Method and device for preparing 2-hydroxy-4-methylthiobutyric acid and intermediates thereof

专利摘要:
Provided by the present invention are a method and device for preparing 2-hydroxy-4-methylthiobutyric acid and intermediates thereof; the intermediates for preparing 2-hydroxy-4-methylthiobutyric acid comprise 3-methylthiopropionaldehyde and 2-hydroxy-4-methylthiobutyronitrile. The method for preparing 2-hydroxy-4-methylthiobutyric acid provided by the invention comprises: step (1), a step of causing acrolein to react with methyl mercaptan to prepare 3-methylthiopropionaldehyde; step (2), a step of causing 3-methylthiopropionaldehyde to react with hydrocyanic acid to prepare 2-hydroxy-4-methylthiobutyronitrile; step (3), a step of hydrating 2-hydroxy-4-methylthiobutyronitrile by using sulfuric acid, and then rehydrolyzing to prepare 2-hydroxy-4-methylthiobutyric acid; in steps (1), (2), and (3), the reaction conditions of the materials are detected online, and the proportions of the materials are controlled according to the detection results such that reactions are performed completely.
公开号:ES2837130A2
申请号:ES202190004
申请日:2019-08-27
公开日:2021-06-29
发明作者:Zhirong Chen；Hong Yin；Baishan Hu；Zhengjiang Wang；Zhixuan Wang；Cong Chen；Guisheng Qiu；Qichuan Li；Qingai Shi
申请人:Shandong Nhu Amino Acid Co Ltd；Zhejiang University ZJU；Zhejiang NHU Co Ltd；
IPC主号:

专利说明:

[0002] Method and device for preparing 2-hydroxy-4-methylthiobutyric acid and intermediates thereof
[0004] TECHNICAL FIELD
[0006] The present disclosure refers to a method and a device for preparing chemicals and, in particular, refers to a method and a device for preparing 2-hydroxy-4-methylthiobutyric acid and intermediates thereof.
[0008] BACKGROUND
[0010] 2-Hydroxy-4-methylthiobutyric acid, also called liquid methionine or hydroxy analog methionine, is used as an animal feed additive and can also be used as a methionine nutritional supplement to stimulate growth and development of animals. According to the literature, liquid methionine has a biological potency that is not very different from that of methionine and the synthetic process is relatively simple, therefore it has good market prospects.
[0012] Currently, the method for producing 2-hydroxy-4-methylthiobutyric acid in industrial setting mainly adopts acrolein (simply called ACR) as raw material. Acrolein is first reacted with methyl mercaptan under the action of the catalyst to prepare and obtain 3-methylthiopropionaldehyde (simply called MMP), and then gaseous or liquid hydrocyanic acid and 3-methylthiopropionaldehyde are used to prepare 2-hydroxy -4-methylthiobutyronitrile (simply called cyanohydrin) under the action of the catalyst, and 2-hydroxy-4-methylthiobutyronitrile is hydrolyzed in the presence of sulfuric acid to obtain 2-hydroxy-4-methylthiobutyric acid, that is, liquid methionine.
[0013] The materials involved in the reaction process mentioned above are either smelly (eg CH3SH) or very toxic (eg HCN and CH2 = CHCHO). Consequently, there are quite strict requirements for operational safety during the production process. Failure to monitor the brewing process in time can lead to considerable safety risks. Also, the excessive addition of the raw materials mentioned above (ie acrolein and hydrocyanic acid) can cause some undesirable side reactions. For example, an excess of acrolein and MMP can cause polymers to form, resulting in the formation of a high-boiling residue; While an excess of HCN (as described in CN1277816C, US4960932 and US4912257) not only reduces the operational safety, but also generates formic acid during the hydrolysis reaction process, ammonium formate is formed after neutralization, therefore that the quality of the ammonium sulfate recovered in the subsequent period is reduced.
[0014] In the patent published as CN101812004A, Degussa proposes a method for the preparation of 3-methylthiopropionaldehyde and 2-hydroxy-4-methylthiobutyronitrile. The reaction is carried out continuously in a fixed reaction bed. In order to maintain a favorable conversion rate and low reagent degradation, a slightly excessive amount of methyl mercaptan has to be kept in the reaction mixture and the excess range is controlled between 0.05% and 0.2%. . If crude MMP is used for the next reaction, the reaction is also carried out in an excessive amount of hydrocyanic acid, the excess range is controlled between 0.05% and 1%, the amount of hydrocyanic acid feed is controlled by using a hydrocyanic acid metering device during the reaction process, and the purity of the cyanohydrin finally obtained is approximately 92%. In the present patent, it is mentioned that acrolein and methyl mercaptan are reacted in substantially equivalent amounts in terms of stoichiometric amount; however, the control method to achieve the objective is not described. Hydrocyanic acid is dosed using a dosing device; Due to the existence of the secondary reaction (i.e. the polymerization of hydrocyanic acid), with the dosage alone it is, in fact, not possible to guarantee that the stoichiometric ratio of raw materials in the system meet the designed requirement. As could be seen from the examples, the cyanohydrin obtained with this method is of low purity and may not be used directly for the preparation of 2-hydroxy-4-methylthiobutyric acid.
[0016] In the patent published as CN1510030A, Novus proposes a method for the preparation of 3-methylthiopropionaldehyde and 2-hydroxy-4-methylthiobutyronitrile, where methyl mercaptan is added in a liquid reaction medium in an amount that is at least substantially equivalent to the stoichiometric amount of acrolein from the point of view of molarity. A slightly excessive amount of methyl mercaptan can be used and the molar ratio of methyl mercaptan to acrolein is about 1 to 1.02. The 3-methylthiopropionaldehyde obtained by the reaction can be directly reacted with hydrocyanic acid and used for the preparation of 2-hydroxy-4-methylthiobutyronitrile without having to remove high-boiling impurities or low-boiling point impurities in advance. Hydrocyanic acid is slightly 2% excessive over 3-methylthiopropionaldehyde. The prepared 2-hydroxy-4-methylthiobutyronitrile is used directly for the preparation of liquid methionine. The 2-hydroxy-4-methylthiobutyric acid obtained by means of extractive steam distillation is an aqueous solution of 85% to 90%. All of the intermediates in the present patent are used directly. Among them, however, the 3-methylthiopropionaldehyde content is 89.9% and there are impurities, such as acrolein and methyl mercaptan. However, regarding the cyanation reaction, the examples show that the distilled 3-methylthiopropionaldehyde is used and a resultant is obtained containing 98.2% of 2-hydroxy-4-methylthiobutyronitrile and 0.03% of 3 - methylthiopropionaldehyde. It can be seen that if 3-methylthiopropionaldehyde and 2-hydroxy-4-methylthiobutyronitrile are used directly in the next reaction without undergoing any treatment, 2-hydroxy-4-methylthiobutyric acid is obtained with low purity.
[0017] In the patent published as CN101735124A, it is proposed that when methylthiopropionaldehyde contains impurities such as mercaptan, these impurities or By-products can corrode reaction vessels and tubes during the hydrolysis process; therefore, the amount of methyl mercaptan needs to be controlled. Herein, distillation is used to purify 3-methylthiopropionaldehyde. If the 2-hydroxy-4-methylthiobutyronitrile does not meet the requirements of the reaction, this substance also has to undergo further treatment or purified by distillation before being introduced in the next step.
[0019] In the patent published as US2745745, Monsanto discloses a method for the preparation of 2-hydroxy-4-methylthiobutyric acid, where cyanohydrin is obtained by reacting MMP and HCN in a medium containing pyridine or amine, HCN is also found in an excessive amount during the reaction process, and the excess HCN has to be removed after the reaction is completed. In the present patent, a method is selected for conducting distillation under a certain pressure to remove excess HCN.
[0021] In the patent published as CN1148041, a method for the preparation of cyanohydrin by reacting gaseous hydrocyanic acid with MMP is disclosed. In this method, a reactive absorption column with plates is used, that is, a gas flow containing hydrocyanic acid is introduced through the bottom of the reactive absorption column with plates, while an aqueous MMP solution containing a buffer solution to the top of the column. To increase the reaction rate, an excessive amount of HCN is also added in MMP. To recover the remaining HCN and unreacted MMP contained in the waste gas of the reactive absorption column, an additional scrub column is installed on top of the reactive absorption column, water is used to wash said HCN and unreacted MMP. react, the water for washing is introduced into the product, which results in the water content in the product reaching approximately 48%. Consequently, the reaction product has to be further subjected to post-treatment operations, such as distillation; otherwise, it may not be used in the next hydrolysis reaction. Regarding the large-scale production of methionine, the above-mentioned distillation method consumes a lot of energy and does not It is desirable. Also, the reaction of the preparation of cyanohydrin by using hydrocyanic acid and methylthiopropionaldehyde is a reversible exothermic reaction and decomposition may occur during the distillation process, such that the yield of the final product is reduced.
[0023] In the patent published as US4225516, the preparation of MMP is carried out in a stirred tank reactor equipped with an external circulation cooling system. If the reaction is not completed in the prescribed residence time, the mixture is then supplied to the second reactor (eg, a plug flow reactor) for a complete reaction to occur. It can be seen that prolonging the residence time of the MMP reaction can also increase the conversion rates of acrolein and methyl mercaptan, and reduce the carryover of acrolein and methyl mercaptan.
[0024] In the patent published as CN103347854, Degussa discloses a method for preparing cyanohydrin. In this method, 3-methylthiopropionaldehyde is reacted with hydrocyanic acid in the presence of an alkaline catalyst in the main reaction zone to form cyanohydrin and HCN is used in an amount of 1.05 mol with respect to 1 mol of 3-methylthiopropionaldehyde. The main reaction zone is a stirred reactor or a loop reactor. Residual gaseous hydrocyanic acid leaving the main reaction zone after completion of the reaction is absorbed and then further reacted with the materials in the post-reaction zone. MMP material usually contains a small amount of methyl mercaptan; Excess methyl mercaptan is reacted with acrolein in the post-reaction zone to form MMP, followed by a reaction with HCN to form cyanohydrin at the same time. Finally, a cyanohydrin product with a content of 86% to 97% is obtained and the cyanohydrin content fluctuates greatly.
[0026] In summary, the raw materials and intermediates involved in the liquid methionine preparation process are smelly or highly toxic, making it difficult to direct sampling and analysis. However, if the performance of each stage is to be improved during the preparation process, the proportions of the raw materials in each stage have to be precisely adjusted, but no solution has been provided in the prior art.
[0028] SUMMARY
[0030] Problems to be solved by the exhibition
[0032] With regard to the problems mentioned above, the present disclosure discloses a method for the continuous preparation of 2-hydroxy-4-methylthiobutyric acid, where acrolein is used as the starting material and first reacted with methyl mercaptan to obtaining 3-methylthiopropionaldehyde; 3-methylthiopropionaldehyde is reacted with hydrocyanic acid to obtain 2-hydroxy-4-methylthiobutyronitrile and 2-hydroxy-4-methylthiobutyronitrile is hydrolyzed using sulfuric acid and then hydrolyzed to obtain acid 2-hydroxy-4-methylthiobutyric. In the present disclosure, the reaction status of the materials is detected by setting up detection devices online at each step of the reaction, and the proportions of the materials are controlled according to the detection results in order to be able to carry out a complete reaction.
[0034] Means to solve problems
[0036] The first aspect of the present discussion is to provide a method for the preparation of 3-methylthiopropionaldehyde as an intermediate of 2-hydroxy-4-methylthiobutyric acid, where the method comprises: reacting acrolein with an excessive amount of methyl mercaptan in the presence of a catalyst to obtain a pre-reaction solution of 3-methylthiopropionaldehyde; carry out an online detection of a hemiacetal content in the pre-reaction solution of 3-methylthiopropionaldehyde, and determine a supplemental amount of acrolein according to the detection results; and mixing and reacting the acrolein supplemented with the previous 3-methylthiopropionaldehyde reaction solution to be able to carry out a complete reaction of the hemiacetal contained in the previous 3-methylthiopropionaldehyde reaction solution, in order to prepare and obtain 3-methylthiopropionaldehyde .
[0038] Also, the feed molar ratio of acrolein and methyl mercaptan is 0.95: 1 to 0.99: 1, preferably 0.97: 1 to 0.98: 1.
[0040] Also, the catalyst is selected from organic bases, inorganic bases or salts formed by tertiary amines and acids, and is preferably a salt formed by a tertiary amine and 2-hydroxy-4-methylthiobutyric acid; the tertiary amine is one or more of triethylamine, tri-n-propylamine, tri-n-butylamine, triisopropylamine and N, N-dimethylbenzylamine; and the molar ratio of the tertiary amine and 2-hydroxy-4-methylthiobutyric acid is 1.05: 1 to 2.0: 1, preferably 1.1: 1 to 1.5: 1.
[0042] Also, the addition amount of the catalyst is between 0.05% and 0.5% and preferably between 0.1% and 0.3% of the total mass of the added acrolein and methyl mercaptan.
[0044] Furthermore, the reaction between acrolein and the excessive amount of methyl mercaptan and the reaction between the supplemented acrolein and the previous 3-methylthiopropionaldehyde reaction solution have a reaction temperature of between 20 and 60 ° C, preferably between 20 and 40 ° C.
[0046] Likewise, the method for the preparation of 3-methylthiopropionaldehyde as an intermediate of 2-hydroxy-4-methylthiobutyric acid also comprises a step of carrying out an on-line detection of the residual amount of hemiacetal in the obtained 3-methylthiopropionaldehyde and of adjusting the supplemental amount of acrolein from according to the detection results.
[0048] Also, a Raman spectroscopic detection method is employed in online detection.
[0050] Likewise, the reaction between acrolein and the excess amount of methyl mercaptan is carried out in a first reactor R1 and the reaction between the supplemented acrolein and the previous 3-methylthiopropionaldehyde reaction solution is carried out in a second reactor R2.
[0052] Also, the first reactor R1 is a recirculation reactor and the second reactor R2 is a plug flow reactor.
[0054] Also, the first reactor R1 is a tower reactor or a multi-pass stirred reactor, preferably a tower reactor with baffle plate (s) arranged inside.
[0056] Also, an online Raman spectroscopy detector D1 is provided at an outlet of the first reactor for the online detection of the hemiacetal content in the 3-methylthiopropionaldehyde pre-reaction solution.
[0058] Also, an online Raman spectroscopy detector D2 is provided at an outlet of the second reactor for online detection of hemiacetal content in 3-methylthiopropionaldehyde.
[0060] Also, a part of the previous 3-methylthiopropionaldehyde reaction solution is introduced into the second reactor R2, and the remaining part is used as circulating materials of the first reactor R1 and the ratio of the amount of materials that are introduced into the second reactor. R2 with respect to the amount of materials used as circulating materials of the first reactor R1 is 1:10 to 1:50, preferably 1:15 to 1:30.
[0061] Also, the 3-methylthiopropionaldehyde obtained by the preparation is used for the preparation of 2-hydroxy-4-methylthiobutyronitrile.
[0063] Also, the 3-methylthiopropionaldehyde obtained by the preparation is used for the preparation of 2-hydroxy-4-methylthiobutyric acid.
[0065] The second aspect of the present disclosure is to provide a method for the preparation of 2-hydroxy-4-methylthiobutyronitrile as an intermediate of 2-hydroxy-4-methylthiobutyric acid, where the method comprises: reacting 3-methylthiopropionaldehyde with an excessive amount of hydrocyanic acid to obtain a pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile; carrying out a detection of the content of hydrocyanic acid in the pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile and determining the supplementary amount of 3-methylthiopropionaldehyde according to the detection results; and mixing and reacting the previous 2-hydroxy-4-methylthiobutyronitrile reaction solution with the supplemented 3-methylthiopropionaldehyde to be able to carry out a complete reaction of the hydrocyanic acid contained in the previous 2-hydroxy-4-methylthiobutyronitrile reaction solution. , in order to prepare and obtain 2-hydroxy-4-methylthiobutyronitrile.
[0067] Also, the feed molar ratio of 3-methylthiopropionaldehyde and hydrocyanic acid is 0.95: 1 to 0.99: 1, preferably 0.97: 1 to 0.98: 1.
[0069] Furthermore, the reaction between 3-methylthiopropionaldehyde and the excessive amount of hydrocyanic acid and the reaction between the supplemented 3-methylthiopropionaldehyde and the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile have a reaction temperature of between 20 and 80 ° C. preferably between 25 and 45 ° C.
[0071] Likewise, the method for the preparation of 2-hydroxy-4-methylthiobutyronitrile as an intermediate of 2-hydroxy-4-methylthiobutyric acid also comprises a step of carrying out performing an online detection of the residual amount of hydrocyanic acid in the obtained 2-hydroxy-4-methylthiobutyronitrile and adjusting the supplemental amount of 3-methylthiopropionaldehyde according to the detection results.
[0073] Also, an online Raman spectroscopic detection method is employed in online detection.
[0075] Likewise, the reaction between 3-methylthiopropionaldehyde and the excessive amount of hydrocyanic acid is carried out in a third reactor R3 and the reaction between the supplemented 3-methylthiopropionaldehyde and the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile is carried out carried out in a fourth reactor R4.
[0077] Also, the third reactor R3 is a recirculating reactor and the fourth reactor R4 is a plug flow reactor.
[0079] Also, the third reactor R3 is a tower reactor or a multi-pass stirred reactor, preferably a tower reactor with baffle plate (s) arranged inside.
[0081] Also, an online Raman spectroscopy detector D3 is provided at an outlet of the third reactor for the online detection of the content of hydrocyanic acid in the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution.
[0083] Also, a D4 on-line Raman spectroscopy detector is provided at an outlet of the fourth reactor R4 for on-line detection of hydrocyanic acid content in 2-hydroxy-4-methylthiobutyronitrile.
[0085] Also, a part of the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution in the third reactor R3 is introduced into the fourth reactor R4, and the remaining part is used as circulating materials of the third reactor R3 and the ratio of the amount of materials that are introduced into the fourth reactor R4 with respect to the amount of materials used as circulating materials of the third reactor R3 is from 1: 5 to 1:30, preferably, from 1:10 to 1:20.
[0087] Also, said 3-methylthiopropionaldehyde is prepared and obtained by using the method provided by the first aspect of the present disclosure.
[0089] Also, the 2-hydroxy-4-methylthiobutyronitrile obtained by the preparation is used for the preparation of 2-hydroxy-4-methylthiobutyric acid.
[0091] The third aspect of the present disclosure is to provide a method for the preparation of 2-hydroxy-4-methylthiobutyric acid, where the method comprises:
[0093] step (1): a step of reacting acrolein with methyl mercaptan to prepare 3-methylthiopropionaldehyde;
[0095] step (2): a step of reacting 3-methylthiopropionaldehyde with hydrocyanic acid to prepare 2-hydroxy-4-methylthiobutyronitrile and
[0097] step (3): a step of hydrating 2-hydroxy-4-methylthiobutyronitrile by using sulfuric acid and then hydrolyzing to prepare 2-hydroxy-4-methylthiobutyric acid.
[0099] where in steps (1), (2) and (3), the reaction state of the materials is detected online and the proportions of the materials are controlled according to the detection results in order to be able to carry out a complete reaction.
[0101] Likewise, said stage (1) comprises:
[0103] reacting acrolein with an excessive amount of methyl mercaptan in the presence of a catalyst in a first reactor R1 to form a pre-reaction solution of 3-methylthiopropionaldehyde; carry out an online detection of the hemiacetal content in the 3-methylthiopropionaldehyde pre-reaction solution and determine the supplemental amount of acrolein according to the detection results; mix the previous reaction solution of 3-methylthiopropionaldehyde with the supplemented acrolein and then allow the mixture to enter a second reactor R2 to be able to carry out a complete reaction of hemiacetal contained in the previous reaction solution of 3- methylthiopropionaldehyde, in order to prepare and obtain a reaction solution of 3-methylthiopropionaldehyde.
[0105] Likewise, the first reactor R1 is a recirculation reactor selected from a tower reactor or a multi-pass stirred reactor and is preferably a tower reactor with baffle plate (s) arranged inside.
[0107] Also, the feed molar ratio of acrolein and methyl mercaptan is 0.95: 1 to 0.99: 1, preferably 0.97: 1 to 0.98: 1.
[0109] Also, a part of the previous 3-methylthiopropionaldehyde reaction solution is introduced into the second reactor R2, and the remaining part is used as circulating materials of the first reactor R1 and the ratio of the amount of materials that are introduced into the second reactor. R2 with respect to the amount of materials used as circulating materials of the first reactor R1 is 1:10 to 1:50, preferably 1:15 to 1:30.
[0111] Also, said step (1) further comprises a step of carrying out an online detection of the residual amount of hemiacetal in 3-methylthiopropionaldehyde and of adjusting the supplemental amount of acrolein according to the detection results.
[0113] Furthermore, the reaction between acrolein and the excessive amount of methyl mercaptan and the reaction between the supplemented acrolein and the previous 3-methylthiopropionaldehyde reaction solution have a reaction temperature of between 20 and 40 ° C.
[0114] Likewise, the catalyst is selected from organic bases, inorganic bases or salts formed by tertiary amines and acids; and the amount of the catalyst is between 0.05% and 0.5% and preferably between 0.1% and 0.3% of the total mass of acrolein and methyl mercaptan.
[0116] Likewise, the catalyst is a salt formed by a tertiary amine and 2-hydroxy-4-methylthiobutyric acid, where the molar ratio of the tertiary amine to 2-hydroxy-4-methylthiobutyric acid is 1.05: 1 to 2 , 0: 1, preferably 1.1: 1 to 1.5: 1, and the tertiary amine is at least one selected from triethylamine, tri-n-propylamine, tri-n-butylamine, triisopropylamine and N, N-dimethylbenzylamine .
[0118] Also, the feed molar ratio of acrolein and methyl mercaptan in the 3-methylthiopropionaldehyde pre-reaction solution is 0.95: 1 to 0.99: 1; preferably 0.97: 1 to 0.98: 1.
[0120] Likewise, said stage (2) comprises:
[0122] reacting 3-methylthiopropionaldehyde with an excessive amount of hydrocyanic acid in a third reactor R3 to form a pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile; carry out an online detection of the hydrocyanic acid content in the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution and determine the supplemental amount of 3-methylthiopropionaldehyde according to the detection results; and mixing the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile with the supplemented 3-methylthiopropionaldehyde and then allowing the mixture to be introduced into a fourth reactor R4 to be able to carry out a complete reaction of hydrocyanic acid contained in 2-hydroxy-4-methylthiobutyronitrile, in order to prepare and obtain 2-hydroxy-4-methylthiobutyronitrile.
[0123] Likewise, the third reactor R3 is selected from a tower reactor or a multi-pass stirred reactor and is preferably a tower reactor with baffle plate (s) arranged inside.
[0125] Also, a part of the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution in the third reactor R3 is introduced into the fourth reactor R4, and the remaining part is used as circulating materials of the third reactor R3 and the ratio of the amount of materials that are introduced into the fourth reactor R4 with respect to the amount of materials used as circulating materials of the third reactor R3 is from 1: 5 to 1:30, preferably, from 1:10 to 1:20.
[0127] Also, the feed molar ratio of 3-methylthiopropionaldehyde and hydrocyanic acid is 0.95: 1 to 0.99: 1, preferably 0.97: 1 to 0.98: 1.
[0129] Furthermore, the reaction between 3-methylthiopropionaldehyde and the excessive amount of hydrocyanic acid and the reaction between the supplemented 3-methylthiopropionaldehyde and the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile have a reaction temperature of between 25 and 45 ° C. .
[0131] Likewise, said step (2) further comprises a step of carrying out an online detection of the residual amount of hydrocyanic acid in 2-hydroxy-4-methylthiobutyronitrile and of adjusting the supplementary amount of 3-methylthiopropionaldehyde according to the results of detection.
[0133] Likewise, said stage (3) comprises:
[0135] subjecting 2-hydroxy-4-methylthiobutyronitrile to a hydration reaction in the presence of sulfuric acid in a hydration reactor R5 to form 2-hydroxy-4-methylthiobutyramide, where the residual amount of 2-hydroxy-4-methylthiobutyronitrile in the reaction solution is detected online and the amount of sulfuric acid to be used is adjusted according to the detection results, in order to be able to carry out a complete hydration reaction; Y
[0137] mixing 2-hydroxy-4-methylthiobutyramide with water, and then allowing the mixture to enter a hydrolysis reactor R6, in order to prepare 2-hydroxy-4-methylthiobutyric acid by the hydrolysis reaction.
[0139] Likewise, the hydration reactor R5 and / or the hydrolysis reactor R6 is a multi-pass stirred reactor with a number of stirring passes from 3 to 20 and preferably from 5 to 15.
[0141] Likewise, said step (3) further comprises the following step: adjusting the pH value of 2-hydroxy-4-methylthiobutyric acid between 1 and 2, in order to obtain a neutralized solution of 2-hydroxy-4-methylthiobutyric acid; allowing the neutralized 2-hydroxy-4-methylthiobutyric acid solution to enter an extraction tower for extraction; and allowing an extraction liquid containing 2-hydroxy-4-methylthiobutyric acid to enter a distillation tower by steam stripping, in order to obtain 2-hydroxy-4-methylthiobutyric acid from the bottom of the distillation tower. by steam entrainment.
[0143] Also, the extraction solvent of the neutralized 2-hydroxy-4-methylthiobutyric acid solution is one selected from methyl isobutyl ketone, butanone, pentanone, hexanone, and tert-butyl methyl ether; and the mass ratio of the extraction solvent and the neutralized 2-hydroxy-4-methylthiobutyric acid solution is 0.3: 1 to 3: 1, preferably 0.5: 1 to 2: 1.
[0145] Also, the extraction tower is a multi-pass agitated extraction tower with a number of agitation steps of 10 to 30 and preferably 15 to 25.
[0147] Also, the steam distillation tower is a plate tower with a number plates from 10 to 40 and preferably 15 to 30.
[0149] Also, online Raman spectroscopic detection is employed in online detection.
[0151] The fourth aspect of the present disclosure is to provide a continuous production device for the preparation of 2-hydroxy-4-methylthiobutyric acid, where the continuous production device comprises:
[0153] a 3-methylthiopropionaldehyde production device, a 2-hydroxy-4-methylthiobutyronitrile production device and a 2-hydroxy-4-methylthiobutyric acid production device connected sequentially;
[0155] The device for the production of 3-methylthiopropionaldehyde comprises a first reactor R1 for the formation of the previous reaction solution of 3-methylthiopropionaldehyde and a second reactor R2 for the preparation and obtaining of 3-methylthiopropionaldehyde, where the outputs of the first reactor R1 and the second reactor R2 are provided, respectively, with a detection device for the detection of the hemiacetal content;
[0157] The device for the production of 2-hydroxy-4-methylthiobutyronitrile comprises a third reactor R3 for the formation of a previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile and a fourth reactor R4 for the preparation and obtaining of 2-hydroxy-4 -methylthiobutyronitrile, where the outlets of the third reactor R3 and the fourth reactor R4 are provided, respectively, with a detection device for the detection of the content of hydrocyanic acid; Y
[0159] The 2-hydroxy-4-methylthiobutyric acid production device comprises a hydration reactor R5 for the formation of 2-hydroxy-4-methylthiobutyramide and a hydrolysis reactor R6 for the preparation of 2-hydroxy-4-methylthiobutyric acid by means of hydrolysis reaction plant, as well as an extraction tower and a steam distillation tower, where the outlet of the hydration reactor R5 is equipped with a detection device for the detection of the content of 2-hydroxy-4-methylthiobutyronitrile.
[0161] Likewise, said device also comprises a display device for the detection results.
[0163] Also, the detection device is an online Raman spectroscopic detection device.
[0165] Likewise, both the first reactor R1 and the third reactor R3 are recirculating reactors, which are selected from tower reactors or multi-pass stirred reactors and, preferably, tower reactors with baffle plate (s) arranged inside. .
[0167] Also, both the second reactor R2 and the fourth reactor R4 are plug flow reactors.
[0169] Also, both the hydration reactor R5 and the hydrolysis reactor R6 are multi-pass stirred reactors with a number of stirring passes from 3 to 20 and preferably from 5 to 15.
[0171] Also, the extraction tower is a multi-pass agitated extraction tower with a number of agitation steps of 10 to 30 and preferably 15 to 25.
[0173] Also, the steam distillation tower is a plate tower with a plate number of 10 to 40 and preferably 15 to 30.
[0175] Advantageous effects of exposure
[0177] Compared with the prior art, the present disclosure is able to achieve the following effects.
[0179] By adopting the preparation method of the present disclosure, it is possible to carry out on-line detection for specific materials (i.e., methyl mercaptan, hydrocyanic acid, and 2-hydroxy-4-methylthiobutyronitrile, and 2-hydroxy-4-methylthiobutyronitrile) that intervene in the reaction system, reduce the safety risks caused by direct sampling during the production process and improve the safety of the production process.
[0181] By adopting the preparation method of the present disclosure, the reaction efficiency of various materials such as acrolein, methyl mercaptan, 3-methylthiopropionaldehyde, hydrocyanic acid and 2-hydroxy-4-methylthiobutyronitrile can be avoided, the remnant of raw materials into intermediates and source products and liquid methionine with a high content is prepared and obtained.
[0183] By adopting the method of preparation of the present disclosure, the proportions of the materials can be strictly controlled such that the 3-methylthiopropionaldehyde and 2-hydroxy-4-methylthiobutyronitrile obtained by the preparation are practically free of impurities and can enter directly into the following processes without undergoing post-treatment, so that not only is production efficiency improved, but the problem of discharging the "three wastes" generated due to post-treatment is also reduced, and thus more environmentally friendly. environment.
[0185] By adopting the preparation method and device of the present disclosure, the product yield is high and it is possible to save raw materials and reduce costs.
[0187] BRIEF DESCRIPTION OF THE DRAWINGS
[0189] Figure 1 is a flow chart of the continuous preparation of 2-hydroxy-4-methylthiobutyric acid.
[0190] Figure 2 shows the comparison between the Raman spectrum of 3-methylthiopropionaldehyde and the Raman spectra of 3-methylthiopropionaldehyde and methyl mercaptan hemiacetal.
[0192] Figure 3 is the Raman spectrum of the mixture of 2-hydroxy-4-methylthiobutyronitrile and hydrocyanic acid.
[0194] Figure 4 is the Raman spectrum of 2-hydroxy-4-methylthiobutyramide.
[0196] Description of reference signs
[0198] 1: the first R1 reactor
[0199] 2: the second reactor R2
[0200] 3: the third R3 reactor
[0201] 4: the fourth R4 reactor
[0202] 5: R5 hydration reactor
[0203] 6: hydrolysis reactor R6
[0204] 7: R7 neutralization reactor
[0205] 8: extraction tower C1
[0206] 9: C2 steam distillation tower
[0207] 10 to 16: static mixers M1 to M7
[0208] 17 to 19: heat exchangers E1 to E3
[0209] 20 to 21: circulation pumps P1 to P2
[0210] 22 to 24: Raman spectrum detection and processing devices LM1 to LM3.
[0211] 25 to 29: Raman detectors D1 to D5
[0213] DETAILED DESCRIPTION
[0215] One aspect of the present discussion is to provide a method for the continuous preparation of 2-hydroxy-4-methylthiobutyric acid, where the method comprises at least the following steps:
[0217] a step of subjecting 2-hydroxy-4-methylthiobutyronitrile to a hydration reaction in the presence of sulfuric acid to form 2-hydroxy-4-methylthiobutyramide, where the residual amount of 2-hydroxy-4-methylthiobutyronitrile is detected in the reaction solution and the amount of sulfuric acid to be used is adjusted according to the detection results, in order to be able to carry out a complete hydration reaction; Y
[0219] a step of subjecting 2-hydroxy-4-methylthiobutyramide to hydrolysis reaction in order to prepare 2-hydroxy-4-methylthiobutyric acid.
[0221] Likewise, the present disclosure also discloses a method for the preparation of 2-hydroxy-4-methylthiobutyronitrile, said method comprising:
[0223] reacting 3-methylthiopropionaldehyde with an excessive amount of hydrocyanic acid to form a pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile; detect the content of hydrocyanic acid in the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution and determine the supplemental amount of 3-methylthiopropionaldehyde according to the detection results; and mixing the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile with the supplemented 3-methylthiopropionaldehyde to allow the 3-methylthiopropionaldehyde to react with the hydrocyanic acid in an equimolar ratio, in order to prepare and obtain 2-hydroxy-4 -methylthiobutyronitrile.
[0225] Likewise, the present disclosure also discloses a method for the preparation of 3-methylthiopropionaldehyde, said method comprising:
[0227] reacting acrolein with an excessive amount of methyl mercaptan in the presence of a catalyst to form a pre-reaction solution of 3-methylthiopropionaldehyde; detecting the hemiacetal content in the 3-methylthiopropionaldehyde pre-reaction solution and determining the supplemental amount of acrolein according to the detection results; and mixing the 3-methylthiopropionaldehyde pre-reaction solution with the supplemented acrolein to allow the acrolein to react with methyl mercaptan in an equimolar ratio, in order to prepare and obtain 3-methylthiopropionaldehyde.
[0229] Catalysts commonly used in the art can be used as the catalyst in the present disclosure, including organic bases, inorganic bases, or salts formed by tertiary amines and acids. Organic bases include low molecular weight amines, high molecular weight amines, among others. As low molecular weight amines, for example, amines having between 1 and 36 carbon atoms can be given. Preferred low molecular weight amines include tri (C1-C12 alkyl) amines, such as triethylamine and triisopropylamine; adialkylalkyl amines, such as dimethylbenzylamine; dialkylaryl amines, such as N, N-dimethylaniline; Heterocyclic amines, such as nicotinamide, imidazole, benzimidazole, N-C1-6 alkylmorpholine, methylpyridine, pyrazine, among others. As high molecular weight amines, there can be exemplified, for example, polyvinylpyrrolidine, diethylaminoethyl polystyrene, diethylaminomethyl polystyrene, dimethylaminomethyl polystyrene, diethylaminomethyl macroreticular resin, diethylaminoethyl polystyrene, among others.
[0231] Alkali metal hydroxides, alkali metal cyanides, alkali metal carbonates, alkali metal bicarbonates, among others, can be used as inorganic bases. Specifically, for example, sodium hydroxide, potassium hydroxide, NaCN, KCN, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, among others. .
[0233] A mixture of a low molecular tertiary amine and an organic acid or an acid Inorganic can be used as the mixture of a tertiary amine and an acid, such that they are able to set the pH in a desired range more easily. Organic acids include short chain fatty acids, organic sulfonic acids, etc. As short chain fatty acids, for example, acetic acid, formic acid, propionic acid, butyric acid, citric acid, among others, are included. As for organic sulfonic acids, trifluoromethanesulfonic acid, among others, can be given as an example. The inorganic acid is preferably sulfuric acid or phosphoric acid.
[0235] Said mixture of a tertiary amine and an acid is preferably a salt formed by a tertiary amine and 2-hydroxy-4-methylthiobutyric acid, where the molar ratio of the tertiary amine to 2-hydroxy-4-methylthiobutyric acid is 1.05: 1 to 2.0: 1, preferably 1.1: 1 to 1.5: 1, and the tertiary amine is at least one selected from triethylamine, tri-n-propylamine, tri-n-butylamine , triisopropylamine and N, N-dimethylbenzylamine.
[0237] Another aspect of the present disclosure is to provide a method for the continuous preparation of 2-hydroxy-4-methylthiobutyric acid, comprising:
[0239] step (1): a step of reacting acrolein with methyl mercaptan to prepare 3-methylthiopropionaldehyde;
[0241] step (2): a step of reacting 3-methylthiopropionaldehyde with hydrocyanic acid to prepare 2-hydroxy-4-methylthiobutyronitrile and
[0243] step (3): a step of hydrating 2-hydroxy-4-methylthiobutyronitrile by using sulfuric acid and then hydrolyzing to prepare 2-hydroxy-4-methylthiobutyric acid;
[0245] where in steps (1), (2) and (3), the reaction state of the materials is detected online and the proportions of the materials are controlled according to the detection results in order to be able to carry out a complete reaction.
[0246] A specific embodiment of the present disclosure comprises the following steps.
[0248] Step (1): a step of reacting acrolein with methyl mercaptan to prepare 3-methylthiopropionaldehyde.
[0250] The preparation of said 3-methylthiopropionaldehyde is carried out in two reactors operating continuously, where the first reactor R1 is a recirculation reactor and the second reactor R2 is a plug flow reactor. First, the acrolein material ACR1 is mixed with the circulating materials in the static mixer M2; then the mixture is mixed together with methyl mercaptan and the catalyst in the static mixer M1, and the mixed materials are first introduced into the first reactor R1 and reacted under conditions between 20 and 40 ° C to obtain a pre-reaction solution of 3-methylthiopropionaldehyde. After the 3-methylthiopropionaldehyde pre-reaction solution has cooled, a part of said pre-reaction solution is removed and supplied to the second reactor R2 for 3-methylthiopropionaldehyde, and the remaining part is recycled and used as the circulating materials. of the first reactor R1.
[0252] In order to guarantee an equimolar ratio of methyl mercaptan and acrolein in the second reactor R2, the Raman detector D1 is provided at the outlet of the circulation pump P1 at the bottom of the first reactor. The supplemental amount of acrolein ACR2 is determined by determining the hemiacetal content in the 3-methylthiopropionaldehyde pre-reaction solution, the supplemented ACR2 and the 3-methylthiopropionaldehyde pre-reaction solution are mixed in the static mixer M3 and then , are introduced into the second reactor R2 and the mixture is further reacted under conditions between 20 and 40 ° C to obtain the 3-methylthiopropionaldehyde reaction solution. The Raman detector D2 is provided at the outlet of the second reactor R2. The amount of ACR2 is adjusted slightly by determining the residual amount of hemiacetal in the 3-methylthiopropionaldehyde reaction solution, in order to ensure a basically complete hemiacetal reaction.
[0254] Step (2): a step of reacting 3-methylthiopropionaldehyde with hydrocyanic acid to prepare 2-hydroxy-4-methylthiobutyronitrile
[0256] The preparation of said 2-hydroxy-4-methylthiobutyronitrile is also carried out in two continuously operating reactors, where the third reactor R3 is a recirculation reactor and the fourth reactor R4 is a plug flow reactor. Most of the MMP1 material in the 3-methylthiopropionaldehyde reaction solution obtained in the previous step is mixed together with the circulating materials and hydrocyanic acid in the static mixer M4, and the mixed materials are introduced into the third reactor R3 and made React under conditions between 25 and 45 ° C to obtain a pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile. A part of the previous 2-hydroxy-4-methylthiobutyronitrile reaction solution is extracted and supplied to the fourth reactor R4 for 2-hydroxy-4-methylthiobutyronitrile after being cooled, and the remaining part is recycled and used as the circulating materials. of the third reactor R3.
[0258] In order to guarantee an equimolar ratio of hydrocyanic acid and 3-methylthiopropionaldehyde in the fourth reactor R4, the Raman detector D3 is provided at the outlet of the circulation pump P2 at the bottom of the first reactor. The supplemental amount of 3-methylthiopropionaldehyde MMP2 is determined by determining the content of hydrocyanic acid in the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution. The supplemented MMP2 and the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution are mixed in the static mixer M5 and then introduced into the fourth reactor R4, and the mixture is reacted under conditions between 25 and 45 ° C to obtain the 2-hydroxy-4-methylthiobutyronitrile reaction solution. The Raman detector D4 is provided at the outlet of the fourth reactor R4. The amount of MMP2 is adjusted slightly by determining the residual amount of hydrocyanic acid in the 2-hydroxy-4-methylthiobutyronitrile reaction solution, in order to ensure a basically complete hydrocyanic acid reaction.
[0260] Step (3): a step of hydrating 2-hydroxy-4-methylthiobutyronitrile by using sulfuric acid and then hydrolyzing to prepare 2-hydroxy-4-methylthiobutyric acid
[0262] The hydrolysis reaction is carried out in two continuous multi-pass stirred reactors connected in series; hydration reactor R5 is a reactor in which 2-hydroxy-4-methylthiobutyronitrile is hydrated to form 2-hydroxy-4-methylthiobutyramide, and hydrolysis reactor R6 is a reactor in which 2-hydroxy-4- Methylthiobutyramide is hydrolyzed to synthesize 2-hydroxy-4-methylthiobutyric acid. The 2-hydroxy-4-methylthiobutyronitrile reaction solution obtained in the previous step and the sulfuric acid solution (70% by weight to 75% by weight) are mixed by means of the static mixer M6 and then introduced in the hydration reaction R5, and the mixture is subjected to hydration reaction under the conditions of 50-70 ° C to obtain the 2-hydroxy-4-methylthiobutyramide reaction solution. This reaction solution and water are mixed together by means of the static mixer M6, and then R6 is introduced into the hydrolysis reactor and the mixture is heated to between 90 and 120 ° C and subjected to a hydrolysis reaction to obtain the 2-hydroxy-4-methylthiobutyric acid reaction solution.
[0264] In order to ensure a complete hydration reaction, a Raman spectroscopy detector D5 is provided at the outlet of the hydration reactor R5. The amount of the sulfuric acid solution is adjusted by determining the remaining 2-hydroxy-4-methylthiobutyronitrile in the reaction solution, and the amount of water that is introduced into the hydrolysis reactor R6 is adjusted at the same time, with in order to ensure that the hydrolysis reaction is basically complete.
[0266] The reaction solution of 2-hydroxy-4-methylthiobutyric acid obtained by the aforementioned hydrolysis reaction is supplied to the continuous neutralization reactor R7 and it is adjusted with ammonia to achieve a pH value between 1 and 2, in order to obtain the neutralized solution of 2-hydroxy-4-methylthiobutyric acid. Then, said neutralized solution is introduced in the upper part of the multi-step extraction tower C1, the solvent is introduced in the lower part of the extraction tower C1 and a countercurrent extraction is carried out under conditions of between 30 and 50 ° C. An extraction liquid containing 2-hydroxy-4-methylthiobutyric acid is obtained from the upper part of the extraction tower C1, and an ammonium sulfate solution is obtained from the lower part. The extraction liquid containing 2-hydroxy-4-methylthiobutyric acid is introduced in the upper part of the C2 steam stripping tower, the steam is introduced in the lower part to carry out the steam extraction, and the Solvent vapor obtained from the upper part of the extraction tower can be applied directly to the extraction tower C1 after being condensed by the condenser E3. The 2-hydroxy-4-methylthiobutyric acid product is obtained from the bottom of the steam distillation tower.
[0268] The method for the continuous preparation of 2-hydroxy-4-methylthiobutyric acid provided by the present disclosure is able to solve the problem existing in the prior art that the detection is not capable of being carried out on-line. In a preferred technical solution of the present disclosure, the Raman spectroscopy detection is used in combination with the process control, which allows the correct control of the proportions of the raw materials of the reaction and, therefore, achieves the objectives of reduce the consumption of raw materials, reduce by-products, reduce the carryover of raw materials and intermediate products, and improve operational safety and process stability.
[0270] By analyzing the Raman spectroscopy signals of the reagents and intermediates at each stage of the reaction, the inventors have found that when methyl mercaptan is reacted with acrolein, if 3-methylthiopropionaldehyde (MMP) is used as the solvent, the methyl mercaptan will react with MMP to form hemiacetal, and its reaction formula is as follows:
[0271]
[0273] The hemiacetal formed by the reaction presents characteristic absorption peaks in the Raman spectrum and the characteristic absorption peaks present maximum absorption at a wave number of 400 cm-1 (see figure 2, characteristic peak A), and the methylmercaptan content in the reaction solution can be accurately determined by using this absorption peak. Consequently, in the present disclosure, the synthesis of MMP is carried out in two reactors connected in series. The MMP product is used as the reaction medium in the first reactor; Most acrolein is first reacted with an excessive amount of methyl mercaptan, the process parameters of the reaction are adjusted to allow for a basically complete reaction of acrolein, and the excess methyl mercaptan is reacted with MMP to form hemiacetal. The methyl mercaptan content can be calculated and obtained by determining the hemiacetal content in the pre-reaction solution at the outlet of the first reactor, and then the acrolein, of which the amount is needed by part of the stoichiometric ratio, is added further at the inlet of the second reactor and the hemiacetal is reacted basically completely in the second reactor.
[0275] The same idea is adopted after reacting MMP with hydrocyanic acid to form 2-hydroxy-4-methylthiobutyronitrile. Through research, hydrocyanic acid and 2-hydroxy-4-methylthiobutyronitrile have been found to exhibit characteristic absorption peaks at wave numbers of about 2080 cm-1 and about 2240 cm-1, respectively (see Figure 3) ( the characteristic peak of cyanohydrin indicated in the figure is the characteristic peak of 2-hydroxy-4-methylthiobutyronitrile), and the content of hydrocyanic acid can be determined by the relative size of the two absorption peaks. Accordingly, 2-hydroxy-4-methylthiobutyronitrile is used as the reaction medium; Most of the MMP is first reacted with an excessive amount of hydrocyanic acid in the third reactor, and the process parameters of the reaction are adjusted to allow a basically complete MMP reaction. The content of hydrocyanic acid in the pre-reaction solution at the outlet of the third reactor is determined, and then the MMP, of which the amount is needed per part of the stoichiometric ratio, is further added at the inlet of the fourth reactor and the hydrocyanic acid is reacted basically completely in the fourth reactor.
[0277] Since 2-hydroxy-4-methylthiobutyronitrile is unstable, in order to ensure that by-products are reduced as much as possible during the hydrolysis reaction, it is necessary to synthesize 2-hydroxy-4-methylthiobutyramide by means of sufficient hydration. at a relatively low temperature in sulfuric acid with a relatively high concentration. For this reason, online Raman spectroscopy is used in the present discussion to monitor the hydration process of 2-hydroxy-4-methylthiobutyronitrile. By monitoring whether the characteristic absorption peak of 2-hydroxy-4-methylthiobutyronitrile (wave number: 2240 cm-1) has been completely converted into the characteristic absorption peak of amide (wave number: 1730 cm-1, See Fig. 4) At the outlet of the hydration reactor, the degree of the hydration reaction is determined, and the feed amount of sulfuric acid and the amount of water in the subsequent hydrolysis reaction are adjusted accordingly.
[0279] Another aspect of the present disclosure is to provide a continuous production device for the preparation of 2-hydroxy-4-methylthiobutyric acid comprising:
[0281] a 3-methylthiopropionaldehyde production device, a 2-hydroxy-4-methylthiobutyronitrile production device and a 2-hydroxy-4-methylthiobutyric acid production device connected sequentially;
[0283] The device for the production of 3-methylthiopropionaldehyde comprises the first reactor (R1) for the formation of a previous reaction solution of 3-methylthiopropionaldehyde and the second reactor (R2) for the preparation and obtaining of 3-methylthiopropionaldehyde, where the outlets of the first reactor (R1) and the second reactor (R2) are provided, respectively, with a detection device for the detection of the hemiacetal content;
[0285] The device for the production of 2-hydroxy-4-methylthiobutyronitrile comprises the third reactor (R3) for the formation of a previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile and the fourth reactor (R4) for the preparation and obtaining of 2-hydroxy-4-methylthiobutyronitrile, where the outlets of the third reactor (R3) and the fourth reactor (R4) are provided, respectively, with a detection device for the detection of the content of hydrocyanic acid; Y
[0287] The 2-hydroxy-4-methylthiobutyric acid production device comprises the hydration reactor (R5) for the formation of a 2-hydroxy-4-methylthiobutyramide and the hydrolysis reactor (R6) for the preparation of 2-hydroxy acid. 4-methylthiobutyric by means of hydrolysis reaction, as well as an extraction tower and a steam distillation tower, where the outlet of the hydration reactor (R5) is equipped with a detection device for the detection of the content of 2 -hydroxy-4-methylthiobutyronitrile.
[0289] Specific equipment such as reactor, extraction tower, steam distillation tower, static mixer, heat exchanger, circulating pump and detector that are specifically used in the present discussion can be obtained. in the market.
[0291] The detection device of the present disclosure is preferably a Raman spectrum detection device comprising a Raman spectroscopic detector (sometimes also referred to as a Raman detector, for example Raman detectors D1 to D5) and a detection device and Raman processing (eg, LM1 to LM3). Said Raman spectrum processing and detection device is used to collect and process the Raman spectroscopic signals collected by the Raman detector and forming a Raman spectrum. Any such Raman detector is connected to a Raman spectrum processing and detection device (multiple Raman detectors can be connected to a single Raman spectrum processing and detection device). Preferably, the connection between the Raman detectors and the Raman spectrum detection and processing devices is selected according to the step of the reaction. In some specific embodiments, the Raman detectors D1 and D2 are connected to the Raman spectrum detection and processing device LM1, the Raman detectors D3 and D4 are connected to the Raman spectrum detection and processing device LM2, and the Raman detector D5 It is connected to the LM3 Raman spectrum detection and processing device.
[0293] By way of example of the present disclosure, both the first reactor (R1) and the third reactor (R3) are recirculating reactors, which are selected from tower reactors or stirred multi-step reactors conventional in the art and, preferably, reactors tower with deflector plate (s) arranged inside. Both the second reactor (R2) and the fourth reactor (R4) are plug flow reactors; both the hydration reactor (R5) and the hydrolysis reactor (R6) are multi-pass stirred reactors with a number of stirring passes from 3 to 20 and preferably from 5 to 15; the extraction tower is a multi-pass agitated extraction tower with a number of agitation passes from 10 to 30 and preferably from 15 to 25; and the steam distillation tower is a plate tower with plate numbers from 10 to 40, and preferably from 15 to 30.
[0295] As used herein, the terms "comprising (s)" or "containing (s)" should be understood to have an open and non-exclusive meaning, that is, "including, but not limited to".
[0297] In this discussion, a percentage refers to a percentage by mass, unless otherwise specified.
[0298] The technical solutions of the present disclosure are explained more specifically below together with the examples.
[0300] Example 1
[0302] The synthesis of 2-hydroxy-4-methylthiobutyric acid was carried out according to the process shown in figure 1, where:
[0304] R1 had a volume of 1 m3 and was a straight tube with an internal diameter of 0.6 m, a length of 3.55 m and 10 deflector plates arranged inside;
[0306] R2 had a volume of 0.2 m3 and was a straight tube with an inside diameter of 0.3 m and a length of 2.85 m;
[0308] R3 had a volume of 0.5 m3 and was a straight tube with an internal diameter of 0.5 m, a length of 2.55 m and 8 deflector plates arranged inside;
[0310] R4 had a volume of 0.1 m3 and was a straight tube with an internal diameter of 0.2 m and a length of 3.20 m;
[0312] R5 had a volume of 1 m3 and was a straight tube with an internal diameter of 0.6 m, a length of 3.55 m and 10 stirring steps arranged inside;
[0314] R6 had a volume of 2 m3 and was a straight tube with an internal diameter of 0.8 m, a length of 4.00 m and 10 stirring steps arranged inside;
[0316] R7 had a volume of 0.2 m3 and was a reaction kettle with an internal stirrer;
[0317] C1 was an extraction tower with a diameter of 1 m and 20 stirring passages arranged inside; Y
[0319] C2 was a tower of plates with a diameter of 1 m and 25 perforated plates arranged inside.
[0320] (1) Preparation of 3-methylthiopropionaldehyde
[0322] The acrolein material ACR1 was mixed, first, with the circulating materials in the static mixer M2 at 545 Kg / hour, then the mixture was mixed together with methyl mercaptan (480 Kg / hour) and the catalyst (triethylamine and 2-hydroxy-4-methylthiobutyric acid were mixed with a molar ratio of 1.2: 1) (1 Kg / hour) in the static mixer M1, and the mixed materials were introduced into the first reactor R1 and were subjected to reaction under conditions between 27 and 30 ° C to obtain a pre-reaction solution of 3-methylthiopropionaldehyde. After the previous 3-methylthiopropionaldehyde reaction solution had cooled, said previous reaction solution (approximately 1026 Kg / hour) was extracted and supplied to the second reactor R2 for 3-methylthiopropionaldehyde, and the amount of materials used as circulating materials of the first reactor R1 was approximately 20000 Kg / hour.
[0324] The supplemental amount of acrolein ACR2 was determined as 16 Kg / hour by using the Raman D1 detector to determine the hemiacetal content in the previous 3-methylthiopropionaldehyde reaction solution. The supplemented ACR2 and the 3-methylthiopropionaldehyde pre-reaction solution were mixed in the static mixer M3 and then introduced into the second reactor R2, and the mixture was further reacted under conditions of between 27 and 28 ° C to Obtain the 3-methylthiopropionaldehyde reaction solution. The residual amount of hemiacetal in the 3-methylthiopropionaldehyde reaction solution was determined by means of the Raman D2 detector to confirm a basically complete reaction of hemiacetal.
[0325] (2) Preparation of 2-hydroxy-4-methylthiobutyronitrile
[0327] Most of the MMP1 material in the 3-methylthiopropionaldehyde reaction solution obtained in the previous stage was mixed together with the circulating materials and the hydrocyanic acid (270 Kg / hour) in the static mixer M4 at 1010 Kg / hour, and the materials mixed were introduced into the third reactor R3 and were reacted under conditions between 33 and 35 ° C to obtain a pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile. The previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile was supplied to the fourth reactor R4 for 2-hydroxy-4-methylthiobutyronitrile at 1280 Kg / hour after being cooled, and the amount of materials used as circulating materials of the second reactor R3 it was 25600 Kg / hour. The supplemental amount of 3-methylthiopropionaldehyde MMP2 was determined as 32 Kg / hour by using the Raman D3 detector to determine the content of hydrocyanic acid in the previous 2-hydroxy-4-methylthiobutyronitrile reaction solution. The supplemented MMP2 and the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution were mixed in the static mixer M5 and then introduced into the fourth reactor R4, and the mixture was reacted under conditions between 33 and 34 ° C to obtain the 2-hydroxy-4-methylthiobutyronitrile reaction solution. The residual amount of hydrocyanic acid in the 2-hydroxy-4-methylthiobutyronitrile reaction solution was determined by means of the Raman D4 detector to confirm a basically complete reaction of hydrocyanic acid.
[0329] (3) Preparation of 2-hydroxy-4-methylthiobutyric acid
[0331] The 2-hydroxy-4-methylthiobutyronitrile reaction solution obtained in the previous step and the sulfuric acid solution (1680 Kg / hour, 70% by weight) were mixed by means of the static mixer M6 and then introduced in the hydration reactor R5, and the mixture was subjected to a hydration reaction under conditions between 55 and 60 ° C to obtain the reaction solution of 2-hydroxy-4-methylthiobutyramide. This solution of reaction and water (2300 Kg / hour) together through the static mixer M6, and then R6 was introduced into the hydrolysis reactor, and the mixture was heated to between 100 and 105 ° C, and was subjected to a hydrolysis reaction to Obtain the 2-hydroxy-4-methylthiobutyric acid reaction solution.
[0333] The hydration reaction process was carried out completely. The amount of the sulfuric acid solution was adjusted by using the Raman D5 spectroscopy detector to determine the remaining 2-hydroxy-4-methylthiobutyronitrile in the reaction solution, and the amount of water that was introduced into the hydrolysis reactor. R6 was adjusted at the same time, in order to ensure that the hydrolysis reaction was basically complete.
[0335] The reaction solution of 2-hydroxy-4-methylthiobutyric acid obtained by the hydrolysis reaction mentioned above was supplied to the continuous neutralization reactor R7 and adjusted with ammonia to achieve a pH value of 1.5, in order to obtain the neutralized solution of 2-hydroxy-4-methylthiobutyric acid. Then, said neutralized solution was introduced in the upper part of the multi-step extraction tower C1, methyl isobutyl ketone was introduced as a solvent in the lower part of the extraction tower C1 at 5000 Kg / hour, and an extraction was carried out. countercurrent under conditions between 35 and 40 ° C. An extraction liquid containing 2-hydroxy-4-methylthiobutyric acid was obtained from the top of the tower and an ammonium sulfate solution was obtained from the bottom at 3630 Kg / hour. The 2-hydroxy-4-methylthiobutyric acid extraction liquid was introduced into the upper part of the C2 steam stripping tower, the steam was introduced in the lower part to carry out the steam extraction, and the steam Solvent obtained from the upper part of the steam distillation tower could be applied directly to the extraction tower C1 after being condensed by the condenser E3. The 2-hydroxy-4-methylthiobutyric acid product was obtained from the lower part of the steam distillation tower at 1685 Kg / hour and said product had a content of 88.92% and a yield of 99.71%. in acrolein terms.
[0337] Example 2
[0339] The synthesis of 2-hydroxy-4-methylthiobutyric acid was carried out according to the process shown in figure 1, where:
[0341] R1 had a volume of 1 m3 and was a straight tube with an internal diameter of 0.6 m, a length of 3.55 m and 10 deflector plates arranged inside;
[0343] R2 had a volume of 0.2 m3 and was a straight tube with an inside diameter of 0.3 m and a length of 2.85 m;
[0345] R3 had a volume of 0.5 m3 and was a straight tube with an internal diameter of 0.5 m, a length of 2.55 m and 8 deflector plates arranged inside;
[0347] R4 had a volume of 0.1 m3 and was a straight tube with an internal diameter of 0.2 m and a length of 3.20 m;
[0349] R5 had a volume of 1 m3 and was a straight tube with an internal diameter of 0.6 m, a length of 3.55 m and 20 stirring steps arranged inside;
[0351] R6 had a volume of 2 m3 and was a straight tube with an internal diameter of 0.8 m, a length of 4.00 m and 20 stirring steps arranged inside;
[0353] R7 had a volume of 0.2 m3 and was a reaction kettle with an internal stirrer;
[0355] C1 was an extraction tower with a diameter of 1 m and 30 shaking passages arranged in inside; Y
[0357] C1 was an extraction tower with a diameter of 1 m and 10 perforated plates arranged inside.
[0359] (1) Preparation of 3-methylthiopropionaldehyde
[0361] The acrolein material ACR1 was first mixed with the circulating materials in the static mixer M2 at 1100 Kg / hour; then, the mixture was mixed together with methyl mercaptan (960 Kg / hour) and the catalyst (the molar ratio of tributylamine and 2-hydroxy-4-methylthiobutyric acid was 1.05; 1) (1 Kg / hour) in the mixer static M1, and the mixed materials were introduced into the first reactor R1 and were reacted under conditions between 35 and 40 ° C to obtain a pre-reaction solution of 3-methylthiopropionaldehyde. After the previous 3-methylthiopropionaldehyde reaction solution had cooled, said previous reaction solution (approximately 2061 Kg / hour) was extracted and supplied to the second reactor R2 for 3-methylthiopropionaldehyde, and the amount of materials used as circulating materials of the first reactor R1 was approximately 21,000 Kg / hour.
[0363] The supplemental amount of acrolein ACR2 was determined as 23 Kg / hour by using the Raman D1 detector to determine the hemiacetal content in the previous 3-methylthiopropionaldehyde reaction solution. The supplemented ACR2 and the 3-methylthiopropionaldehyde pre-reaction solution were mixed in the static mixer M3 and then introduced into the second reactor R2, and the mixture was further reacted under conditions between 35 and 36 ° C to Obtain the 3-methylthiopropionaldehyde reaction solution. The residual amount of hemiacetal in the 3-methylthiopropionaldehyde reaction solution was determined by means of the Raman D2 detector to confirm a basically complete reaction of hemiacetal.
[0364] (2) Preparation of 2-hydroxy-4-methylthiobutyronitrile
[0366] Most of the MMP1 material in the 3-methylthiopropionaldehyde reaction solution obtained in the previous stage was mixed together with the circulating materials and the hydrocyanic acid (540 Kg / hour) in the static mixer M4 at 2063 Kg / hour, and the materials mixed were introduced into the third reactor R3 and were reacted under conditions between 40 and 45 ° C to obtain a pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile. The previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile was supplied to the fourth reactor R4 for 2-hydroxy-4-methylthiobutyronitrile at 2603 Kg / hour after being cooled, and the amount of materials used as circulating materials of the second reactor R3 it was 13100 Kg / hour.
[0368] The supplemental amount of 3-methylthiopropionaldehyde MMP2 was determined as 21 kg / hour by using the Raman D3 detector to determine the content of hydrocyanic acid in the previous 2-hydroxy-4-methylthiobutyronitrile reaction solution. The supplemented MMP2 and the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution were mixed in the static mixer M5 and then introduced into the fourth reactor R4, and the mixture was reacted under conditions between 40 and 41 ° C to obtain the 2-hydroxy-4-methylthiobutyronitrile reaction solution. The residual amount of hydrocyanic acid in the 2-hydroxy-4-methylthiobutyronitrile reaction solution was determined by means of the Raman D4 detector to confirm a basically complete reaction of hydrocyanic acid.
[0370] (3) Preparation of 2-hydroxy-4-methylthiobutyric acid
[0372] The 2-hydroxy-4-methylthiobutyronitrile reaction solution obtained in the previous step and the sulfuric acid solution (2613 Kg / hour, 75% by weight) were mixed by means of the static mixer M6 and then introduced in the hydration reactor R5, and the mixture was subjected to a hydration reaction under conditions between 65 and 70 ° C to Obtain the reaction solution of 2-hydroxy-4-methylthiobutyramide. This reaction solution and water (3750 Kg / hour) were mixed together by means of the static mixer M6 and then R6 was introduced into the hydrolysis reactor and the mixture was heated to between 115 and 120 ° C and subjected hydrolysis reaction to obtain the 2-hydroxy-4-methylthiobutyric acid reaction solution.
[0374] The hydration reaction process was carried out completely. The amount of the sulfuric acid solution was adjusted by using the Raman D5 spectroscopy detector to determine the remaining 2-hydroxy-4-methylthiobutyronitrile in the reaction solution, and the amount of water that was introduced into the hydrolysis reactor. R6 was adjusted at the same time, in order to ensure that the hydrolysis reaction was basically complete.
[0376] The reaction solution of 2-hydroxy-4-methylthiobutyric acid obtained by the hydrolysis reaction mentioned above was supplied to the continuous neutralization reactor R7 and adjusted with aqueous ammonia to achieve a pH value of 2, in order to obtain the neutralized solution of 2-hydroxy-4-methylthiobutyric acid. Then, said neutralized solution was introduced in the upper part of the multi-step extraction tower C1, tert-butyl methyl ether was introduced as a solvent in the lower part of the extraction tower C1 at 2800 Kg / hour, and carried out a countercurrent extraction under conditions between 45 and 50 ° C. An extraction liquid containing 2-hydroxy-4-methylthiobutyric acid was obtained from the top of the tower, and an ammonium sulfate solution was obtained from the bottom at 5955 Kg / hour. The 2-hydroxy-4-methylthiobutyric acid extraction liquid was introduced into the upper part of the C2 steam stripping tower, the steam was introduced in the lower part to carry out the steam extraction, and the steam Solvent obtained from the upper part of the steam distillation tower could be applied directly to the extraction tower C1 after being condensed by the condenser E3. The 2-hydroxy-4-methylthiobutyric acid product was obtained from the bottom of the distillation tower by steam stripping at 3372 Kg / hour and said product had a content of 88.85% and a yield of 99.60% in terms of acrolein.
[0378] Example 3
[0380] The synthesis of 2-hydroxy-4-methylthiobutyric acid was carried out according to the process shown in figure 1, where:
[0382] R1 had a volume of 1 m3 and was a straight tube with an internal diameter of 0.6 m, a length of 3.55 m and 10 deflector plates arranged inside;
[0384] R2 had a volume of 0.2 m3 and was a straight tube with an inside diameter of 0.3 m and a length of 2.85 m;
[0386] R3 had a volume of 0.5 m3 and was a straight tube with an internal diameter of 0.5 m, a length of 2.55 m and 8 deflector plates arranged inside;
[0388] R4 had a volume of 0.1 m3 and was a straight tube with an internal diameter of 0.2 m and a length of 3.20 m;
[0390] R5 had a volume of 1 m3 and was a straight tube with an internal diameter of 0.6 m, a length of 3.55 m and 3 stirring steps arranged inside;
[0392] R6 had a volume of 2 m3 and was a straight tube with an internal diameter of 0.8 m, a length of 4.00 m and 3 stirring steps arranged inside;
[0394] R7 had a volume of 0.2 m3 and was a reaction kettle with an internal stirrer;
[0395] C1 was an extraction tower with a diameter of 1 m and 10 stirring passages arranged inside; Y
[0397] C2 was a plate tower with a diameter of 1 m and 40 perforated plates arranged inside.
[0399] (1) Preparation of 3-methylthiopropionaldehyde
[0401] The acrolein material ACR1 was first mixed with the circulating materials in the static mixer M2 at 266 Kg / hour; then, the mixture was mixed together with methyl mercaptan (240 Kg / hour) and the catalyst (the molar ratio of N, N-dimethylbenzylamine and 2-hydroxy-4-methylthiobutyric acid was 2: 1) (2 Kg / hour) in the static mixer M1, and the mixed materials were introduced into the first reactor R1 and were reacted under conditions of between 20 and 22 ° C to obtain a pre-reaction solution of 3-methylthiopropionaldehyde. After the previous 3-methylthiopropionaldehyde reaction solution had cooled, said previous reaction solution (approximately 508 Kg / hour) was extracted and supplied to the second reactor R2 for 3-methylthiopropionaldehyde, and the amount of materials used as circulating materials of the first reactor R1 was approximately 25000 Kg / hour.
[0403] The supplemental amount of acrolein ACR2 was determined as 15 Kg / hour by using the Raman D1 detector to determine the hemiacetal content in the previous 3-methylthiopropionaldehyde reaction solution. The supplemented ACR2 and the previous 3-methylthiopropionaldehyde reaction solution were mixed in the static mixer M3 and then introduced into the second reactor R2, and the mixture was further reacted under conditions of between 20 and 21 ° C to Obtain the 3-methylthiopropionaldehyde reaction solution. The residual amount of hemiacetal in the 3-methylthiopropionaldehyde reaction solution was determined by means of the Raman D2 detector to confirm a basically complete reaction of hemiacetal.
[0404] (2) Preparation of 2-hydroxy-4-methylthiobutyronitrile
[0406] Most of the MMP1 material in the 3-methylthiopropionaldehyde reaction solution obtained in the previous stage was mixed together with the circulating materials and the hydrocyanic acid (135 Kg / hour) in the static mixer M4 at 497 Kg / hour, and the materials mixed were introduced into the third reactor R3 and were reacted under conditions between 25 and 27 ° C to obtain a pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile. The previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile was supplied to the fourth reactor R4 for 2-hydroxy-4-methylthiobutyronitrile at 632 Kg / hour after being cooled, and the amount of materials used as circulating materials of the second reactor R3 it was 18900 Kg / hour.
[0408] The supplemental amount of 3-methylthiopropionaldehyde MMP2 was determined as 26 Kg / hour by using the Raman D3 detector to determine the content of hydrocyanic acid in the previous 2-hydroxy-4-methylthiobutyronitrile reaction solution. The supplemented MMP2 and the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution were mixed in the static mixer M5 and then introduced into the fourth reactor R4, and the mixture was reacted under conditions between 25 and 26 ° C to obtain the 2-hydroxy-4-methylthiobutyronitrile reaction solution. The residual amount of hydrocyanic acid in the 2-hydroxy-4-methylthiobutyronitrile reaction solution was determined by means of the Raman D4 detector to confirm a basically complete reaction of hydrocyanic acid.
[0410] (3) Preparation of 2-hydroxy-4-methylthiobutyric acid
[0412] The 2-hydroxy-4-methylthiobutyronitrile reaction solution obtained in the previous step and the sulfuric acid solution (1360 Kg / hour, 72% by weight) were mixed by means of the static mixer M6 and then introduced in the hydration reactor R5, and the The mixture was subjected to a hydration reaction under the conditions of 50-55 ° C to obtain the 2-hydroxy-4-methylthiobutyramide reaction solution. This reaction solution and water (1700 Kg / hour) were mixed together by means of the static mixer M6 and then R6 was introduced into the hydrolysis reactor and the mixture was heated to between 90 and 95 ° C and subjected hydrolysis reaction to obtain the 2-hydroxy-4-methylthiobutyric acid reaction solution.
[0414] The hydration reaction process was carried out completely. The amount of the sulfuric acid solution was adjusted by using the Raman D5 spectroscopy detector to determine the remaining 2-hydroxy-4-methylthiobutyronitrile in the reaction solution, and the amount of water that was introduced into the hydrolysis reactor. R6 was adjusted at the same time, in order to ensure that the hydrolysis reaction was basically complete.
[0416] The reaction solution of 2-hydroxy-4-methylthiobutyric acid obtained by the hydrolysis reaction mentioned above was supplied to the continuous neutralization reactor R7 and adjusted with ammonia to achieve a pH value of 1, in order to obtain the solution neutralized 2-hydroxy-4-methylthiobutyric acid. Then, said neutralized solution was introduced in the upper part of the multi-step extraction tower C1, butanone was introduced as a solvent in the lower part of the extraction tower C1 at 11900 Kg / hour, and an extraction was carried out. countercurrent under conditions between 30 and 35 ° C. An extraction liquid containing 2-hydroxy-4-methylthiobutyric acid was obtained from the top of the tower, and an ammonium sulfate solution was obtained from the bottom at 3130 Kg / hour. The 2-hydroxy-4-methylthiobutyric acid extraction liquid was introduced into the upper part of the C2 steam stripping tower, the steam was introduced in the lower part to carry out the steam extraction, and the steam Solvent obtained from the upper part of the steam distillation tower could be applied directly to the extraction tower C1 after being condensed by the condenser E3. The 2-hydroxy-4-methylthiobutyric acid product was obtained from the part bottom of the steam distillation tower at 843 Kg / hour and said product had a content of 88.97% and a yield of 99.65% in terms of acrolein.
[0418] The above examples are illustrative of the technical solutions of the present disclosure, and are not intended to limit the scope of the present disclosure to the previous examples. Accordingly, the scope of protection claimed by the present disclosure is not limited to the above examples, and any technical solution reached by equivalent substitution falls within the scope of protection of the present disclosure.

权利要求:
Claims (61)
[1]
1. Method for the preparation of 3-methylthiopropionaldehyde as an intermediate of 2-hydroxy-4-methylthiobutyric acid, where the method comprises: reacting acrolein with an excessive amount of methyl mercaptan in the presence of a catalyst to obtain a previous reaction solution of 3-methylthiopropionaldehyde; carrying out an on-line detection of a hemiacetal content in the 3-methylthiopropionaldehyde pre-reaction solution, and determining a supplementary amount of acrolein according to the detection results; and mixing and reacting the acrolein supplemented with the previous 3-methylthiopropionaldehyde reaction solution to be able to carry out a complete reaction of the hemiacetal contained in the previous 3-methylthiopropionaldehyde reaction solution, in order to prepare and obtain 3-methylthiopropionaldehyde .
[2]
Method according to claim 1, wherein a feed molar ratio of acrolein and methyl mercaptan is 0.95: 1 to 0.99: 1, preferably 0.97: 1 to 0.98: 1.
[3]
3. Method according to claim 1, wherein the catalyst is selected from organic bases, inorganic bases or salts formed by tertiary amines and acids, and is preferably a salt formed by a tertiary amine and 2-hydroxy-4-methylthiobutyric acid; the tertiary amine is one or more of triethylamine, tri-n-propylamine, tri-n-butylamine, triisopropylamine and N, N-dimethylbenzylamine; and a molar ratio of the tertiary amine and 2-hydroxy-4-methylthiobutyric acid is 1.05: 1 to 2.0: 1, preferably 1.1: 1 to 1.5: 1.
[4]
Method according to claim 3, wherein an addition amount of the catalyst is between 0.05% and 0.5% and preferably between 0.1% and 0.3% of a total mass of the acrolein and methyl mercaptan added.
[5]
5. Method according to claim 1, wherein a reaction between acrolein and Excessive amount of methyl mercaptan and a reaction between the supplemented acrolein and the previous 3-methylthiopropionaldehyde reaction solution have a reaction temperature of between 20 and 60 ° C, preferably between 20 and 40 ° C.
[6]
6. Method according to claim 1, wherein the method for the preparation of 3-methylthiopropionaldehyde as an intermediate of 2-hydroxy-4-methylthiobutyric acid also comprises a step of carrying out an on-line detection of a residual amount of hemiacetal on the 3-methylthiopropionaldehyde obtained and adjusting the supplemental amount of acrolein according to the detection results.
[7]
7. Method according to claim 1, wherein an online Raman spectroscopic detection method is used in the online detection.
[8]
Method according to claim 6, wherein an online Raman spectroscopic detection method is used in the online detection.
[9]
9. Method according to claim 1, wherein a reaction between acrolein and the excessive amount of methyl mercaptan is carried out in a first reactor R1, and a reaction between the supplemented acrolein and the previous reaction solution of 3-methylthiopropionaldehyde is carried out in a second reactor R2.
[10]
10. Method according to claim 9, wherein the first reactor R1 is a recirculating reactor, and the second reactor R2 is a plug flow reactor.
[11]
11. Method according to claim 10, wherein the first reactor R1 is a tower reactor or a multi-pass stirred reactor, preferably a tower reactor with baffle plate (s) arranged inside. .
[12]
12. Method according to claim 9, wherein a detector of D1 on-line Raman spectroscopy at an outlet of the first reactor for on-line detection of the hemiacetal content in the 3-methylthiopropionaldehyde pre-reaction solution.
[13]
13. Method according to claim 9, wherein an online Raman spectroscopy detector D2 is provided at an outlet of the second reactor for online detection of hemiacetal content in 3-methylthiopropionaldehyde.
[14]
14. Method according to any of claims 10 to 13, wherein a part of the previous reaction solution of 3-methylthiopropionaldehyde is introduced into the second reactor R2, the remaining part is used as circulating materials of the first reactor R1, and a The ratio of the amount of materials that are introduced into the second reactor R2 with respect to the amount of materials used as circulating materials of the first reactor R1 is from 1:10 to 1:50, preferably, from 1:15 to 1:30.
[15]
15. Method according to any one of claims 1 to 14, wherein the 3-methylthiopropionaldehyde obtained by the preparation is used for the preparation of 2-hydroxy-4-methylthiobutyronitrile.
[16]
16. Method according to any one of claims 1 to 14, wherein the 3-methylthiopropionaldehyde obtained by the preparation is used for the preparation of 2-hydroxy-4-methylthiobutyric acid.
[17]
17. Method for the preparation of 2-hydroxy-4-methylthiobutyronitrile as an intermediate of 2-hydroxy-4-methylthiobutyric acid, where the method comprises: reacting 3-methylthiopropionaldehyde with an excessive amount of hydrocyanic acid to obtain a reaction solution 2-hydroxy-4-methylthiobutyronitrile prerequisite; carrying out a detection of a hydrocyanic acid content in the pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile and determining a supplementary amount of 3-methylthiopropionaldehyde according to the detection results; and mixing and reacting the previous 2-hydroxy-4-methylthiobutyronitrile reaction solution with the 3-methylthiopropionaldehyde supplemented to be able to carry out a complete reaction of the hydrocyanic acid contained in the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile, in order to prepare and obtain 2-hydroxy-4-methylthiobutyronitrile.
[18]
18. Method according to claim 17, wherein a feed molar ratio of 3-methylthiopropionaldehyde and hydrocyanic acid is 0.95: 1 to 0.99: 1, preferably 0.97: 1 to 0.98: 1.
[19]
19. Method according to claim 17, wherein a reaction between 3-methylthiopropionaldehyde and the excessive amount of hydrocyanic acid and a reaction between the supplemented 3-methylthiopropionaldehyde and the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile have a temperature reaction between 20 and 80 ° C, preferably between 25 and 45 ° C.
[20]
20. Method according to claim 17, wherein the method for the preparation of 2-hydroxy-4-methylthiobutyronitrile as an intermediate of 2-hydroxy-4-methylthiobutyric acid also comprises a step of carrying out an on-line detection of a residual amount of hydrocyanic acid in the obtained 2-hydroxy-4-methylthiobutyronitrile and adjusting the supplemental amount of 3-methylthiopropionaldehyde according to the detection results.
[21]
21. Method according to claim 17, wherein an online Raman spectroscopic detection method is used in the online detection.
[22]
Method according to claim 20, wherein an online Raman spectroscopic detection method is used in the online detection.
[23]
23. Method according to claim 17, wherein a reaction between 3-methylthiopropionaldehyde and the excessive amount of hydrocyanic acid is carried out in a third reactor R3, and a reaction between the supplemented 3-methylthiopropionaldehyde and the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution is carried out in a fourth reactor R4.
[24]
24. Method according to claim 23, wherein the third reactor R3 is a recirculation reactor, and the fourth reactor R4 is a plug flow reactor.
[25]
25. Method according to claim 26, wherein the third reactor R3 is a tower reactor or a multi-pass stirred reactor, preferably a tower reactor with baffle plate (s) arranged inside. .
[26]
26. Method according to claim 23, wherein an online Raman spectroscopy detector D3 is provided at an outlet of the third reactor R3 for the online detection of the content of hydrocyanic acid in the previous reaction solution of 2-hydroxy-4 -methylthiobutyronitrile.
[27]
27. Method according to claim 23, wherein an on-line Raman spectroscopy detector D4 is provided at an outlet of the fourth reactor R4 for the on-line detection of the content of hydrocyanic acid in 2-hydroxy-4-methylthiobutyronitrile.
[28]
28. Method according to any of claims 23 to 27, wherein a part of the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile in the third reactor R3 is introduced into the fourth reactor R4, the remaining part is used as circulating materials of the third reactor R3, and a ratio of the amount of materials that are introduced into the fourth reactor R4 with respect to the amount of materials used as circulating materials of the third reactor R3 is from 1: 5 to 1:30, preferably, from 1:10 to 1:20.
[29]
29. Method according to claim 17, wherein the 3-methylthiopropionaldehyde is prepared and obtained by the method of any of claims 1 to 14.
[30]
30. Method according to any of claims 17 to 29, wherein the 2-hydroxy-4-methylthiobutyronitrile obtained by the preparation is used for the Preparation of 2-hydroxy-4-methylthiobutyric acid.
[31]
31. Method for the preparation of 2-hydroxy-4-methylthiobutyric acid, where the method comprises:
step (1): a step of reacting acrolein with methyl mercaptan to prepare 3-methylthiopropionaldehyde;
step (2): a step of reacting 3-methylthiopropionaldehyde with hydrocyanic acid to prepare 2-hydroxy-4-methylthiobutyronitrile; Y
step (3): a step of hydrating 2-hydroxy-4-methylthiobutyronitrile by using sulfuric acid and then hydrolyzing to prepare 2-hydroxy-4-methylthiobutyric acid;
where in stages (1), (2) and (3), the reaction state of the materials is detected online and the proportions of the materials are controlled according to the detection results, in order to be able to carry out run a complete reaction.
[32]
32. Method according to claim 31, wherein said step (1) comprises: reacting acrolein with an excessive amount of methyl mercaptan in the presence of a catalyst in a first reactor R1 to form a pre-reaction solution of 3-methylthiopropionaldehyde; carrying out an on-line detection of a hemiacetal content in the 3-methylthiopropionaldehyde pre-reaction solution, and determining a supplementary amount of acrolein according to the detection results; mix the previous reaction solution of 3-methylthiopropionaldehyde with the supplemented acrolein and then allow the mixture to enter a second reactor R2 to be able to carry out a complete reaction of hemiacetal contained in the previous reaction solution of 3- methylthiopropionaldehyde, in order to prepare and obtain a reaction solution of 3-methylthiopropionaldehyde.
[33]
33. Method according to claim 32, wherein the first reactor R1 is a recirculation reactor selected from a tower reactor or a multi-pass stirred reactor and is preferably a tower reactor with baffle plate (s) ) arranged inside.
[34]
34. Method according to claim 32 or 33, wherein a feed molar ratio of acrolein and methyl mercaptan is 0.95: 1 to 0.99: 1, preferably 0.97: 1 to 0.98: 1 .
[35]
35. Method according to claim 32 or 33, wherein a part of the previous reaction solution of 3-methylthiopropionaldehyde is introduced into the second reactor R2, the remaining part is used as circulating materials of the first reactor R1, and the ratio of the amount of materials that are introduced into the second reactor R2 relative to the amount of materials used as circulating materials of the first reactor R1 is 1:10 to 1:50, preferably 1:15 to 1:30.
[36]
36. Method according to claim 32, wherein said step (1) further comprises a step of carrying out an on-line detection of a residual amount of hemiacetal in 3-methylthiopropionaldehyde and of adjusting the supplemental amount of acrolein according to the detection results.
[37]
37. Method according to claim 32, wherein a reaction between acrolein and the excessive amount of methyl mercaptan and a reaction between the supplemented acrolein and the previous reaction solution of 3-methylthiopropionaldehyde have a reaction temperature of between 20 and 40 ° C.
[38]
38. Method according to any of claims 31 to 33, wherein the catalyst is selected from organic bases, inorganic bases or salts formed by tertiary amines and acids; and an amount of the catalyst is between 0.05% and 0.5% and preferably between 0.1% and 0.3% of a total mass of acrolein and methyl mercaptan.
[39]
39. Method according to claim 38, where the catalyst is a salt formed by a tertiary amine and 2-hydroxy-4-methylthiobutyric acid, where a molar ratio of the tertiary amine to 2-hydroxy-4-methylthiobutyric acid is 1.05: 1 to 2.0: 1, preferably 1.1: 1 to 1.5: 1, and the tertiary amine is at least one selected from triethylamine, tri-n-propylamine, tri-n -butylamine, triisopropylamine and N, N-dimethylbenzylamine.
[40]
40. Method according to any of claims 31 to 39, wherein a molar ratio of acrolein and methyl mercaptan in the previous 3-methylthiopropionaldehyde reaction solution is 0.95: 1 to 0.99: 1, preferably 0 , 97: 1 to 0.98: 1.
[41]
41. Method according to any of claims 31 to 40, wherein said step (2) comprises:
reacting 3-methylthiopropionaldehyde with an excessive amount of hydrocyanic acid in a third reactor R3 to form a pre-reaction solution of 2-hydroxy-4-methylthiobutyronitrile; carrying out an on-line detection of a hydrocyanic acid content in the 2-hydroxy-4-methylthiobutyronitrile pre-reaction solution and determining a supplementary amount of 3-methylthiopropionaldehyde according to the detection results; and mixing the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile with the supplemented 3-methylthiopropionaldehyde and then allowing the mixture to be introduced into a fourth reactor R4 to be able to carry out a complete reaction of hydrocyanic acid contained in 2-hydroxy-4-methylthiobutyronitrile, in order to prepare and obtain 2-hydroxy-4-methylthiobutyronitrile.
[42]
42. Method according to claim 41, wherein the third reactor R3 is selected from a tower reactor or a multi-pass stirred reactor and is preferably a tower reactor with baffle plate (s) arranged (s) ) inside.
[43]
43. Method according to claim 41, wherein a part of the reaction solution 2-hydroxy-4-methylthiobutyronitrile in the third reactor R3 is introduced into the fourth reactor R4, the remaining part is used as circulating materials of the third reactor R3, and a ratio of the amount of materials that are introduced into the fourth reactor R4 with respect to the amount of materials used as circulating materials of the third reactor R3 is 1: 5 to 1:30, preferably 1:10 to 1:20.
[44]
44. Method according to claim 41, wherein a feed molar ratio of 3-methylthiopropionaldehyde and hydrocyanic acid is 0.95: 1 to 0.99: 1, preferably 0.97: 1 to 0.98: 1.
[45]
45. Method according to claim 41, wherein a reaction between 3-methylthiopropionaldehyde and the excessive amount of hydrocyanic acid and a reaction between the supplemented 3-methylthiopropionaldehyde and the previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile have a temperature reaction between 25 and 45 ° C.
[46]
46. Method according to claim 41, wherein said step (2) further comprises a step of carrying out an on-line detection of a residual amount of hydrocyanic acid in 2-hydroxy-4-methylthiobutyronitrile and of adjusting the supplementary amount of 3- methylthiopropionaldehyde according to the detection results.
[47]
47. Method according to any of claims 31 to 46, wherein said step (3) comprises:
subjecting 2-hydroxy-4-methylthiobutyronitrile to hydration reaction in the presence of sulfuric acid in a hydration reactor R5 to form 2-hydroxy-4-methylthiobutyramide, where a residual quantity of 2-hydroxy-4-methylthiobutyronitrile in reaction solution is detects online and an amount of sulfuric acid to be used is adjusted according to the detection results, in order to be able to carry out a complete hydration reaction; Y
Mix 2-hydroxy-4-methylthiobutyramide with water, then allow the mixture to settle introduce into a hydrolysis reactor R6, in order to prepare 2-hydroxy-4-methylthiobutyric acid by hydrolysis reaction.
[48]
48. Method according to claim 47, wherein the hydration reactor R5 and / or the hydrolysis reactor R6 is a multi-step stirred reactor with a number of stirring steps from 3 to 20 and, preferably, from 5 to 15 .
[49]
49. Method according to claim 47, wherein said step (3) further comprises the following steps: adjusting the pH value of 2-hydroxy-4-methylthiobutyric acid between 1 and 2, in order to obtain a neutralized solution of 2-hydroxy-4-methylthiobutyric acid; allowing the neutralized 2-hydroxy-4-methylthiobutyric acid solution to enter an extraction tower for extraction; and allowing an extraction liquid containing 2-hydroxy-4-methylthiobutyric acid to enter a distillation tower by steam stripping, in order to obtain 2-hydroxy-4-methylthiobutyric acid from the bottom of the distillation tower. by steam entrainment.
[50]
50. Method according to claim 49, wherein an extraction solvent for the neutralized solution of 2-hydroxy-4-methylthiobutyric acid is one selected from methyl isobutyl ketone, butanone, pentanone, hexanone and tert-butyl methyl ether; and a mass ratio of the extraction solvent and the neutralized 2-hydroxy-4-methylthiobutyric acid solution is 0.3: 1 to 3: 1, preferably 0.5: 1 to 2: 1.
[51]
51. Method according to claim 49, wherein the extraction tower is a multi-pass agitated extraction tower with a number of agitation steps from 10 to 30 and preferably from 15 to 25.
[52]
52. Method according to claim 49, wherein the steam distillation tower is a plate tower with a number of plates from 10 to 40 and preferably from 15 to 30.
[53]
53. Method according to any one of claims 31 to 52, wherein online Raman spectroscopy detection is employed in online detection.
[54]
54. Continuous production device for the preparation of 2-hydroxy-4-methylthiobutyric acid, where the continuous production device comprises: a 3-methylthiopropionaldehyde production device, a 2-hydroxy-4-methylthiobutyronitrile production device and a sequentially connected 2-hydroxy-4-methylthiobutyric acid production device;
The device for the production of 3-methylthiopropionaldehyde comprises a first reactor R1 for the formation of a previous reaction solution of 3-methylthiopropionaldehyde and a second reactor R2 for the preparation and obtaining of 3-methylthiopropionaldehyde, where the outputs of the first reactor R1 and the second reactor R2 are equipped, respectively, with a detection device for detecting a hemiacetal content;
The device for the production of 2-hydroxy-4-methylthiobutyronitrile comprises a third reactor R3 for the formation of a previous reaction solution of 2-hydroxy-4-methylthiobutyronitrile and a fourth reactor R4 for the preparation and obtaining of 2-hydroxy- 4-methylthiobutyronitrile, where the outlets of the third reactor R3 and the fourth reactor R4 are provided, respectively, with a detection device for the detection of a content of hydrocyanic acid; Y
The 2-hydroxy-4-methylthiobutyric acid production device comprises a hydration reactor R5 for the formation of 2-hydroxy-4-methylthiobutyramide and a hydrolysis reactor R6 for the preparation of 2-hydroxy-4-methylthiobutyric acid by means of of hydrolysis reaction, as well as an extraction tower and a steam distillation tower, where an outlet of the hydration reactor R5 is equipped with a detection device for the detection of a content of 2-hydroxy-4-methylthiobutyronitrile .
[55]
55. Device according to claim 54, wherein the device further comprises a display device for the detection results.
[56]
56. Device according to claim 54 or 55, wherein the detection device is an online Raman spectroscopic detection device.
[57]
57. Device according to claim 54, wherein both the first reactor R1 and the third reactor R3 are recirculation reactors, which are selected from tower reactors or multi-pass stirred reactors and, preferably, tower reactors with plate (s ) deflector (s) arranged inside.
[58]
58. Device according to claim 54, wherein both the second reactor R2 and the fourth reactor R4 are plug flow reactors.
[59]
59. Device according to claim 54, wherein both the hydration reactor R5 and the hydrolysis reactor R6 are multi-step stirred reactors with a number of stirring steps from 3 to 20 and, preferably, from 5 to 15.
[60]
Device according to claim 54, wherein the extraction tower is a multi-pass agitated extraction tower with a number of agitation passes from 10 to 30 and preferably from 15 to 25.
[61]
61. Device according to claim 54, wherein the steam distillation tower is a plate tower with a number of plates from 10 to 40 and preferably from 15 to 30.

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同族专利:

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公开号 | 公开日

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US20210147350A1|2021-05-20|

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US11130732B2|2021-09-28|

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WO2020088060A1|2020-05-07|

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CN111116437B|2021-02-05|

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CN111116437A|2020-05-08|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2745745A|1952-10-30|1956-05-15|Monsanto Chemicals|Poultry feed|

---

FR2314917B1|1975-06-20|1977-12-02|Rhone Poulenc Ind|

---

FR2590896B1|1985-12-03|1988-07-22|Aec Chim Organ Biolog|PROCESS FOR THE PREPARATION OF AN AQUEOUS SOLUTION OF AN ALKALINE SALT OF METHIONINE|

---

ES2005784A6|1988-02-22|1989-03-16|Desarrollo Tecnico Ind S A Soc|Process for the preparation of aqueous solutions of 2-hydroxy-4-methylthio-butyric acid.|

---

US5352837A|1993-06-08|1994-10-04|Novus International, Inc.|Process for the preparation of 3-propanal|

---

FR2733231B1|1995-04-24|1997-07-04|Rhone Poulenc Nutrition Animal|PROCESS FOR CONDENSING CYANHYDRIC ACID WITH AN ALDEHYDE|

---

US5856567A|1995-06-07|1999-01-05|Novus International, Inc.|Continuous hydrolysis process for preparing 2-hydroxy-4-methylthiobutanioc acid or salts thereof|

---

US5663409A|1995-06-07|1997-09-02|Novus International, Inc.|Process for the preparation of 3- propanal and 2-hydroxy-4- butanenitrile|

---

US6342651B1|1999-08-05|2002-01-29|Novus International, Inc.|Reductive combustion of ammonium salts of sulfuric acid|

---

EP1413573A1|2002-10-24|2004-04-28|Adisseo France S.A.S.|Process for the production of 3-methylthiopropanal|

---

DE102004038053A1|2004-08-05|2006-04-27|Degussa Ag|Process for the preparation of 3- propanal|

---

JP2010111642A|2008-11-07|2010-05-20|Sumitomo Chemical Co Ltd|Method for producing methionine|

---

DE102010064250A1|2010-12-28|2012-06-28|Evonik Degussa Gmbh|Process for the preparation of methylmercaptopropionaldehyde|

---

MX337247B|2011-02-23|2016-02-19|Evonik Degussa Gmbh|Method for producing 2-hydroxy-4-butanenitrile from 3-propanal and hydrogen cyanide.|

---

EP2679579A1|2012-06-27|2014-01-01|Evonik Industries AG|Integrated method for producing acrolein and 3-Methylmercapto propionaldehyde|

---

CN102796030A|2012-08-31|2012-11-28|重庆紫光天化蛋氨酸有限责任公司|Method and device for preparing 3-methylmercapto-propionaldehyde through liquid-liquid reaction of methyl mercaptan and acraldehyde|

---

CN103420883A|2013-08-28|2013-12-04|重庆紫光化工股份有限公司|Method for using crude hydrocyanic acid gas for preparing 2-hydroxy-4-methylmercapto-butyronitrile|

---

CN103467348B|2013-10-08|2015-09-16|重庆紫光化工股份有限公司|The preparation method of macrobead crystal formation high-bulk-density MHA calcium|

---

CN104262216A|2014-10-15|2015-01-07|重庆紫光化工股份有限公司|Preparation method of MHA butyric acid)|

---

CN105732450A|2016-01-22|2016-07-06|曾庆云|Preparation device and preparation method of 3-methylmercapto propionaldehyde|

---

EP3205643A1|2016-02-15|2017-08-16|Evonik Degussa GmbH|Method for the preparation of 3-methylthiopropionaldehyde|

---

CN107628976B|2017-09-27|2019-06-04|山东新和成氨基酸有限公司|A kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid|

---

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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CN201811296139.XA|CN111116437B|2018-11-01|2018-11-01|Method and apparatus for producing 2-hydroxy-4-methylthiobutyric acid and intermediate thereof|

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PCT/CN2019/102680|WO2020088060A1|2018-11-01|2019-08-27|Method and device for preparing 2-hydroxy-4-methylthiobutyric acid and intermediates thereof|

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