CN113620905A - Industrial production method of tebuthiuron technical - Google Patents
Industrial production method of tebuthiuron technical Download PDFInfo
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- CN113620905A CN113620905A CN202111071416.9A CN202111071416A CN113620905A CN 113620905 A CN113620905 A CN 113620905A CN 202111071416 A CN202111071416 A CN 202111071416A CN 113620905 A CN113620905 A CN 113620905A
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- 238000000034 method Methods 0.000 title claims abstract description 32
- HBPDKDSFLXWOAE-UHFFFAOYSA-N Tebuthiuron Chemical compound CNC(=O)N(C)C1=NN=C(C(C)(C)C)S1 HBPDKDSFLXWOAE-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000009776 industrial production Methods 0.000 title claims abstract description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 43
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 38
- UMEJBYJALNGUQF-UHFFFAOYSA-N 5-tert-butyl-n-methyl-1,3,4-thiadiazol-2-amine Chemical compound CNC1=NN=C(C(C)(C)C)S1 UMEJBYJALNGUQF-UHFFFAOYSA-N 0.000 claims abstract description 37
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000007112 amidation reaction Methods 0.000 claims abstract description 20
- 239000012442 inert solvent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000006552 photochemical reaction Methods 0.000 claims abstract description 10
- -1 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole toluene Chemical compound 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004557 technical material Substances 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000005660 chlorination reaction Methods 0.000 description 9
- 238000004321 preservation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 125000002252 acyl group Chemical group 0.000 description 8
- 230000009435 amidation Effects 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 238000005917 acylation reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000010933 acylation Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 3
- UBBJYJXRQJNARS-UHFFFAOYSA-N 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1-methylurea Chemical compound CC(C)(C)C1=NN=C(S1)N(C(=O)N)C UBBJYJXRQJNARS-UHFFFAOYSA-N 0.000 description 2
- NXXBCDHYUFWPFQ-UHFFFAOYSA-N 2-tert-butyl-1,3,4-thiadiazole Chemical compound CC(C)(C)C1=NN=CS1 NXXBCDHYUFWPFQ-UHFFFAOYSA-N 0.000 description 2
- RMFWSFGZAHFNAF-UHFFFAOYSA-N 5-tert-butyl-n-methyl-1,3,4-thiadiazol-2-amine;hydrochloride Chemical compound Cl.CNC1=NN=C(C(C)(C)C)S1 RMFWSFGZAHFNAF-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 238000012432 intermediate storage Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229940057054 1,3-dimethylurea Drugs 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- HFCYZXMHUIHAQI-UHFFFAOYSA-N Thidiazuron Chemical compound C=1C=CC=CC=1NC(=O)NC1=CN=NS1 HFCYZXMHUIHAQI-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- FGRLDFOPXIJTFS-UHFFFAOYSA-N formyl chloride methanamine Chemical compound C(=O)Cl.CN FGRLDFOPXIJTFS-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GRRYSIXDUIAUGY-UHFFFAOYSA-N n-methylcarbamoyl chloride Chemical compound CNC(Cl)=O GRRYSIXDUIAUGY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LAYPMCGIWDGYKX-UHFFFAOYSA-N trichloromethyl hydrogen carbonate Chemical compound OC(=O)OC(Cl)(Cl)Cl LAYPMCGIWDGYKX-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
- C07D285/135—Nitrogen atoms
Abstract
The invention discloses an industrial production method of tebuthiuron technical, which comprises the following steps: (1) dissolving a raw material 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole in an inert solvent to prepare an inert solvent solution with a certain concentration; (2) 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole toluene solution and phosgene or a diphosphor triphosgene solution are added for photochemical reaction; (3) removing phosgene from the material after the photochemical reaction is finished; (4) carrying out amidation reaction on the material subjected to phosgene removal and monomethylamine gas; (5) and (3) carrying out post-treatment on the material after the amidation reaction is finished to obtain the product tebuthiuron. The product quality of the invention is more stable. The investment of the device is reduced, the production capacity of the device is improved, the process flow is simpler and more convenient, and the continuous automatic control operation of the device is facilitated.
Description
Technical Field
The invention relates to an industrial production method of tebuthiuron technical.
Background
Thidiazuron, also known as Tebuthiuron, is chemically 1- (5-tert-butyl-1, 3, 4-thiadiazol-2-yl) -1, 3-diurea. The crude drug is white powder, has melting point of 162.85 deg.C, vapor pressure of 0.04mPa (25 deg.C), solubility in water of 2.57g/l (20 deg.C) at 25 deg.C, is stable in water with pH of 5 and 9, can be slowly dissolved in water with pH of 9, and is stable to heat. DT50(25 ℃) is hydrolyzed with 64d (pH3, 6 and 9), is a biocidal urea herbicide, has good control effect on annual and perennial grassy and broadleaf weeds, and can be used for preventing and killing non-cultivated land weeds, shrubs in pastures and grassy and broadleaf weeds in sugarcane fields.
The tebuthiuron has four synthetic methods according to domestic and foreign literature reports
(1) The synthesis of tebuthiuron from the reaction of 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and methyl isocyanate is reported in documents such as U.S. Pat. No. 4,4283543, GB1195672, DE3113328, etc. The process has high product yield and good quality, but the methyl isocyanate as the raw material is flammable and explosive, has extremely high toxicity, has extremely high safety risk in the production process, and is limited in raw material source.
(2) CN105669592B reports that 2-halide or 2-methylsulfonyl ester of 5-tert-butyl-1, 3, 4-thiadiazole is reacted with 1, 3-dimethylurea to synthesize tebuthiuron, which aims to avoid using extremely toxic raw materials such as methyl isocyanate or phosgene, but the conversion rate of the 2-halide or 2-methylsulfonyl ester of the reaction raw material 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is low, and a byproduct N, N' -bis (N-methyl-N- (5-tert-butyl-1, 3, 4-thiadiazole-2 yl)) urea is generated, which brings difficulty to post-treatment and is not favorable for realizing industrial production.
(3) CN200910100138 reports that 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and methylamine formyl chloride react under the action of an acid-binding agent to synthesize tebuthiuron. The production of methylamino formyl chloride still needs to use phosgene or diphosphine (trichloromethyl chloroformate) and triphosgene (bis (trichloromethyl carbonic acid)) as raw materials for production, the product yield and content are not high, more industrial wastewater exists, the cost is high, and the whole production process is not economical.
(4) CN100579971C reports that 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole raw material is used as a substrate in an inert solvent, triphosgene is dripped or phosgene is introduced for reaction at about 50 ℃, and then the reaction product reacts with monomethylamine to synthesize tebuthiuron. In the acylation reaction process, the intermediate product 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole can generate side reaction under the condition of insufficient phosgene or triphosgene amount to generate N, N' -bis (N-methyl-N- (5-tert-butyl-1, 3, 4-thiadiazolyl-2 yl)) urea, so that the product yield and quality are low, the post-treatment is difficult, and the industrial production is difficult to realize.
(5) The CN102603672B literature reports that the CN100579971C technology has the defects, and the technology is improved by adopting the processes of salifying, passing light and then aminating. According to the process, 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole serving as a raw material is subjected to salt formation protection by hydrochloric acid or hydrogen chloride to form 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole hydrochloride, and then reacts with phosgene or triphosgene to synthesize an intermediate 2-methylaminoformyl chloride-5-tert-butyl-1, 3, 4-thiadiazole, so that the generation of a byproduct N, N' -bis (N-methyl-N- (5-tert-butyl-1, 3, 4-thiadiazole-2 yl)) urea is greatly reduced, the product quality and yield are greatly improved, and the following defects exist:
(a) hydrochloric acid or hydrogen chloride and 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole are salified and dehydrated, and due to the use of the hydrochloric acid or the hydrogen chloride and an organic solvent, the material corrosion is strong, the requirement on equipment materials is high, and the device investment is large.
(b) Salifying and dehydrating are carried out, and the energy consumption is high.
(c) The product production table is long and the device efficiency is low.
(d) The 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole hydrochloride is insoluble solid in organic inert solvents such as toluene, chlorobenzene and the like, so the device is not beneficial to realizing continuous self-control operation.
Therefore, how to solve the problems encountered in the above tebuthiuron production process is the subject of the present invention.
Disclosure of Invention
The invention aims to provide a simple, convenient and efficient industrialized production method of tebuthiuron technical.
The technical solution of the invention is as follows:
an industrial production method of tebuthiuron technical, which is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving a raw material 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole in an inert solvent to prepare an inert solvent solution with a certain concentration;
(2) carrying out photochemical reaction on the inert solvent solution of 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and phosgene or a diphosphor triphosgene solution;
(3) removing phosgene from the material after the photochemical reaction is finished;
(4) carrying out amidation reaction on the material subjected to phosgene removal and monomethylamine gas;
(5) and (3) carrying out post-treatment on the material after the amidation reaction is finished to obtain the product tebuthiuron.
The specific steps of the step (2) are as follows: in a continuous photochemical reactor, pumping 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole toluene solution through a DCS control system according to a certain material ratio and a certain flow rate, introducing phosgene or adding triphosgene solution to carry out photochemical reaction, wherein the reaction system always keeps excess phosgene or triphosgene, and the temperature of the reaction system keeps a certain range. The reaction system always keeps the excess of phosgene or triphosgene, which means that the molar instantaneous amount of the phosgene or the triphosgene added into the reaction system is always larger than the molar instantaneous amount of the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole added.
The specific steps of the step (3) are as follows: and (4) feeding the material after the photochemical reaction is finished into a phosgene removing tower to remove phosgene.
The specific steps of the step (4) are as follows: and (3) simultaneously feeding the materials after the materials are qualified after polishing and monomethylamine gas into amidation reaction equipment according to a certain molar ratio for amidation reaction.
And (5) carrying out post-treatment including water washing, layering and crystallization.
Distilling the crystallization mother liquor to recover the product, and returning the solvent to the ingredients for reuse.
The inert solvent is one or a mixture of more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloroethane and carbon tetrachloride.
In the step (1), the content range of the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole in the inert solvent is 5% -50%, and the optimal content is 10% -20%; the reaction temperature of the step (2) is 50-110 ℃, and the optimal temperature is 80-100 ℃; the molar ratio of phosgene or phosgene, triphosgene and 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is as follows: 5-1.01: 1; optimally: 1.5-1.1: 1; in the step (1), the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole solution is added in the following manner: the addition is carried out dropwise or on the atomized liquid surface, preferably on the atomized liquid surface.
And (3) adopting a triphosgene solution as a reaction system, wherein the solvent of the triphosgene solution is consistent with the inert solvent in the step (1).
And (4) amidation reaction, wherein the reaction equipment is tubular reactor equipment.
In the amidation reaction, the molar ratio of monomethylamine to 5-tert-butyl-1, 3, 4-thiadiazole-2-methylamino formyl chloride is as follows: (1.5-3.0) 1; reaction temperature: 10-80 ℃.
The method has the advantages that:
1. in the acyl chlorination reaction process, the hydrogen chloride generated in the reaction process of 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole-2-methylamino formyl chloride is used for the rapid reaction principle of 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole salification, the salification protection process of 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and hydrogen chloride and the reaction process of phosgene (or triphosgene) and 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole-2-methylamino formyl chloride are carried out simultaneously, so that the non-salified 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and 5-tert-butyl-1 in a liquid phase are avoided, 3, 4-thiadiazole-2-methylamino formyl chloride undergoes side reaction. The product quality is more stable.
2. The organic integration of salification and acylation processes saves an independent salification reaction step, not only cancels a salification reaction device, but also reduces the requirements on equipment materials and reduces the device investment.
3. Both the acyl chlorination and the amidation adopt a co-feeding method, thereby greatly improving the product quality, reducing the energy consumption of the product when saving reaction tables, and improving the production capacity of the device.
4. The salifying process and the acylation process are integrated, so that the process flow is simpler and more convenient, and the continuous automatic control operation of the device is facilitated.
5. The crystallization mother liquor is recycled, so that the product cost is reduced.
Drawings
FIG. 1 is a schematic view of the production process of the product of the present invention.
The invention is further illustrated by the following figures and examples.
Detailed Description
Example 1:
(1) 500kg of 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and 3000L of toluene are put into a 5000L batching kettle, and the temperature is raised to 70 ℃ to be completely dissolved. And (5) standby. The batching kettles are two groups, and are switched with each other to realize uninterrupted continuous feeding.
(2) 1000L of toluene is added into an acyl chlorination reactor with a reflux device, the temperature is increased to 80 ℃, a DCS system is used for controlling, the phosgene flow is set to be 10 m3/h, and phosgene is fed in advance for 30 minutes.
(3) And pumping the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole toluene solution in the batching kettle. Is controlled by a DCS system and is fed into the acyl chlorination reactor at the flow rate (800-. Meanwhile, phosgene is required to be introduced for reaction with the molar ratio of 1.2:1 of phosgene to 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole. The flow rate of phosgene is 25-35 m3And h is adjusted. The reaction temperature was maintained at 80-100 ℃. The light tail gas is catalyzed and hydrolyzed into hydrochloric acid by a phosgene tail gas treatment device 7501.
(4) And after the reaction liquid is detected to be qualified (the content of the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is less than 1.5 percent), the reaction liquid is extracted from the side line of the acylation reactor and enters a heat preservation reactor. The reaction is carried out for 2 hours under the condition of 90-100 ℃ to ensure that the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is completely reacted. Two groups of heat preservation reactors are switched with each other to realize the continuity of front and back posts.
(5) And after the heat preservation reaction is finished (the content of the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is less than 0.2 percent), continuously pumping the reaction liquid into a phosgene removing tower, and removing light by using nitrogen. The flash temperature is 80-90 ℃, and the nitrogen flow is 25 m3H is used as the reference value. Cooling and separating the expelled phosgene and hydrogen chloride, and reusing the phosgene in acyl chlorination reaction. The N-methyl N- (5-tert-butyl-1, 3, 4-thiadiazole) -aminomethyl is qualified after the light emission (the free chlorine is less than 0.5 percent)And (3) introducing the acyl chloride toluene solution into an intermediate transfer storage tank, and keeping the temperature to be more than 45 ℃ for later use.
Content of N-methyl N- (5-tert-butyl-1, 3, 4-thiadiazole) -carbamoyl chloride in N-methyl N- (5-tert-butyl-1, 3, 4-thiadiazole) -carbamoyl chlorotoluene: greater than 20%. The conversion of the raw material was 99.8%. The product selectivity is 98.5%.
(6) And the mixed solution is fed into the amidation pipeline circulating reactor at the flow rate of 800-. Meanwhile, monomethylamine gas is introduced into the reactor to react with the molar ratio of 2.0:1 of monomethylamine to 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole. The total flow rate of monomethylamine is 15-25 m3And h is adjusted. The reaction temperature was maintained at 15-25 ℃. The pH value of the material is controlled at 8.5 during the extraction. Entering a heat preservation reaction tower, and staying for 2 hours at the temperature of 60-80 ℃. Entering a water washing delayer.
(7) And in a water washing delaminator, the reaction liquid after acid water at the temperature of 75-80 ℃ and amidation is neutralized and washed in a countercurrent mode at 800-. The organic layer flows into a phase separator and then enters a vacuum falling-film evaporator, and the distilled solvent is used as auxiliary materials. The concentrated solution enters a circulating crystallizer again for crystallization. And (4) continuously centrifuging and discharging the product, and then carrying out vacuum drying to obtain the tebuthiuron product. The content of tebuthiuron is 98% and the product yield is 96% (based on thiadiazole) through detection. Returning one part of the centrifugal mother liquor to the crystallizer for cyclic application, extracting the other part of the centrifugal mother liquor, removing desolventizing, and recovering the product.
(8) And the water phase separated out by the phase separator is 75-80 ℃, enters a monomethylamine recovery tower through an intermediate storage tank and a pump, is pumped into a liquid alkali reaction to escape monomethylamine gas, and is subjected to alkali drying and then is subjected to amidation pipeline circulating reaction to be used as a raw material monomethylamine. Neutralizing the alkaline water containing sodium chloride and the acidic water, and evaporating to obtain a byproduct sodium chloride. The distilled water is cooled to 75-80 ℃ and then is removed from a washing delayer to be used as washing water for reuse.
Example 2:
(1) 500kg of 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and 3000L of toluene are put into a 5000L batching kettle, the temperature is raised to 70-80 ℃, and the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and the toluene are completely dissolved. And adding 30L of triethylamine as a triphosgene decomposition catalyst for later use. The batching kettles are two groups, and are switched with each other to realize uninterrupted continuous feeding.
(2) And 500kg of triphosgene and 1500kg of toluene are put into a 3000L batching kettle and stirred for dissolution. A25% triphosgene in toluene solution was prepared. And (5) standby. The batching kettles are two groups, and are switched with each other to realize uninterrupted continuous feeding.
(3) Adding 500L of toluene into an acyl chlorination reactor with a reflux device, heating to 85 ℃, and pumping triphosgene toluene liquid by a metering pump at 200kg/h for 10 minutes under the control of a DCS system.
(3) And the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole toluene solution in the material mixing kettle is fed into the acyl chlorination reactor at the flow rate of 800-. Meanwhile, triphosgene toluene liquid is pumped to react according to the requirement that the molar ratio of the triphosgene to the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is 0.5: 1. The flow rate of the triphosgene toluene liquid is adjusted between 460 and 600kg/h, and the reaction temperature is kept between 80 and 100 ℃. The light tail gas is catalyzed and hydrolyzed into hydrochloric acid by a phosgene tail gas treatment device 7501.
(4) And the qualified reaction liquid (the content of the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is less than 1.5 percent) is extracted from the lateral line of the acylation reactor, enters a heat preservation reactor, and reacts for 2 hours at the temperature of 90-100 ℃ in a heat preservation way, so that the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is completely reacted. Two groups of heat preservation reactors are arranged, and are switched with each other, so that the continuity of front and rear posts is realized.
(5) And continuously pumping the reaction liquid after the heat preservation reaction is qualified (the content of the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is less than 0.2 percent) into a phosgene removing tower, and removing light by using nitrogen. The flashing temperature is kept between 80 and 90 ℃, and the nitrogen flow is 25 m3H is used as the reference value. Cooling and separating the expelled phosgene and hydrogen chloride, and reusing the phosgene in acyl chlorination reaction. And (3) adding the N-methyl N- (5-tert-butyl-1, 3, 4-thiadiazole) -carbamyl chloride toluene solution which is polished to be qualified (the free chlorine is less than 0.5%) into a middle transfer storage tank, and keeping the temperature to be more than 45 ℃ for later use.
Content of N-methyl N- (5-tert-butyl-1, 3, 4-thiadiazole) -carbamoyl chloride in N-methyl N- (5-tert-butyl-1, 3, 4-thiadiazole) -carbamoyl chlorotoluene: greater than 20%. The conversion of the raw material was 99.8%. The product selectivity is 98.5%.
(6) And the mixed solution is fed into the amidation pipeline circulating reactor at the flow rate of 800-. Meanwhile, monomethylamine gas is introduced for reaction, wherein the molar ratio of the monomethylamine to the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is 2.05: 1. The total flow rate of monomethylamine is 15-25 m3And h is adjusted. The reaction temperature was maintained at 15-25 ℃. The pH value of the material is controlled at 8 during the extraction. Entering a heat preservation reaction tower, and staying for 2 hours at the temperature of 60-80 ℃. Entering a water washing delayer.
(7) And in a water washing delaminator, the reaction liquid after acid water at the temperature of 75-80 ℃ and amidation is neutralized and washed in a countercurrent mode at 800-. The organic layer flows into a phase separator and then enters a vacuum falling-film evaporator, the evaporated solvent is used for material blending and application, and the concentrated solution enters a circulating crystallizer for crystallization. And (4) continuously centrifuging and discharging the product, and then carrying out vacuum drying to obtain the tebuthiuron product. The detection shows that the content of tebuthiuron is 97.5%. The product yield is calculated to be 95 percent (calculated by thiadiazole). Returning one part of the centrifugal mother liquor to the crystallizer for cyclic application, extracting the other part of the centrifugal mother liquor, removing desolventizing, and recovering the product.
(8) And the water phase separated out by the phase separator is 75-80 ℃, enters a monomethylamine recovery tower through an intermediate storage tank and a pump, is pumped into a liquid alkali reaction to escape monomethylamine gas, and is subjected to alkali drying and then is subjected to amidation pipeline circulating reaction to be used as a raw material monomethylamine. The alkaline water containing sodium chloride is neutralized with the acidic water and evaporated. Sodium chloride is a byproduct. The distilled water is cooled to 75-80 ℃ and then is removed from a washing delayer to be used as washing water for reuse.
The above examples are merely examples to help a skilled person better understand the technology of the present invention for a process. The invention is in the scope of protection of the process for the acylation and chlorination of 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole by co-feeding 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and phosgene or triphosgene solution.
Claims (10)
1. An industrial production method of tebuthiuron technical, which is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving a raw material 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole in an inert solvent to prepare an inert solvent solution with a certain concentration;
(2) carrying out photochemical reaction in a co-feeding mode by using an inert solvent solution of 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole and phosgene or adding a diphosphor triphosgene solution;
(3) removing phosgene from the material after the photochemical reaction is finished;
(4) carrying out amidation reaction on the material subjected to phosgene removal and monomethylamine gas;
(5) and (3) carrying out post-treatment on the material after the amidation reaction is finished to obtain the product tebuthiuron.
2. The method for industrially producing a tebuthiuron technical material as claimed in claim 1, which is characterized in that: the specific steps of the step (2) are as follows: in a continuous photochemical reactor, phosgene or triphosgene solution is pumped in through a DCS control system according to a certain material ratio and a certain flow rate to carry out photochemical reaction in a feeding mode of pumping 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole toluene solution, the excess of phosgene or triphosgene is always kept in a reaction system, and the temperature of the reaction system is kept in a certain range.
3. The method for industrially producing a tebuthiuron technical material as claimed in claim 1, which is characterized in that: the specific steps of the step (3) are as follows: and (4) feeding the material after the photochemical reaction is finished into a phosgene removing tower to remove phosgene.
4. The method for industrially producing a tebuthiuron technical material as claimed in claim 1, which is characterized in that: the specific steps of the step (4) are as follows: and (3) simultaneously feeding the materials after the materials are qualified after polishing and monomethylamine gas into amidation reaction equipment according to a certain molar ratio for amidation reaction.
5. The method for industrially producing a tebuthiuron technical material as claimed in claim 1, which is characterized in that: and (5) carrying out post-treatment including water washing, layering and crystallization.
6. The method for industrially producing a tebuthiuron technical material as claimed in claim 5, which is characterized in that: distilling the crystallization mother liquor to recover the product, and returning the solvent to the ingredients for reuse.
7. The method for industrially producing a tebuthiuron technical product as claimed in claim 1, 2, 3,4, 5 or 6, wherein: the inert solvent is one or a mixture of more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloroethane and carbon tetrachloride.
8. The method for industrially producing a tebuthiuron technical product as claimed in claim 1, 2, 3,4, 5 or 6, wherein: in the step (1), the content range of the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole in the inert solvent is 5% -50%, and the optimal content is 10% -20%; the reaction temperature of the step (2) is 50-110 ℃, and the optimal temperature is 80-100 ℃; the molar ratio of phosgene or phosgene, triphosgene and 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole is as follows: 5-1.01: 1; optimally: 1.5-1.1: 1; in the step (1), the 2-methylamino-5-tert-butyl-1, 3, 4-thiadiazole solution is added in the following manner: the addition is carried out dropwise or on the atomized liquid surface, preferably on the atomized liquid surface.
9. The method for industrially producing a tebuthiuron technical product as claimed in claim 1, 2, 3,4, 5 or 6, wherein: and (3) adopting a triphosgene solution as a reaction system, wherein the solvent of the triphosgene solution is consistent with the inert solvent in the step (1).
10. The method for industrially producing a tebuthiuron technical product as claimed in claim 1, 2, 3,4, 5 or 6, wherein: and (4) amidation reaction, wherein the reaction equipment is tubular reactor equipment.
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