile continuous feed To the CSTR, the 115 acid / nitrile mole ratio 'was formed into an aqueous hydrolysis mixture. After standing in C s T R for 60 minutes at 50, the hydrolysis mixture contained 46% amidine and 0.1% nitrile. The product stream of the nitrile hydrolysis reactor leaving the CSTR is sent to a second CSTR for completion of 80-90% of the amidine hydrolysis. After staying in the second CSTR for 4 hours, the NlCl hydrochloride hydrolysis slurry was cooled to 5 ° C to remove NH4C1 by centrifugation. The mother liquor of the centrifugation was transferred to a plug flow reactor operated under 80 ° C by using a jacket. Or outside preheater. PFR is not agitated, because NH ^ l is dissolved at this temperature and exists as a concentrate in PFR. After standing in PFR for 2 hours, the completed aqueous hydrolysate contains 0.4% ammonium amine and 0.04 % Nitrile. Although the rainbow is easy to accept various modifications and alternative forms, its specific embodiments have been shown by the examples in the drawings and have been described in detail herein. However, it should be understood that it is not intended to limit the invention In the special meter's form disclosed, on the contrary, the present invention covers all modifications, equivalents, and substitutions within the spirit and scope of the present invention, which is covered by the attached patent application 71-This paper standard applies Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) (Please read the precautions on the back before filling this page)

Claims (1)

495500 Patent application No. 085106567 Chinese patent application scope jipp private (⑴ 芊 June) 1. A method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, comprising: introducing an aqueous mineral acid into a nitrile hydrolysis reactor containing a first continuous stirred tank reactor; and introducing 2-hydroxy-4- Methylthiobutyronitrile is introduced into the nitrile hydrolysis reactor; 2 -hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed in the nitrile hydrolysis reactor to produce a nitrile hydrolysis reactor product containing 2-hydroxy-4-methylthiobutyramine Stream; introducing water and the product stream of the nitrile hydrolysis reactor into the amidine hydrolytic flow reactor: and continuously hydrolyzing 2-hydroxy-4-methylthiobutaneamine in the amidine hydrolytic flow reactor to produce a 2- # i Aqueous hydrolysate of methyl-4-methiobutyric acid 2. The method according to item 1 of the scope of patent application, wherein the water and the nitrile hydrolysis reactor product stream are mixed to form a complete reaction stream, so that when the complete reaction stream When flowing through the ammonium hydrolysis flow reactor, the hydrolysis of 2-hydroxy-4-methanebutanamine is essentially complete. 3. The method according to item 2 of the scope of patent application, wherein the nitrile hydrolysis reaction product stream is diluted with the water before the nitrile hydrolysis reactor product stream is introduced into the amidine hydrolysis flow reactor. 4. The method according to item 2 of the scope of patent application, wherein the water stream is heated before being introduced into the mixer for diluting the nitrile hydrolysis reactor product stream to form the completed reaction stream and preventing liquid phase separation. 5. · A method for separating 2-hydroxy-4-methylthiobutyric acid or a salt thereof, comprising: introducing an aqueous mineral acid into a nitrile hydrolysis reactor including a first continuous stirred tank reactor; the paper size is applicable to Chinese national standards ( CNS) A4 size (210 X 297 mm) Binding m 495500 AB c D VI. Application scope of patent Introducing 2-hydroxy-4-methylthiobutyronitrile into the nitrile hydrolysis reactor; Continuous hydrolysis of 2-hydroxy-4-methylthiobutyronitrile in the nitrile hydrolysis reactor produces Product stream of nitrile hydrolysis reactor of 2 -hydroxy-4-methanebutanidine; The product stream of nitrile hydrolysis reactor leaving the nitrile hydrolysis reactor and water are introduced into the continuous ammonium hydrolysis of the reactor containing the second continuous stirred tank The reactor, so that a substantial portion of the 2-hydroxy-4-methylthiobutanamine contained in the product stream of the nitrile hydrolysis reactor is hydrolyzed in the second continuous stirred tank reactor to form a complete reaction stream; Continuous introduction into the amidine hydrolysis flow reactor; and continuous hydrolysis of 2-hydroxy-4-methylthiobutaneamine in the amidine hydrolysis flow reactor to produce a finished aqueous solution containing 2-hydroxy-4-methylthiobutane acid Hydrolysate 06. The method according to item 1 or 5 of the scope of the patent application, wherein H 2 S 〇 4 is introduced into the nitrile hydrolysis reactor, and there is between 50% by weight and 70% by weight in the acid stream. The intensity of H2S04. 7. The method according to item 1 or 5 of the scope of patent application, wherein 112304 is introduced into the nitrile hydrolysis reactor, and has an intensity between 70% by weight and 99% by weight in the acid stream &lt; H2S04, and The acid stream is continuously introduced into the nitrile hydrolysis reactor while water is introduced, and H 2 S 0 4 is formed in the nitrile hydrolysis reactor based on the strength between 50% by weight and 70% by weight of no organic matter. 8. A method according to item 1 or 5 of the scope of the patent application, wherein at least 90% of 2-hydroxy-4-methylthiobutyronitrile is converted to 2-hydroxy-4-methylthiobutaneamine in the nitrile hydrolysis reactor. 9. The method according to item 1 or 5 of the scope of patent application, wherein the water-based mineral acid is _ -2. The paper size is suitable for the national standard (CNS) Α4 specification (21GX 297 公 #) &quot; &quot; The scope of patent application H2S04, and the molar ratio of h2s〇4 to 2-quinyl-4-methystyronitrile introduced into the nitrile hydrolysis reactor was between 0.6 and 1.5. ι〇. The method according to item 1 or 5 of the scope of the patent application, wherein the aqueous mineral acid is H2S04, and the mole of h2S04,2-quinyl-4-methyvalantonitrile introduced into the nitrile hydrolysis reactor The ratio is between 0.9 and 1.2. 11. The method according to item 1 or 5 of the scope of the patent application, wherein during the period between the start of the process and the establishment of a stable state in the amidine hydrolysis flow reactor, the H2S04-2-hydroxy group introduced into the nitrile hydrolysis reactor is introduced. -4-Molar ratio of methylthiobutyronitrile is between 1.0 and 2.0, and then the molar ratio of H2S04 to 2-hydroxy-4-methylthiobutyronitrile is between 0.6 and 1.5. 12. The method according to item 1 or 5 of the scope of patent application, wherein the H2S04-2-hydroxy group introduced into the nitrile hydrolysis reactor is introduced between the start of the process and the establishment of a stable condition in the amidine hydrolysis flow reactor. The molar ratio of -4-methylthiobutyronitrile is between 1.0 and 1.5, and then the molar ratio of 112304 and 2-hydroxy-4-methylthiobutyronitrile is 0.9 to 1.2. . 13. The method according to item 1 or 5 of the scope of the patent application, wherein the rate of flowing into the amidine hydrolytic flow reactor and the rate of flowing into the amidine hydrolytic flow reactor are 2-hydroxy-4-methylthiobutamine and 2- The ratio of the rate of hydroxy-4-methylthiobutyronitrile is controlled to provide a chemistry that is greater than that of the 2-hydroxy-4-methylthiobutyramine and 2-hydroxy-4-methylthiobutyronitrile introduced into the amidine hydrolysis flow reactor. Measure an equivalent amount of excess mineral acid in an excess of at least 5% mole. 14. A method according to item 13 of the scope of application for a patent, wherein the mineral acid and 2-hydroxy-4-methylthiobutyronitrile are introduced at a relative rate effective to provide the excess in the ammonium hydrolysis flow reactor. Nitrile hydrolysis reactor. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 495500 8 8 8 8 AB c D 15. The method according to item ”or 5 of the scope of patent application, wherein in a stable condition, the completed aqueous hydrolysate at the outlet of the ammonium hydrolysis flow reactor contains at least 36% by weight 2 -Hydroxy-4-methylthiobutyric acid, at least 8% by weight ammonium salt, at least 20% by weight water, up to 0.05% by weight amidine and up to 0.05% by weight nitrile. 16. The method according to item 5 of the scope of patent application, wherein after the process starts, the resulting aqueous hydrolysate contains up to 0.05 wt. /. And up to 0. 05 wt% nitrile. 17. The method according to item 1 or 5 of the scope of patent application, wherein the nitrile hydrolysis reactor product contains up to 16% by weight of 2-hydroxy-4-methylthiobutanoic acid, up to 12% by weight of ammonium salt, and at least 6% by weight Water, at least 30 wt.%. Amidine and up to 2% by weight nitrile. 18. The method according to item 5 of the application, wherein the ammonium hydrolysis flow reactor is a plug flow reactor, and the flow of the completed reaction flow through the plug flow reactor is disturbed. 19. A method according to item 5 of the patent application, wherein the product stream of the nitrile hydrolysis reactor is diluted with the water before being introduced into the continuous amidine hydrolysis reactor. 20. A method according to item 2 or 5 of the patent application Wherein the ammonium hydrolysis flow reactor includes a packed column reactor, and the completed reaction stream flows through the packed column reactor at a threshold speed equal to or higher than the threshold of the packed column reactor. 21. The method according to item 2 or 5 of the scope of patent application, wherein the ammonium hydrolysis flow reactor includes a pipeline reactor, and the completion of the reaction flow to disturb the flow path -4- The paper size applies to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 495500 A8 B8 C8 ------- D8 __ VI. Scope of patent application Pass the pipeline reactor. 22. The method according to item 21 of the scope of patent application, wherein the ammonium hydrolyzation flow reaction is prepared with a Reynolds number greater than 3,000. 23. A method according to item 21 of the scope of patent application, wherein the amidine hydrolysis flow reactor is operated with a Reynolds number greater than 5,000. 24. The method according to item 1 or 5 of the scope of the patent application, wherein the ammonium hydrolysis flow reactor is a plug flow reactor, which operates at a Pickeret number of at least 50. 'Peak temperature 9 0 to 1 2 0 ° C and dwell time between 30 and 90 minutes. 25. A method according to item 1 or 5 of the scope of patent application, wherein the amidine hydrolysis flow reactor is operated substantially adiabatically. 26. The method according to item 1 or 5 of the scope of patent application, wherein the amidine hydrolysis flow reactor is operated substantially at isothermal temperature. 27. The method according to item 1 or 5 of the scope of patent application, wherein the amidine hydrolysis flow reactor is operated under adiabatic and autothermal conditions. 28. The method according to item 1 or 5 of the scope of the patent application, wherein the recovery of 2-hydroxy-4-methylthiobutyric acid is carried out by neutralizing the completed aqueous hydrolysate to form 2-methyl-4-thiomethylbutanoic acid. The organic phase and the aqueous phase are separated, and the organic phase and the aqueous phase are separated to recover the 2-chido-4-methylthiobutanoic acid. 29. The method according to item 1 or 5 of the scope of patent application, wherein the vapor radiated from the method is not higher than 2-acryl-4-methylthiobutanoic acid 0.5 scf 〇30 per 1,000 broken products. 30. According to the scope of patent application The method of item 29, wherein the vapor radiated from the method is not higher than 0.3 scf 2-hydroxy-4-methylthiobutanoic acid-5- per 1,000 pounds of product. This paper is in accordance with China National Standard (CNS) A4 specifications ( 210X 297 mm) 495500 A8 B8 C8 ___D8 ____ 6. Scope of patent application &quot; 31. The method according to item 5 of the scope of patent application, wherein at least 80% of 2-hydroxy-4-methylthiobutane is formed in the nitrile hydrolysis reactor. Amines are converted into 2-mercapto-4 -methanethiobutyric acid in this continuous amidine hydrolysis reactor. 32. The method according to item 9 of the scope of patent application, wherein the continuous amidine hydrolysis reactor is operated at a temperature ranging from 70 ° C to 120 ° C. 33. The method according to item 5 of the scope of patent application, wherein the aqueous mineral acid, the water stream and the guess hydrolysis reaction product stream are mixed to form an amine fermentation hydrolysis mixture, which is introduced into a continuous hydrazine hydrolysis reactor. 34 · —A method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, comprising: introducing an aqueous mineral acid and 2-light-4-methylthiobutyronitrile into a nitrile hydrolysis reactor; 9 hydrolyzing the nitrile In the reactor, 2-hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed to produce a product stream of a nitrile hydrolysis reactor containing 2-hydroxy-4-methylthiobutyramine; water, aqueous mineral acid, and the nitrile hydrolysis reactor The product stream is introduced into a hydrazone hydrolysis stream reactor; and continuous hydrolysis of 2-hydroxy-4-methylthiobutaneamine in the hydrazone hydrolysis reactor produces a finished aqueous solution containing 2-hydroxy-4-methylthiobutane acid. Hydrolyzate. 35. The method according to item 34 of the scope of patent application, wherein the molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile added to the nitrile hydrolysis reactor is between 0.5 and 0.95, and The total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 0.6 and 0.95. 36. A method according to item 35 of the scope of application for a patent, wherein the molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile added to the nitrile hydrolysis reactor is 0.8 to 0.95. And the total molar ratio of mineral acid to 2-hydroxy-4 -methylthiobutyronitrile, -6- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) &quot; 495500 AB c D 6 The scope of patent application is between 0.85 and 0.95. 37. The method according to item 34 of the scope of patent application, wherein the nitrile hydrolysis reactor includes a first continuous stirred tank reactor, and the 2-hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed in the nitrile hydrolysis reactor. The nitrile hydrolysate stream is introduced into the amidine hydrolysis reactor, which comprises an amidine hydrolysis flow reactor, and the 2-hydroxy-4-methylthiobutane amidine is continuously hydrolyzed in the amidine hydrolysis flow reactor. 38. The method according to item 34 of the application, wherein the nitrile hydrolysis reactor comprises a first continuous stirred tank reactor in which the 2-hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed, and the nitrile The product stream of the hydrolysis reactor is introduced into a continuous ammonium hydrolysis reactor containing a second continuous stirred tank reactor, and 2-hydroxy-4-methylthiobutamide is continuously hydrolyzed in the second continuous stirred tank reactor to form a completed reaction stream. The completion reaction stream is introduced into the hydrazine hydrolysis reactor containing the hydrazine hydrolysis flow reactor, and when the completion reaction stream flows through the hydrazine hydrolysis flow reactor, the 2-hydroxy-4-methanbutamine The hydrolysis is essentially complete. 39. A method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, comprising: simultaneously 2-hydroxy-4-methylthiobutyronitrile, having a weight ratio between 70% and 99% by weight The strength H2S04 stream and water are introduced into a container in which 2-hydroxy-4-methylthiobutyronitrile is hydrolyzed. Water and sulfuric acid are added in this relative proportion to provide a strength of 50 to 70% by weight. A mixture (exclusive of organics); hydrolyzing 2-hydroxy-4-methylthiobutyronitrile in the container to produce a nitrile hydrolysate stream containing 2-hydroxy-4-methylthiobutamide; and hydrolyzing 2-hydroxy- 4-Methiobutanamine produces 2-hydroxy-4-Methiobutanoic acid. This paper is again applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 495500 Six Λ8 B8 C8 _____ D8, scope of patent application A redundant aqueous hydrolysis product. 40. The method according to item 39 of the scope of the patent application, wherein the container is a nitrile hydrolysis reactor containing a first continuous stirred tank reactor, and the 2-hydroxy-4-methylthiobutyronitrile is continuously in the nitrile hydrolysis reactor. Hydrolysis, the nitrile hydrolysate stream is introduced into the amidine hydrolysis flow reactor, and in this amidine hydrolysis flow reactor, 2-methyl-4-butanil is continuously hydrolyzed. 41. The method according to item 39 of the scope of patent application, wherein the container is a nitrile hydrolysis reactor including a first continuous stirred tank reactor, and in the nitrile hydrolysis reactor, 2-hydroxy-4-methylthiobutyronitrile is continuously For hydrolysis, the product stream of the nitrile hydrolysis reactor is introduced into a continuous ammonium hydrolysis reactor containing a second continuous stirred tank reactor. The amine is continuously hydrolyzed to form a complete reaction stream, which is introduced into the amidine hydrolysis flow reactor. When the complete reaction stream flows through the amidine hydrolysis flow reactor, the The hydrolysis is essentially complete. 42. The method according to claim 1, 5, or 39, which further comprises recovering 2-hydroxy-4-methylthiobutanoic acid or a salt or derivative thereof from the completed aqueous hydrolysate. 43. The method according to claim 1, 5, or 39, wherein 2-hydroxy-4-methylthiobutane is recovered by extracting 2-hydroxy-4-methylthiobutanoic acid from the completed aqueous hydrolysate. acid. 44. The method according to item 39 of the scope of the patent application, wherein the vapor radiated from the method is not higher than 0.5 scf of 2-hydroxy-4-methylthiobutyric acid per 1,000 pounds of product. 45 · —A method for preparing 2-hydroxy-4-methylthiobutyric acid or a salt thereof, comprising: introducing 2-hydroxy-4-methylthiobutyronitrile and an aqueous mineral acid into a solution containing 2-hydroxy-4-methyl-8-methyl This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 8 8 8 8 AB c D 495500 6. Application scope of patents Thiobutamine, mineral acid, and unreacted 2-hydroxy-4- Methylthiobutyronitrile in an aqueous hydrolysis mixture; the 2-hydroxy-4-methylthiobutyronitrile in the hydrolysis mixture is covered with a backmixing reaction zone and is in communication with the backmixing reaction zone in fluid flow) Hydrolysis in a continuous nitrile hydrolysis reactor in a zone (the cycle zone includes a cycle line); the aqueous hydrolysis mixture is continuously circulated in a recycle stream withdrawn from the backmixing reaction zone, and passes back to the backmixing reaction through the cycle zone Zone, the recycle stream containing unreacted 2-hydroxy-4-methylthiobutyronitrile when withdrawn from the backmixing reaction zone, a portion of the aqueous hydrolysis mixture that removes the cycle from the forward flow port in the recycle zone is Nitrile hydrolysis reactor product stream and conveying the nitrile hydrolysis reactor product stream to the amine fermentation stream Reactor; the nitrile hydrolysis reactor product stream is provided downstream of the forward flow port and diluted with water to provide a completed reaction stream; the hydroxylamine hydrolysis flow reactor contains 2-hydroxy-4-methyl formamidine in the completed reaction stream Thiobutamide is hydrolyzed to produce a completed aqueous hydrolysate containing 2-hydroxy-4-methylthiobutyric acid. The residence time of the circulating stream in the upstream of the circulation zone of the forward flow port and the forward flow port The sum of the dwell times of the nitrile hydrolysis reactor product stream before dilution, and before the nitrile hydrolysis reactor product stream is diluted, is sufficient to substantially distinguish the remaining 2-hydroxy-4-methylthiobutyronitrile. 46. The method according to item 1 or 45 of the scope of the patent application, wherein the aqueous mineral acid, the water stream and the nitrile hydrolysis reaction product stream are mixed to form a completed reaction stream, which is introduced into the amidine hydrolysis flow reactor. -9- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) &quot; ~ 一 495500 A8 B8 C8 D8 6. Application for patent scope 47.—A method for preparing 2-hydroxy-4-methylthiobutanoic acid or its salt, including: 2-hydroxy-4-methylthiobutyronitrile and aqueous mineral acid introduced containing 2 -Hydroxy-4 -methanbutamine, mineral acid and unreacted 2-hydroxy-4-methylthiobutyronitrile in an aqueous hydrolysis mixture; communicate with the backmixed reaction zone in a backmixed reaction zone and fluid flow The continuous nitrile hydrolysis reactor in the circulation zone (the circulation zone contains the circulation line) is hydrolyzed to the 2-hydroxy-4-methylthiobutyronitrile in the hydrolysis mixture; it will be drawn back into the circulation stream from the back-mixed reaction zone. The aqueous hydrolysis mixture continuously passes through the circulation zone, and then returns to the back mixing reaction zone, and the circulating stream contains unreacted 2-hydroxy-4-methylthiobutyronitrile when withdrawn from the back mixing reaction zone; A portion of the circulating aqueous hydrolysis mixture in the forward flow port in the circulation zone is the product stream of the nitrile hydrolysis reactor, and the product of the nitrile hydrolysis reactor is sent to the continuous ammonium hydrolysis reactor; downstream of the forward flow port Dilute the guess hydrolysis reaction with water as the product stream to provide ammonium water Mixture; feeding the amidine hydrolysis mixture or the nitrile hydrolysis reactor product stream and water to a continuous amidine hydrolysis reactor containing a substantial portion of 2-hydroxy-4-methylthiobutane in the amidine hydrolysis mixture Amine hydrolysis forms a complete reaction stream; transports the complete reaction stream to the amidine hydrolysis flow reactor; and hydrolyzes 2-hydroxy-4 -methanbutamine in the amidine hydrolysis flow reactor in the amidine hydrolysis flow reactor to produce Completed hydrolysate containing 2-hydroxy-4-methylthiobutyric acid; residence time of the circulating stream in the upstream of the circulation zone at the forward flow port and production of the nitrile hydrolysis reactor at the forward flow port The downstream of the logistics is diluted to -10- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Packing 495500 A8 B8 C8 _ __ _ D8 VI. Patent Application Range _ ^ 'The sum of the dwell time before the patent application, before the product stream of the nitrile hydrolysis reactor is diluted, it is enough to distinguish the remaining 2-hydroxy-4-methylthiobutyronitrile. 48. The method according to item 47 of the scope of application, wherein the product of the nitrile hydrolysis reactor is diluted with water in the continuous amidine hydrolysis reactor. 49. A method according to item 45 or 47 of the scope of the patent application, wherein the 2-hydroxy-4-methylthiobutyronitrile remaining in the product stream of the nitrile hydrolysis reactor at the dilution point is based on the content contained in the product stream The sum of 2-hydroxy-4-methylthiobutaneamine and 2-rozyl-4-methylthiobutanoic acid is not more than 0.01% by weight. 50. The method according to item 45 or 47 of the scope of the application for a patent, wherein in the aqueous hydrolysis mixture leaving the nitrile hydrolysis reaction, the remaining 2—acid base · 4 · methylthiobutyronitrile is based on the water content The sum of 2-methyl-4-methylthiobutanamine and 2-methyl-4 -methylthiobutyric acid in the hydrolysis mixture is at least 0.05% by weight. 51. The method according to item 45 or 47 of the scope of patent application, wherein the mud movement system in the circulation line is substantially disturbed, and the temperature of the circulation flow is at least 50 ° C in the entire circulation area. The dwell time upstream of the circulation zone of the forward flow port is at least 3 seconds. 52. The method according to claim 45 or 47, wherein the temperature of the product stream of the nitrile hydrolysis reactor is at least 50 ° C and the residence time is at least 30 seconds between the forward flow port and the dilution point. . 53. The method according to item 52 of the scope of patent application, wherein the flow in the zone between the amidine hydrolysis flow reactor and the dilution point is disturbed. 54. The method according to item 47 of the scope of patent application, wherein the flow regime and dwell time are such that at least one of the nitrile elimination reaction zones provided in the upstream portion of the circulation zone including the forward flow port is sequentially backmixed to the reaction zone And among them -11 _ This paper is suitable for "Family Standards (cNS) A4 ^ grid (21G x 297 public funds) ------- 495500 A BCD VI. Patent application scope The product of this nitrile reactor flows in An equivalent amount of forward flow reaction zone flowing between the forward flow port and the dilution point or the continuous amidine hydrolysis reactor. 55. The method according to item 47 of the scope of patent application, wherein in the forward flow reaction zone, the product stream of the nitrile reactor is between the forward flow port and the dilution point or the continuous amidine hydrolysis reactor, The flow system is thin-layered, and the flow system and dwell time are the same amounts that result in at least one sequential backmixing reaction zone provided in the forward flow reaction zone. 56. The method according to item 45 or 47 of the scope of the patent application, wherein the temperature in the amidine hydrolysis flow reactor is controlled to maintain the color of the completed aqueous hydrolysate based on a Garner color scale of less than 10 . 57. A method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, comprising: introducing 2-hydroxy-4-methylthiobutyronitrile and an aqueous mineral acid into a solution containing 2-hydroxy-4-methylthiobutane In an aqueous hydrolysis mixture of amine, mineral acid and unreacted 2-hydroxy-4-methylthiobutyronitrile; in a circulation zone containing a backmixed reaction zone and communicating with the backmixed reaction zone in fluid flow (the circulation zone contains In the continuous nitrile hydrolysis reactor of the circulation line), the 2-hydroxy-4-methylthiobutyronitrile in the hydrolysis mixture is hydrolyzed; the aqueous hydrolysis mixture in the circulation stream withdrawn from the back-mixing reaction zone is continuously circulated, Pass through the circulation zone and back to the back mixing reaction zone, and the circulating stream withdrawn from the back mixing reaction zone contains unreacted 2-hydroxy-4-methylthiobutyronitrile; removed from the forward flow port in the circulation zone A part of the circulating aqueous hydrolysis mixture is the nitrile hydrolysis reactor product stream, and then the nitrile hydrolysis reactor product stream is transported to the amidine hydrolysis flow reactor; the nitrile hydrolysis reactor product is diluted with water downstream of the forward flow port -12-_ This paper size applies to China National Standard (CNS) A4 (21 0 X 297 mm) 495500 6. Apply for a patent scope stream and provide a complete reaction stream; In this amine hydrolysis flow reaction H towel hydrolyzes the 2-hydroxy-4_methanbutamine in the reaction stream containing tritium to produce Completed aqueous hydrolysis product of 2_hydroxy_4_methylthiobutyric acid; the residence time of the circulating stream in the upstream of the circulation zone of the forward flow π and the nitrile hydrolysis reaction of the forward flow port before dilution The sum of the residence times downstream of the reactor product stream is at least 20 seconds. 58. According to the method of the Chinese government, the sum of dwell time is between 30 seconds and 5 minutes. 59. According to the application, the method in the scope of patent No. 57 wherein the flow system in the circulation line is substantially disturbed, and the residence time of the circulation flow in the upstream of the circulation area of the forward flow port is at least 3 seconds. 60. According to the request, please enclose the line of item 57 in which the residence time between the forward flow port and the dilution point is at least 30 seconds. 6L The method according to item 45 or 57 of the patent application, wherein the flow system and the dwell time are such that at least one of the nitrile elimination reaction zones provided in the upstream portion of the circulation zone including the forward flow port is sequentially backmixed. Zone and the equivalent of a forward flow reaction zone in which the nitrile reactor product flows between the forward flow port and the dilution port. 62. The method according to claim 45, 47 or 57 in which the external heat exchanger is located in the circulation line. 63. The method according to item 62 of the application, wherein the forward flow port is located upstream of the circulation line of the external heat exchanger. 64. The method according to item 62 of the patent application scope, wherein the aqueous mineral acid is introduced into 495500 A8 B8 C8 D8 into the aqueous hydrolysing mixture at the mouth of the external heat exchange device downstream of the circulation line. 65. According to the method of claim 45, 47, or 57 of the patent application, the wax hydrolysate reactor product stream is transported to the dilution point through a vertically lower conduit. 66. The method according to item 47 or 57 of the scope of the patent application, wherein the aqueous mineral acid, the water stream and the nitrile hydrolysis reaction product stream are mixed to form a completed reaction stream, which is introduced into the amidine hydrolysis flow reactor. 67. The method according to item 46 of the scope of the patent application, wherein the molar ratio of the mineral acid to the 2--5-yl-4-methylthiobutyronitrile added to the water of the month is between 0.6 and 1.5. And the total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 0.7 and 1.5. 68. The method according to item 66 of the scope of the patent application, wherein the molar ratio of the mineral compound to the 2-¾-4-methylthiobutanyl added to the hydrolytic reactor is between 0.6 and 1.5. The total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 0.7 and 1.5. 69. The method according to item 67 of the scope of the patent application, wherein the molar ratio of the mineral acid to the 2-hydroxy-4-methylthiobutyronitrile added to the hydrocyanic hydrolysis reactor is between 0.8 and 2. And, the total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 0.9 and 丨 · 2. 70. The method according to item 68 of the scope of the patent application, wherein the molar ratio of the mineral acid to the 2-hydroxy-4-methylthiobutyronitrile added to the moonlight hydrolysis reactor is between 0.8 and 2. And the total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 09 and 12. 71. The method according to item 4 5 or 57 of the scope of patent application, in which the bet -14-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 495500 The flow of the AB c D reactor product flow in the forward flow reaction zone between the forward flow port and the dilution point is made as a thin layer, and the flow system and the dwell time are such that the forward flow reaction is provided for the forward flow reaction. At least one of the zones is sequentially back-mixed with the equivalent of the reaction zone. 72. The method according to claim 55, wherein the flow regime and the dwell time are equivalent to the sequential back-mixing reaction zone provided between 2 and 3 in the forward flow reaction zone. 73. The method according to item 71 of the scope of the patent application, wherein the flow regime and the dwell time are equivalent to the sequential back-mixing reaction zone provided between 2 and 3 in the forward flow reaction zone. 74. A method according to claim 45, 47, or 57 in which the flow of the nitrile reactor product in a forward flow reaction zone between the forward flow port and the dilution point is made turbulent And the flow system and dwell time are the equivalents of at least one sequential backmixing reaction zone provided in the forward flow reaction zone. 75. The method according to claims 4, 5, 47, or 57 in the scope of the patent application, wherein the completed aqueous hydrolysate contains up to 0.05 wt% amidine. 76. The method according to claim 45, 47, or 57 wherein the flow regime and residence time are equivalents that cause at least two of the amine hydrolysis flow reactors to be sequentially mixed back into the reaction zone. 77. The method according to item 45, 47, or 57 of the patent application, wherein the flow system and the dwell time are the equivalents of at least 35 sequentially back-mixed reaction zones provided in the amidine hydrolysis flow reactor. 78. An aqueous hydrolysate composition, which is used for the preparation of methionine supplement -15- This paper size is applicable to the Chinese National Standard (CMS) A4 specification (210 X 297 mm) t Ding_ Scope of patent application ^ (2 -Nitrate_ 4-A concentrated aqueous solution of methylthiobutyric acid, the composition contains at least 36% by weight of 1% 2-hydroxymethylthiobutyric acid, at least 18% by weight of ammonium salt, and at least 15. fragrant '&quot; W * ^ / (\ -7 ^ Gu 21, south to 0.05% by weight of amidine and up to 0.05% by weight. / 0 Nitrile, the composition has a color based on the Garner color scale of not more than 10. 79 A composition according to item 78 of the patent application scope, which comprises at least $ 0 wt% ammonium salt and at least 25% by weight of water. 80. A composition according to item 78 of the patent application scope, wherein the composition is The color is between 5 and 10 based on the Garner color scale. 81 · —A method for preparing 2-methyl methiobutanoic acid, comprising: introducing mineral acid into a first reactor containing a continuous stirred tank reactor; 2- # 里 基 -4-methylthiobutyronitrile is introduced into the first reactor; ′, molt hydrolyzes 2-hydroxy-4-methylthiobutyronitrile in the first reactor, and continuously moves The heat of guess hydrolysis from the reaction mixture in the first reactor to produce an intermediate liquid hydrolysis solution containing 2-hydroxymethylthiobutanamine, and the 2-hydroxy-4-methylthiobutyronitrile is converted in the first reactor It is at least 90% of 2-hydroxy-4-methylthiobutamide; it continuously introduces water and the intermediate liquid hydrolysis solution into the flow reactor; it continuously hydrolyzes 2_hydroxyf-thiobutamide in the flow reactor to A liquid hydrolyzed hydrolysate solution containing 2-hydroxymethylthiobutyric acid is produced. 82. The method according to item 81 of the scope of the claimed patent, wherein the intermediate liquid hydrolysis / 4 liquid contains not more than 2% by weight of 2-hydroxy group-4- Methidine. 83. The method according to item 82 of the scope of patent application, wherein the intermediate liquid hydrolysis / valley liquor contains Nanda 11% by weight of 2-hydroxy-4-methylthiobutanoic acid, at least Water and at least 35 wt% amidine. __16- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) --------- 495500 A8 B8 C8 D8 6. Application scope of patent 84 · —A method for preparing 2-hydroxy-4-methylthiobutanoic acid, comprising: introducing mineral acid into a first reactor containing a continuous stirred tank reactor; and introducing 2-hydroxy-4-methylthio Butyronitrile is introduced into the first reactor; Continuously hydrolyzing 2- # to 4-methylthiobutyronitrile in the first reactor, while continuously removing the heat of nitrile hydrolysis from the reaction mixture in the first reactor to produce 2-hydroxy-4- An intermediate liquid hydrolysis solution of methotrexamide, in which the 2-hydroxy-4-methylthiobutyronitrile is converted to 2-epi-4-methylthiobutamide in the first reactor at least 90%; The intermediate liquid hydrolysis solution and water stream of the first reactor are continuously introduced into the second continuous stirred tank reactor, so that a substantial part of the 2-mercapto-4 -methanidine in the intermediate solution is continuously Hydrolysis in the stirred tank reactor to form the final reaction solution; the final reaction solution is continuously introduced into the flow reactor; A substantially single-phase reaction mixture in the flow reactor to produce a liquid hydrolysate solution containing 2-hydroxy-4 methiobutanoic acid. 85. The method according to item 34, 45, 47, 57, 81, or 84 of the scope of patent application, wherein the mineral acid is sulfuric acid. -17- This paper size applies to China National Standard (CNS) A4 (210X 297 mm)