CN115894313B - Preparation method and production system of 2-hydroxy-4-methylthiobutyrate - Google Patents
Preparation method and production system of 2-hydroxy-4-methylthiobutyrate Download PDFInfo
- Publication number
- CN115894313B CN115894313B CN202211508543.5A CN202211508543A CN115894313B CN 115894313 B CN115894313 B CN 115894313B CN 202211508543 A CN202211508543 A CN 202211508543A CN 115894313 B CN115894313 B CN 115894313B
- Authority
- CN
- China
- Prior art keywords
- hydroxy
- reactor
- metal hydroxide
- methylthiobutanoic acid
- methylthiobutyrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PICCHNWCTUUCAQ-UHFFFAOYSA-N 2-hydroxypentanethioic s-acid Chemical compound CCCC(O)C(O)=S PICCHNWCTUUCAQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 67
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000725 suspension Substances 0.000 claims abstract description 52
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 claims abstract description 40
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 claims abstract description 38
- INTUDBWOILOBCE-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanamide Chemical compound CSCCC(O)C(N)=O INTUDBWOILOBCE-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 38
- 230000003068 static effect Effects 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 36
- 239000007795 chemical reaction product Substances 0.000 claims description 33
- 238000003860 storage Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 9
- 239000005750 Copper hydroxide Substances 0.000 claims description 9
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 9
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 9
- 229960004887 ferric hydroxide Drugs 0.000 claims description 9
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 9
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 9
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 9
- 229940007718 zinc hydroxide Drugs 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 8
- 229960004452 methionine Drugs 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229930182817 methionine Natural products 0.000 description 7
- 235000006109 methionine Nutrition 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- YOMQFQLHVWGMPB-UHFFFAOYSA-L calcium;2-hydroxypentanethioate Chemical compound [Ca+2].CCCC(O)C([O-])=S.CCCC(O)C([O-])=S YOMQFQLHVWGMPB-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- -1 2-hydroxy-4-methylthiobutyrate amide Chemical class 0.000 description 3
- JDZSNXJQAUQFGC-UHFFFAOYSA-L copper;2-hydroxypentanethioate Chemical compound [Cu+2].CCCC(O)C([O-])=S.CCCC(O)C([O-])=S JDZSNXJQAUQFGC-UHFFFAOYSA-L 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical group CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229930195722 L-methionine Natural products 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ACJRGZWFVGDQMO-UHFFFAOYSA-L zinc;2-hydroxypentanethioate Chemical compound [Zn+2].CCCC(O)C([O-])=S.CCCC(O)C([O-])=S ACJRGZWFVGDQMO-UHFFFAOYSA-L 0.000 description 2
- DOLNLDKZJKDWLS-UHFFFAOYSA-N 2-hydroxypentanethioamide Chemical compound CCCC(O)C(N)=S DOLNLDKZJKDWLS-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004470 DL Methionine Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QHLMLVDNVYRKAG-UHFFFAOYSA-N [Fe].OC(C(=S)O)CCC Chemical compound [Fe].OC(C(=S)O)CCC QHLMLVDNVYRKAG-UHFFFAOYSA-N 0.000 description 1
- MSKJMDSWCGWTKX-UHFFFAOYSA-N [Mn].OC(C(=S)O)CCC Chemical compound [Mn].OC(C(=S)O)CCC MSKJMDSWCGWTKX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- GYJIUFKWWIHWRF-UHFFFAOYSA-M potassium;2-hydroxypentanethioate Chemical compound [K+].CCCC(O)C([O-])=S GYJIUFKWWIHWRF-UHFFFAOYSA-M 0.000 description 1
- 229930182852 proteinogenic amino acid Natural products 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SCDZGULHLNQMOU-UHFFFAOYSA-M sodium;2-hydroxypentanethioate Chemical compound [Na+].CCCC(O)C([O-])=S SCDZGULHLNQMOU-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method and a production system of 2-hydroxy-4-methylthiobutyrate. The preparation method comprises the following steps: 1) Under the catalysis of a metal hydroxide dilute suspension, 2-hydroxy-4-methylthiobutyronitrile reacts with hydrogen peroxide in a first reactor to generate 2-hydroxy-4-methylthiobutanoic acid amide; 2) 2-hydroxy-4-methylthiobutanoic acid amide is subjected to hydrolysis reaction under the catalysis of a metal hydroxide suspension to generate 2-hydroxy-4-methylthiobutanoic acid; 3) Continuously feeding a metal hydroxide solid into the third reactor, and reacting the 2-hydroxy-4-methylthiobutanoic acid with the metal hydroxide under stirring to produce the 2-hydroxy-4-methylthiobutanoic acid salt. By adopting the preparation method provided by the invention, inorganic salt wastewater can not be generated in a reaction system, and the purity of a target product is high.
Description
Technical Field
The invention particularly relates to a preparation method and a production system of 2-hydroxy-4-methylthiobutyrate.
Background
The methionine used in the current feed is divided into solid and liquid methionine, the chemical components of the methionine are different, the solid methionine is DL-methionine (the mixture of D-type and L-type accounts for 50 percent respectively), and the L-methionine is natural proteinogenic amino acid and can be directly utilized by organisms. Liquid methionine is actually 2-hydroxy-4-methylthiobutanoic acid (also known as 2-hydroxy-4-methylthiobutanoic acid or liquid 2-hydroxy-4-methylthiobutanoic acid), which can also be converted to L-methionine in the organism, thereby having the same biological function as solid methionine. And 2-hydroxy-4-methylthiobutyrate (also called 2-hydroxy-4-methylthiobutyrate, such as calcium, copper, manganese, zinc, chromium, iron and other salts) belongs to a third-generation animal trace element additive, and has the characteristics of stable structure, environmental protection and high-efficiency absorption.
The current preparation methods of 2-hydroxy-4-methylthiobutyrate mainly fall into the following two categories:
The 2-hydroxy-4-methylthiobutanoic acid is prepared by reacting 2-hydroxy-4-methylthiobutanoic acid with a metal source such as a metal oxide or hydroxide, etc. For example, chinese patent CN1493560a discloses the preparation of calcium 2-hydroxy-4-methylthiobutyrate by direct reaction of commercial 2-hydroxy-4-methylthiobutyrate with calcium oxide or calcium hydroxide; for another example, chinese patent CN104356035A discloses that 2-hydroxy-4-methylthiobutanoic acid is reacted with one or more calcium sources under the introduction of ammonium bisulfate as a catalyst to prepare calcium 2-hydroxy-4-methylthiobutanoate. However, 2-hydroxy-4-methylthiobutanoic acid as a raw material is generally obtained by hydrolyzing 2-hydroxy-4- (methylthio) butanenitrile under acidic or basic conditions, which involve hydration, hydrolysis, extraction, mother liquor ammoniation and crystallization processes under acidic conditions, and a large amount of by-product ammonium salts are produced, which are removed as ammonia gas during hydrolysis under basic conditions (basic hydrolysis), alkaline waste water is produced, and processes involving acidification, extraction and the like are involved in the middle, and a large amount of waste salts are also produced. In addition, when 2-hydroxy-4-methylthiobutanoic acid is prepared from 2-hydroxy-4-methylthiobutanoic acid by reaction, a small amount of impurities such as extractant and sulfate may be mixed, which is disadvantageous for improving the purity of the product.
The other is to prepare the target 2-hydroxy-4-methylthiobutyrate by taking 2-hydroxy-4-methylthiobutyrate derivatives such as 2-hydroxy-4-methylthiobutyrate, 2-hydroxy-4-methylthiobutyrate amide or 2-hydroxy-4-methylthiobutyrate and the like as raw materials through reaction. For example, chinese patent CN103641757a discloses that 2-hydroxy-4- (methylthio) butyronitrile is hydrolyzed to 2-hydroxy-4-methylthio butanoic acid sodium salt or 2-hydroxy-4-methylthio butanoic acid potassium salt under the catalysis of a base such as sodium hydroxide or potassium hydroxide, which is then subjected to a metathesis reaction with a soluble calcium salt to prepare calcium 2-hydroxy-4-methylthiobutyrate; for another example, patent CN102399176a discloses that 2-hydroxy-4- (methylthio) butyronitrile is hydrolyzed under concentrated hydrochloric acid, neutralized with sodium hydroxide and crystallized to give D, L-2-hydroxy-4-methylthiobutyramide, which is then reacted with excess calcium hydroxide to produce calcium 2-hydroxy-4-methylthiobutyrate. In the preparation method, strong acid or strong alkali is used as a catalyst, reaction byproducts are inorganic salts, and the inorganic salts or the catalyst are easy to be entrained in the 2-hydroxy-4-methylthiobutyrate product, so that the purity of the product is not high enough.
Disclosure of Invention
The invention aims to provide a preparation method of 2-hydroxy-4-methylthiobutyrate, which does not generate inorganic salt byproducts and inorganic salt wastewater, has environment-friendly process and ensures that the obtained 2-hydroxy-4-methylthiobutyrate has high purity.
It is another object of the present invention to provide a production system for preparing 2-hydroxy-4-methylthiobutyrate, which can realize environmentally-friendly production of 2-hydroxy-4-methylthiobutyrate having high purity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A process for the preparation of 2-hydroxy-4-methylthiobutyrate, said process comprising the steps of:
1) Under the catalysis of a metal hydroxide dilute suspension, 2-hydroxy-4-methylthiobutyronitrile reacts with hydrogen peroxide in a first reactor to obtain a first reaction product containing 2-hydroxy-4-methylthiobutanoic acid amide and metal hydroxide;
2) Mixing the first reaction product with a metal hydroxide suspension, and adding the mixture into a second reactor, wherein the 2-hydroxy-4-methylthiobutanoic acid amide undergoes hydrolysis reaction under the catalysis of the metal hydroxide suspension to obtain a second reaction product containing 2-hydroxy-4-methylthiobutanoic acid and metal hydroxide;
3) Introducing the second reaction product into a third reactor, continuously feeding a metal hydroxide solid into the third reactor, and reacting the 2-hydroxy-4-methylthiobutanoic acid with the metal hydroxide under stirring to generate the 2-hydroxy-4-methylthiobutanoic acid salt;
the metal hydroxide is selected from one or more of calcium hydroxide, copper hydroxide, manganese hydroxide, zinc hydroxide, chromium hydroxide and ferric hydroxide;
The mass percentage of the solute in the metal hydroxide dilute suspension in the step 1) is 0.2-0.4%;
the mass percentage of the solute in the metal hydroxide suspension in the step 2) is 5-8%.
The corresponding reaction route of the preparation method is as follows:
In some embodiments, in step 1), the 2-hydroxy-4-methylthiobutyronitrile is added in the form of an aqueous solution, the mass concentration of the aqueous solution being 75-82%.
In some embodiments, in step 1), the hydrogen peroxide is present in a mass concentration of 25-30%.
In some embodiments, in step 1), the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to hydrogen peroxide in hydrogen peroxide is 1:1.02-1.05.
In some embodiments, in step 1), the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to metal hydroxide is 1:0.02-0.04.
In some embodiments, in step 1), the temperature of the reaction is from 20 to 30 ℃.
In some embodiments, in step 1), the reaction time is 1 to 1.2 hours.
In some embodiments, in step 2), the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid amide to the metal hydroxide is 1:0.09-0.1.
In some embodiments, in step 2), the temperature of the hydrolysis reaction is from 40 ℃ to 50 ℃:
In some embodiments, in step 2), the hydrolysis reaction is for a period of time ranging from 1 to 1.3 hours.
In some embodiments, in step 3), the molar ratio of 2-hydroxy-4-methylthiobutanoic acid to metal hydroxide is 1:0.95-0.98.
In some embodiments, in step 3), the temperature of the reaction is 80-90 ℃.
In some embodiments, in step 3), the reaction time is 1 to 2 hours.
In some embodiments, the method of making comprises the steps of:
1) Respectively feeding a 2-hydroxy-4-methylthiobutyronitrile aqueous solution and hydrogen peroxide into a first static mixer for mixing to obtain a first mixture, respectively feeding a metal hydroxide dilute suspension and the first mixture into a first reactor, wherein the first reactor is a first tubular reactor, and the 2-hydroxy-4-methylthiobutyronitrile and the hydrogen peroxide react under the catalysis of the metal hydroxide dilute suspension to obtain a first reaction product containing 2-hydroxy-4-methylthiobutanoic acid amide and metal hydroxide;
2) Feeding the first reaction product and the metal hydroxide suspension into a second static mixer respectively for mixing to obtain a second mixture, feeding the second mixture into a second reactor, wherein the second reactor is a second tubular reactor, and the 2-hydroxy-4-methylthiobutanoic acid amide undergoes hydrolysis reaction under the catalysis of the metal hydroxide suspension to obtain a second reaction product containing 2-hydroxy-4-methylthiobutanoic acid and metal hydroxide;
3) Feeding the second reaction product into a third reactor, wherein the third reactor is a conical reactor, the conical reactor is provided with a solid feeding hole, the metal hydroxide is continuously fed into the conical reactor through the solid feeding hole, and the 2-hydroxy-4-methylthiobutanoic acid reacts with the metal hydroxide under stirring to generate the 2-hydroxy-4-methylthiobutanoic acid salt.
In some embodiments, the conical reactor further comprises a body having a chamber therein, a feed channel for introducing the second reaction product, a first gas channel for discharging gas, a discharge port, and a stirring paddle, wherein the lower portion of the body is conical, the discharge port is disposed at the bottom of the conical portion body, and the stirring paddle is disposed within the conical portion body.
The first gas passage may be used for the discharge of ammonia gas generated by the reaction.
In some embodiments, the feed channel, the first gas channel, the solid feed port are disposed at an upper end of the body; and/or the outside of the first tubular reactor and the outside of the second tubular reactor are provided with water circulation channels.
In some embodiments, the method of preparing further comprises the step of introducing the first reaction product into a storage tank provided with a second gas passage for venting gas at an upper end thereof, prior to feeding the first reaction product to the second static mixer.
The second gas passage may be used for the discharge of oxygen generated by the reaction.
The invention also provides a production system for the preparation method of the 2-hydroxy-4-methylthiobutyrate, which comprises a first static mixer, a first tubular reactor, a second static mixer, a second tubular reactor and a conical reactor which are connected in sequence; the first static mixer is provided with a 2-hydroxy-4-methylthiobutyronitrile feeding channel and a hydrogen peroxide feeding channel; the first tubular reactor is provided with a metal hydroxide dilute suspension feeding channel; the second static mixer is provided with a metal hydroxide suspension feeding channel; the conical reactor is provided with a solid feed inlet.
The above-mentioned sequential connection generally means that the first static mixer, the first tubular reactor, the second static mixer, the second tubular reactor and the conical reactor each have an inlet and an outlet and are communicated by necessary pipes. For example, the 2-hydroxy-4-methylthiobutyronitrile feeding channel and the hydrogen peroxide feeding channel are inlets of the first static mixer, an outlet of the first static mixer is communicated with an inlet of the first tubular reactor, the metal hydroxide dilute suspension feeding channel is also communicated with an inlet of the first tubular reactor, an outlet of the first tubular reactor and the metal hydroxide suspension feeding channel are both communicated with an inlet of the second static mixer, and an outlet of the second static mixer is communicated with an inlet of the conical reactor.
In some embodiments, the conical reactor further comprises a body having a chamber therein, a feed channel for introducing the second reaction product, a first gas channel for discharging gas, a discharge port, and a stirring paddle, wherein the lower portion of the body is conical, the discharge port is disposed at the bottom of the conical portion body, and the stirring paddle is disposed within the conical portion body. The stirring paddle is arranged in the conical part main body, so that the water-insoluble 2-hydroxy-4-methylthiobutyrate target product is facilitated to be continuously settled, the reaction is promoted, the water content of the crude product is reduced, and the energy is saved for the subsequent purification processes such as filtration and drying.
In some embodiments, the feed channel, the first gas channel, the solid feed port are disposed at an upper end of the body.
In some embodiments, the first tubular reactor and the second tubular reactor are each provided with a water circulation channel outside. Water may be used as a heating or cooling medium.
In some embodiments, the production system further comprises a storage tank disposed between the first tubular reactor and the second static mixer, the storage tank for storing the first reaction product, the storage tank being provided at an upper end with a second gas passage for discharging gas.
Preferably, the storage tank is provided with a stirrer.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1) The invention adopts 2-hydroxy-4-methylthiobutyronitrile and hydrogen peroxide to react under the catalysis of metal hydroxide dilute suspension to generate 2-hydroxy-4-methylthiobutanoic acid amide, the 2-hydroxy-4-methylthiobutanoic acid amide is hydrolyzed under the catalysis of metal hydroxide suspension and provided alkaline conditions to obtain 2-hydroxy-4-methylthiobutanoic acid, and the 2-hydroxy-4-methylthiobutanoic acid amide is reacted with continuously added metal hydroxide solid to finally prepare the 2-hydroxy-4-methylthiobutanoic acid salt. In the reaction system, the metal hydrogen hydroxide is used as a reaction raw material and a catalyst. The byproducts in the whole preparation method only comprise ammonia and oxygen, and both can be discharged from the reaction system, so that the preparation method of the invention does not produce inorganic salt wastewater, and is very environment-friendly.
2) The method has few reaction steps, does not involve the use of an organic solvent and does not need separation operations such as crystallization, so that the obtained 2-hydroxy-4-methylthiobutyrate has high purity.
Drawings
FIG. 1 is a schematic diagram of a production system of 2-hydroxy-4-methylthiobutyrate used in the examples of the present invention;
Wherein, 1 is 2-hydroxy-4-methylthiobutyronitrile feed channel, 2 is hydrogen peroxide feed channel, 3 is metal hydroxide thin suspension feed channel, 4 is metal hydroxide suspension feed channel, 5 is first static mixer, 6 is first tubular reactor, 7 is second static mixer, 8 is second tubular reactor, 9 is conical reactor, 10 is main part, 11 is feed channel, 12 is first gas channel, 13 is the discharge gate, 14 is the stirring rake, 15 is solid feed port, 16 is holding vessel, 17 is water circulation channel, 18 is agitator, 19 is second gas channel.
Detailed Description
When 2-hydroxy-4-methylthiobutyrate is synthesized in the prior art, a large amount of inorganic salt wastewater is generated, the environmental-friendly treatment cost is extremely high, and the purity of the finally obtained target product is not high enough. The invention is characterized in that 2-hydroxy-4-methylthiobutyronitrile and hydrogen peroxide are adopted to react under the catalysis of metal hydroxide dilute suspension to generate 2-hydroxy-4-methylthiobutanoic acid amide, the 2-hydroxy-4-methylthiobutanoic acid amide is hydrolyzed under the catalysis of the metal hydroxide suspension and the provided alkaline condition to obtain 2-hydroxy-4-methylthiobutanoic acid, and the 2-hydroxy-4-methylthiobutanoic acid amide is reacted with continuously added metal hydroxide solid to finally prepare the 2-hydroxy-4-methylthiobutanoic acid salt. In the prior art, 2-hydroxy-4-methylthiobutanoic acid amide is usually subjected to alkaline hydrolysis in the presence of other strong bases such as sodium hydroxide or potassium hydroxide, and the 2-hydroxy-4-methylthiobutanoic acid obtained by the hydrolysis reacts with other metal hydroxides to prepare the target 2-hydroxy-4-methylthiobutanoic acid salt, so that other inorganic salts can be produced, while the invention directly adopts the metal hydroxide of the same metal element as that in the target 2-hydroxy-4-methylthiobutanoic acid salt as a catalyst for alkaline hydrolysis of the 2-hydroxy-4-methylthiobutanoic acid amide, and the synthetic route is a brand-new synthetic route, and for the two preparation methods in the prior art, the byproducts of the synthetic route are only ammonia and oxygen, and no inorganic salt byproducts and inorganic salt wastewater with extremely high environmental protection treatment cost can be produced.
The invention has the further innovation that the first static mixer and the second static mixer are matched with the first tubular reactor and the second tubular reactor to carry out production, and the reaction temperature and the mass transfer problem can be better controlled by adopting the device, so that the unit consumption of hydrogen peroxide which is one of reaction raw materials is lower, the production cost can be further reduced, and the utilization rate of the hydrogen peroxide is improved. And mother liquor after separation of the target product can be completely used in the first and second tubular reactors or can be used for preparing metal hydroxide dilute suspension or metal hydroxide suspension.
The invention is further innovative in that a conical reactor with a conical lower part is adopted to enable the 2-hydroxy-4-methylthiobutanoic acid to react with the metal hydroxide, and a stirring paddle is arranged in a conical main body part, wherein the conical main body part can promote the sedimentation of insoluble 2-hydroxy-4-methylthiobutanoic acid salt of a target product to form a prefiltering effect, reduce the water content of the target crude product, save energy for the subsequent drying process of the product, and on the other hand, the continuous sedimentation of the target crude product is beneficial to the reaction of the 2-hydroxy-4-methylthiobutanoic acid and the metal hydroxide to move towards the positive reaction direction, so that the yield of the product is improved, and the yield of the reaction product can reach 99.9%.
The production system of the present invention may be embodied as follows:
As shown in fig. 1, the production system comprises a first static mixer 5, a first tubular reactor 6, a second static mixer 7, a second tubular reactor 8 and a conical reactor 9 which are connected in sequence; the first static mixer 5 is provided with a 2-hydroxy-4-methylthiobutyronitrile feeding channel 1 and a hydrogen peroxide feeding channel 2; the first tubular reactor 6 is provided with a metal hydroxide dilute suspension feed channel 3; the second static mixer 7 is provided with a metal hydroxide suspension feed channel 4; the conical reactor 9 is provided with a solids feed inlet 15. The conical reactor 9 further comprises a main body 10 internally provided with a chamber, a feed channel 11 for introducing a second reaction product, a first gas channel 12 for discharging gas, a discharge port 13 and a stirring paddle 14, wherein the lower part of the main body 10 is conical, the discharge port 13 is arranged at the bottom of the conical part main body, and the stirring paddle 14 is arranged in the conical part main body. The feed passage 11, the first gas passage 12, and the solid feed port 15 are provided at the upper end of the main body 10. The outside of the first tubular reactor 6 and the second tubular reactor 8 are each provided with a water circulation passage 17. The production system further comprises a storage tank 16 arranged between the first tubular reactor 6 and the second static mixer 7, the storage tank 16 being adapted to store the first reaction product, the storage tank 16 being provided at its upper end with a second gas channel 19 for the exhaust gas, the storage tank being further adapted to be provided with a stirrer 18. The ammonia gas generated by the reaction in the second tubular reactor 8 is partly inferior to the ammonia gas discharged from the first gas passage 12 of the conical reactor 9 and accumulated in the upper portion of the second tubular reactor 8, and in this case, the second tubular reactor 8 is brought into a state of slight negative pressure in actual operation.
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention, but is not intended to limit the scope of the present invention.
Example 1
The embodiment provides a preparation method of copper 2-hydroxy-4-methylthiobutyrate, which comprises the following steps:
an aqueous solution of 2-hydroxy-4-methylthiobutyronitrile having a mass concentration of 80% and hydrogen peroxide having a mass concentration of 30% are fed at room temperature, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to hydrogen peroxide is 1:1.02, which are uniformly mixed by a first static mixer 5, then are mixed with a dilute copper hydroxide suspension (solute accounts for 0.2 wt%) and then pass through a first tubular reactor 6, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to copper hydroxide is 1:0.02, the reaction temperature in the first tubular reactor 6 was 20℃and the residence time was 1.2h, and after formation of 2-hydroxy-4-methylthiobutanoic acid amide, the reaction product was fed into the storage tank 16, while the oxygen produced was discharged from the second gas passage 19 in the storage tank 16.
The mixture of 2-hydroxy-4-methylthiobutanoic acid amide and water is stirred in a storage tank 16, the mass percentage of water in the mixture is 45%, then the mixture and copper hydroxide suspension (solute accounting for 5 wt%) are jointly fed into a second static mixer 7, the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid amide to the copper hydroxide is 1:0.09, after mixing, the mixture is fed into a second tubular reactor 8, the reaction temperature in the second tubular reactor 8 is 40 ℃ and the residence time is 1h, the generated 2-hydroxy-4-methylthiobutanoic acid and the copper hydroxide suspension are fed into a conical reactor 9 together, and simultaneously the generated ammonia gas is discharged through a first gas channel 12 in the conical reactor 9. Continuously feeding copper hydroxide solids into a conical reactor 9 through a solid feeding port 15 in the conical reactor 9, and carrying out reaction under the stirring of a stirring paddle 14, wherein the molar ratio of 2-hydroxy-4-methylthiobutanoic acid to copper hydroxide is 1:0.95, the reaction temperature of the conical reactor 9 is 80 ℃, the residence time is 1.5h, and discharging after the reaction is finished. The water mass percentage in the discharged slurry is 59-61.5%, the 2-hydroxy-4-methylthio copper butyrate is finally obtained after further drying, and the yield of the step is 93.5% and the product purity is 96.8% by calculation.
Example 2
The embodiment provides a preparation method of 2-hydroxy-4-methylthio manganese butyrate, which comprises the following steps:
An aqueous solution of 2-hydroxy-4-methylthiobutyronitrile having a mass concentration of 80% and hydrogen peroxide having a mass concentration of 28% are fed at room temperature, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to hydrogen peroxide is 1:1.05, uniformly mixing the two materials by a first static mixer 5, then mixing the materials with a manganese hydroxide dilute suspension (the solute accounts for 0.3 weight percent), and then passing the mixture through a first tubular reactor 6, wherein the molar ratio of the 2-hydroxy-4-methylthiobutyronitrile to the manganese hydroxide is 1:0.04, the reaction temperature in the first tubular reactor 6 was 30℃and the residence time was 1h, and after formation of 2-hydroxy-4-methylthiobutanoic acid amide, the reaction product was fed into the storage tank 16, while the oxygen produced was discharged from the second gas passage 19 in the storage tank 16.
The mixture of 2-hydroxy-4-methylthiobutanoic acid amide and water is stirred in a storage tank 16, the mass percentage of water in the mixture is 45%, then the mixture and manganese hydroxide suspension (solute accounting for 5 wt%) are jointly fed into a second static mixer 7, the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid amide to the manganese hydroxide is 1:0.09, after mixing, the mixture is fed into a second tubular reactor 8, the reaction temperature in the second tubular reactor 8 is 40 ℃ and the residence time is 1h, the generated 2-hydroxy-4-methylthiobutanoic acid and the manganese hydroxide suspension are fed into a conical reactor 9 together, and simultaneously the generated ammonia gas is discharged through a first gas channel 12 in the conical reactor 9. Continuously feeding manganese hydroxide solids into a conical reactor 9 through a solid feeding port 15 in the conical reactor 9, and carrying out reaction under the stirring of a stirring paddle 14, wherein the molar ratio of 2-hydroxy-4-methylthiobutanoic acid to manganese hydroxide is 1:0.96, the reaction temperature of the conical reactor 9 is 80 ℃, the residence time is 1.5h, and discharging after the reaction is finished. After further drying, 2-hydroxy-4-methylthiobutanoic acid manganese is finally obtained, and the yield in this step is calculated to be 96.9% and the product purity is 99.2%.
Example 3
The embodiment provides a preparation method of zinc 2-hydroxy-4-methylthiobutyrate, which comprises the following steps:
An aqueous solution of 2-hydroxy-4-methylthiobutyronitrile having a mass concentration of 80% and hydrogen peroxide having a mass concentration of 30% are fed at room temperature, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to hydrogen peroxide is 1:1.03, the two are uniformly mixed by a first static mixer 5, then are mixed with zinc hydroxide dilute suspension (solute accounts for 0.2 wt%) and then pass through a first tubular reactor 6, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to zinc hydroxide is 1:0.03, the reaction temperature in the first tubular reactor 6 was 20℃and the residence time was 1.2h, and after formation of 2-hydroxy-4-methylthiobutanoic acid amide, the reaction product was fed into the storage tank 16, while the oxygen gas formed was discharged from the second gas passage 19 in the storage tank 16.
The mixture of 2-hydroxy-4-methylthiobutanoic acid amide and water is stirred in a storage tank 16, the mass percentage of water in the mixture is 45%, then the mixture and zinc hydroxide suspension (solute accounting for 5 wt%) are jointly fed into a second static mixer 7, the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid amide to the zinc hydroxide is 1:0.1, after mixing, the mixture is fed into a second tubular reactor 8, the reaction temperature in the second tubular reactor 8 is 40 ℃, the residence time is 1.3h, the generated 2-hydroxy-4-methylthiobutanoic acid and the zinc hydroxide suspension are fed into a conical reactor 9 together, and simultaneously the generated ammonia gas is discharged through a first gas channel 12 in the conical reactor 9. The zinc hydroxide solid is continuously put into the conical reactor 9 through a solid feed port 15 in the conical reactor 9, and the reaction is carried out under the stirring of a stirring paddle 14, wherein the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid to the zinc hydroxide is 1:0.98, the reaction temperature of the conical reactor 9 is 80 ℃, the residence time is 1.5h, and the material is discharged after the reaction is finished. After further drying, zinc 2-hydroxy-4-methylthiobutyrate is finally obtained, and the yield of the step is calculated to be 95.5%, and the product purity is calculated to be 96.7%.
Example 4
The embodiment provides a preparation method of 2-hydroxy-4-methylthio chromium butyrate, which comprises the following steps:
An aqueous solution of 2-hydroxy-4-methylthiobutyronitrile having a mass concentration of 80% and hydrogen peroxide having a mass concentration of 30% are fed at room temperature, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to hydrogen peroxide is 1:1.04, which are uniformly mixed by a first static mixer 5, then are mixed with a chromium hydroxide dilute suspension (solute accounts for 0.4 wt%) and then pass through a first tubular reactor 6, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to chromium hydroxide is 1:0.04, the reaction temperature in the first tubular reactor 6 was 20℃and the residence time was 1.2h, and after formation of 2-hydroxy-4-methylthiobutanoic acid amide, the reaction product was fed into the storage tank 16, while the oxygen formed was discharged from the second gas passage 19 in the storage tank 16.
The mixture of 2-hydroxy-4-methylthiobutanoic acid amide and water is stirred in a storage tank 16, the mass percentage of water in the mixture is 45%, then the mixture and chromium hydroxide suspension (solute accounting for 5 wt%) are jointly fed into a second static mixer 7, the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid amide to the chromium hydroxide is 1:0.1, after mixing, the mixture is fed into a second tubular reactor 8, the reaction temperature in the second tubular reactor 8 is 50 ℃ and the residence time is 1h, the generated 2-hydroxy-4-methylthiobutanoic acid and the chromium hydroxide suspension are fed into a conical reactor 9 together, and simultaneously the generated ammonia gas is discharged through a first gas channel 12 in the conical reactor 9. The chromium hydroxide solid is continuously put into the conical reactor 9 through a solid feed port 15 in the conical reactor 9, and the reaction is carried out under the stirring of a stirring paddle 14, wherein the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid to the chromium hydroxide is 1:0.96, the reaction temperature of the conical reactor 9 is 80 ℃, the residence time is 1.5h, and the material is discharged after the reaction is finished. After further drying, 2-hydroxy-4-methylthiobutanoic acid chromium is finally obtained, and the yield in this step is calculated to be 92.3% and the product purity is calculated to be 94.4%.
Example 5
The embodiment provides a preparation method of 2-hydroxy-4-methylthiobutanoic acid iron, which comprises the following steps:
An aqueous solution of 2-hydroxy-4-methylthiobutyronitrile having a mass concentration of 80% and hydrogen peroxide having a mass concentration of 29% are fed at room temperature, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to hydrogen peroxide is 1:1.05, which are uniformly mixed by a first static mixer 5, then are mixed with ferric hydroxide dilute suspension (solute accounts for 0.4 wt%) and then pass through a first tubular reactor 6, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to ferric hydroxide is 1:0.03, the reaction temperature in the first tubular reactor 6 was 25℃and the residence time was 1.2h, and after formation of 2-hydroxy-4-methylthiobutanoic acid amide, the reaction product was fed into the storage tank 16, while the oxygen gas formed was discharged from the second gas passage 19 in the storage tank 16.
The mixture of 2-hydroxy-4-methylthiobutanoic acid amide and water is stirred in a storage tank 16, the mass percentage of water in the mixture is 45%, then the mixture and ferric hydroxide suspension (solute accounting for 5 wt%) are jointly fed into a second static mixer 7, the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid amide to the ferric hydroxide is 1:0.1, after mixing, the mixture is fed into a second tubular reactor 8, the reaction temperature in the second tubular reactor 8 is 45 ℃ and the residence time is 1.2h, the generated 2-hydroxy-4-methylthiobutanoic acid and the ferric hydroxide suspension are fed into a conical reactor 9 together, and simultaneously the generated ammonia gas is discharged through a first gas channel 12 in the conical reactor 9. Continuously feeding ferric hydroxide solids into the conical reactor 9 through a solid feeding port 15 in the conical reactor 9, and carrying out reaction under the stirring of a stirring paddle 14, wherein the molar ratio of 2-hydroxy-4-methylthiobutanoic acid to ferric hydroxide is 1:0.98, the reaction temperature of the conical reactor 9 is 80 ℃, the residence time is 1.5h, and discharging after the reaction is finished. After further drying, iron 2-hydroxy-4-methylthiobutyrate was finally obtained, and the yield in this step was calculated to be 97.6% and the product purity was 99.1%.
Example 6
The embodiment provides a preparation method of calcium 2-hydroxy-4-methylthiobutyrate, which comprises the following steps:
An aqueous solution of 2-hydroxy-4-methylthiobutyronitrile having a mass concentration of 80% and hydrogen peroxide having a mass concentration of 25% are fed at room temperature, wherein the molar ratio of 2-hydroxy-4-methylthiobutyronitrile to hydrogen peroxide is 1:1.02, the two are uniformly mixed by a first static mixer 5, then are mixed with a calcium hydroxide thin suspension (solute accounts for 0.2 wt%) and then pass through a first tubular reactor 6, wherein the molar ratio of the 2-hydroxy-4-methylthiobutyronitrile to the calcium hydroxide is 1:0.02, the reaction temperature in the first tubular reactor 6 was 20℃and the residence time was 1.2h, and after formation of 2-hydroxy-4-methylthiobutanoic acid amide, the reaction product was fed into the storage tank 16, while the oxygen produced was discharged from the second gas passage 19 in the storage tank 16.
The mixture of 2-hydroxy-4-methylthiobutanoic acid amide and water is stirred in a storage tank 16, the mass percentage of water in the mixture is 45%, then the mixture and a calcium hydroxide suspension (solute accounting for 5 wt%) are jointly fed into a second static mixer 7, the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid amide to the calcium hydroxide is 1:0.09, the mixture is fed into a second tubular reactor 8 after being mixed, the reaction temperature in the second tubular reactor 8 is 40 ℃ and the residence time is 1h, the generated 2-hydroxy-4-methylthiobutanoic acid and the calcium hydroxide suspension are fed into a conical reactor 9 together, and simultaneously the generated ammonia gas is discharged through a first gas channel 12 in the conical reactor 9. Continuously feeding calcium hydroxide solids into a conical reactor 9 through a solid feeding port 15 in the conical reactor 9, and carrying out reaction under the stirring of a stirring paddle 14, wherein the molar ratio of 2-hydroxy-4-methylthiobutanoic acid to calcium hydroxide is 1:0.95, the reaction temperature of the conical reactor 9 is 80 ℃, the residence time is 1.5h, and discharging is carried out after the reaction is finished. After further drying, calcium 2-hydroxy-4-methylthiobutyrate was finally obtained, and the yield in this step was calculated to be 96.3% and the product purity was 97.5%.
Comparative example 1
This comparative example provides a process for the preparation of copper 2-hydroxy-4-methylthiobutyrate, which differs substantially from example 1 only in that: the conical reactor 9 was replaced by a conventional cylindrical reactor in which stirring paddles were also provided. The results were: the discharge of the common cylindrical reactor is mixed slurry, and the mass percentage of water in the slurry is 76-82%.
Compared with comparative example 1, the invention can greatly reduce the water content of the final product slurry by adopting the conical reactor, and has obvious effects of energy conservation and consumption reduction for reducing the operation load of the subsequent drying device.
Comparative example 2
This comparative example provides a process for the preparation of copper 2-hydroxy-4-methylthiobutyrate, which differs substantially from example 1 only in that: the first tubular reactor 6 and the second tubular reactor 8 were replaced with a common batch-tank stirred reactor, respectively. The results were: the kettle type reactor is operated in a gap mode, the operation auxiliary time is long, the production efficiency of products is low, two reaction kettles are needed, and the investment is relatively large. While the continuous tubular reactor is adopted for continuous operation in the embodiment 1, the production efficiency of the product is high, and the investment is small.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (11)
1. A process for the preparation of 2-hydroxy-4-methylthiobutyrate, characterized in that it comprises the steps of:
1) Under the catalysis of a metal hydroxide dilute suspension, 2-hydroxy-4-methylthiobutyronitrile reacts with hydrogen peroxide in a first reactor to obtain a first reaction product containing 2-hydroxy-4-methylthiobutanoic acid amide and metal hydroxide;
2) Mixing the first reaction product with a metal hydroxide suspension, and adding the mixture into a second reactor, wherein the 2-hydroxy-4-methylthiobutanoic acid amide undergoes hydrolysis reaction under the catalysis of the metal hydroxide suspension to obtain a second reaction product containing 2-hydroxy-4-methylthiobutanoic acid and metal hydroxide;
3) Introducing the second reaction product into a third reactor, continuously feeding a metal hydroxide solid into the third reactor, and reacting the 2-hydroxy-4-methylthiobutanoic acid with the metal hydroxide under stirring to generate the 2-hydroxy-4-methylthiobutanoic acid salt;
the metal hydroxide is selected from one or more of calcium hydroxide, copper hydroxide, manganese hydroxide, zinc hydroxide, chromium hydroxide and ferric hydroxide;
The mass percentage of the solute in the metal hydroxide dilute suspension in the step 1) is 0.2-0.4%;
the mass percentage of the solute in the metal hydroxide suspension in the step 2) is 5-8%.
2. The method for producing 2-hydroxy-4-methylthiobutyrate according to claim 1, wherein: in the step 1), the 2-hydroxy-4-methylthiobutyronitrile is added in the form of an aqueous solution, and the mass concentration of the aqueous solution is 75-82%; and/or, in the step 1), the mass concentration of the hydrogen peroxide is 25-30%.
3. The method for producing 2-hydroxy-4-methylthiobutyrate according to claim 1, wherein: in the step 1), the molar ratio of the 2-hydroxy-4-methylthiobutyronitrile to the hydrogen peroxide in the hydrogen peroxide is 1:1.02-1.05; and/or, in step 1), the molar ratio of the 2-hydroxy-4-methylthiobutyronitrile to the metal hydroxide is 1:0.02-0.04.
4. The method for producing 2-hydroxy-4-methylthiobutyrate according to claim 1, wherein: in the step 1), the temperature of the reaction is 20-30 ℃; and/or, in step 1), the reaction time is 1-1.2h.
5. The method for producing 2-hydroxy-4-methylthiobutyrate according to claim 1, wherein: in the step 2), the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid amide to the metal hydroxide is 1:0.09-0.1; and/or, in the step 2), the temperature of the hydrolysis reaction is 40-50 ℃; and/or, in the step 2), the time of the hydrolysis reaction is 1-1.3h.
6. The method for producing 2-hydroxy-4-methylthiobutyrate according to claim 1, wherein: in step 3), the molar ratio of the 2-hydroxy-4-methylthiobutanoic acid to the metal hydroxide is 1:0.95-0.98.
7. The method for producing 2-hydroxy-4-methylthiobutyrate according to claim 1, wherein: in the step 3), the temperature of the reaction is 80-90 ℃; and/or, in step 3), the reaction time is 1-2h.
8. The process for the preparation of 2-hydroxy-4-methylthiobutyrate according to any one of claims 1 to 7, wherein: the preparation method comprises the following steps:
1) Respectively feeding a 2-hydroxy-4-methylthiobutyronitrile aqueous solution and hydrogen peroxide into a first static mixer for mixing to obtain a first mixture, respectively feeding a metal hydroxide dilute suspension and the first mixture into a first reactor, wherein the first reactor is a first tubular reactor, and the 2-hydroxy-4-methylthiobutyronitrile and the hydrogen peroxide react under the catalysis of the metal hydroxide dilute suspension to obtain a first reaction product containing 2-hydroxy-4-methylthiobutanoic acid amide and metal hydroxide;
2) Feeding the first reaction product and the metal hydroxide suspension into a second static mixer respectively for mixing to obtain a second mixture, feeding the second mixture into a second reactor, wherein the second reactor is a second tubular reactor, and the 2-hydroxy-4-methylthiobutanoic acid amide undergoes hydrolysis reaction under the catalysis of the metal hydroxide suspension to obtain a second reaction product containing 2-hydroxy-4-methylthiobutanoic acid and metal hydroxide;
3) Feeding the second reaction product into a third reactor, wherein the third reactor is a conical reactor, the conical reactor is provided with a solid feeding hole, the metal hydroxide is continuously fed into the conical reactor through the solid feeding hole, and the 2-hydroxy-4-methylthiobutanoic acid reacts with the metal hydroxide under stirring to generate the 2-hydroxy-4-methylthiobutanoic acid salt.
9. The method for producing 2-hydroxy-4-methylthiobutyrate according to claim 8, wherein: the conical reactor further comprises a main body, a feeding channel, a first gas channel, a discharge hole and a stirring paddle, wherein the main body is internally provided with a cavity, the feeding channel is used for introducing the second reaction product, the first gas channel is used for discharging gas, the lower part of the main body is conical, the discharge hole is arranged at the bottom of the main body of the conical part, and the stirring paddle is arranged in the main body of the conical part.
10. The method for producing 2-hydroxy-4-methylthiobutyrate according to claim 9, wherein: the feeding channel, the first gas channel and the solid feeding port are arranged at the upper end of the main body; and/or the outside of the first tubular reactor and the outside of the second tubular reactor are provided with water circulation channels.
11. The method for producing 2-hydroxy-4-methylthiobutyrate according to claim 8, wherein: the preparation method further comprises the step of introducing the first reaction product into a storage tank, the upper end of which is provided with a second gas channel for discharging gas, before feeding the first reaction product to the second static mixer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211508543.5A CN115894313B (en) | 2022-11-29 | 2022-11-29 | Preparation method and production system of 2-hydroxy-4-methylthiobutyrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211508543.5A CN115894313B (en) | 2022-11-29 | 2022-11-29 | Preparation method and production system of 2-hydroxy-4-methylthiobutyrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115894313A CN115894313A (en) | 2023-04-04 |
| CN115894313B true CN115894313B (en) | 2024-04-30 |
Family
ID=86487660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211508543.5A Active CN115894313B (en) | 2022-11-29 | 2022-11-29 | Preparation method and production system of 2-hydroxy-4-methylthiobutyrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115894313B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155277A (en) * | 1994-08-12 | 1997-07-23 | 德古萨股份公司 | Process for the preparation of 2-hydroxy-4-methylthiobutyric acid (MHA) and its use as a feed supplement |
| JPH1175885A (en) * | 1997-07-10 | 1999-03-23 | Nippon Soda Co Ltd | Production of calcium 2-hydroxy-4-methylthiobutanoate |
| CN1704435A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Continuous method for preparing syndiotactic polyvinyl aromatic hydrocarbon |
| CN109232336A (en) * | 2018-11-09 | 2019-01-18 | 禄丰天宝磷化工有限公司 | Clean and environment-friendly production method of methionine hydroxy analogue |
| CN113753935A (en) * | 2021-08-12 | 2021-12-07 | 贵州省化工研究院 | Method and device for co-producing nano barium sulfate and nano calcium carbonate |
-
2022
- 2022-11-29 CN CN202211508543.5A patent/CN115894313B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155277A (en) * | 1994-08-12 | 1997-07-23 | 德古萨股份公司 | Process for the preparation of 2-hydroxy-4-methylthiobutyric acid (MHA) and its use as a feed supplement |
| JPH1175885A (en) * | 1997-07-10 | 1999-03-23 | Nippon Soda Co Ltd | Production of calcium 2-hydroxy-4-methylthiobutanoate |
| CN1704435A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Continuous method for preparing syndiotactic polyvinyl aromatic hydrocarbon |
| CN109232336A (en) * | 2018-11-09 | 2019-01-18 | 禄丰天宝磷化工有限公司 | Clean and environment-friendly production method of methionine hydroxy analogue |
| CN113753935A (en) * | 2021-08-12 | 2021-12-07 | 贵州省化工研究院 | Method and device for co-producing nano barium sulfate and nano calcium carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115894313A (en) | 2023-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103664719B (en) | Thick hydrocyanic acid is utilized to produce D continuously, the method for METHIONINE and device | |
| CN100396733C (en) | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| US20120141359A1 (en) | Process for preparing ammonium metatungstate | |
| CN110698357A (en) | Method for continuously preparing glycine from hydroxyacetonitrile by using microchannel reactor | |
| CN104844485B (en) | The clean preparation method of methionine | |
| US20240010608A1 (en) | Kettle-type continuous production method for glycine | |
| CN113336684A (en) | Production process and production system of methionine and methionine hydroxy analogue | |
| US12275692B2 (en) | Method for preparing sodium taurate as taurine intermediate, and method for preparing taurine | |
| CN101462985B (en) | Clean production process for azobisformamide | |
| CN100396734C (en) | Method for producing the yellow pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| CN115894313B (en) | Preparation method and production system of 2-hydroxy-4-methylthiobutyrate | |
| CN112707850A (en) | Preparation method of low-oligomer hydroxymethionine metal chelate | |
| CN106044853B (en) | A kind of ammonium metavanadate depth removes the purification process of silicon | |
| CN102659650A (en) | Device and method for preparing DL-methionine salt | |
| CN213231531U (en) | Continuous nitric oxide production device | |
| US20240083862A1 (en) | Method for preparing acesulfame potassium | |
| CN110759880A (en) | Preparation method of potassium isoascorbate | |
| CN102229549B (en) | Method for preparing isooctyl mercaptoacetate | |
| CN111978222B (en) | Preparation method of feed additive DL-methionine complex zinc | |
| CN101531604B (en) | Method for synthesizing betaine | |
| CN110272368B (en) | Preparation method of C15 sulfone | |
| CN205368191U (en) | N - isopropyl azanol production system | |
| CN113501753A (en) | Method for synthesizing potassium diformate based on phase transfer catalyst | |
| CN107382725A (en) | A kind of method of continuous production dihydroxy acetic acid MENTHOL ester | |
| CN218794974U (en) | Acidized tail gas absorption system in sodium nitrate production process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |