CN108997418A - A kind of improvement technique synthesizing omethoate - Google Patents
A kind of improvement technique synthesizing omethoate Download PDFInfo
- Publication number
- CN108997418A CN108997418A CN201810886441.4A CN201810886441A CN108997418A CN 108997418 A CN108997418 A CN 108997418A CN 201810886441 A CN201810886441 A CN 201810886441A CN 108997418 A CN108997418 A CN 108997418A
- Authority
- CN
- China
- Prior art keywords
- omethoate
- crude oil
- thiophosphate
- oxy
- thick
- 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.)
- Granted
Links
- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000006872 improvement Effects 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 239000010779 crude oil Substances 0.000 claims abstract description 82
- 150000002148 esters Chemical class 0.000 claims abstract description 71
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000001556 precipitation Methods 0.000 claims abstract description 46
- 238000002360 preparation method Methods 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000006227 byproduct Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 40
- 238000004321 preservation Methods 0.000 claims description 32
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- 235000019270 ammonium chloride Nutrition 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 238000000605 extraction Methods 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 14
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- IHBBREPROWBPRG-UHFFFAOYSA-N pentaazanium;phosphate;sulfate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O.[O-]S([O-])(=O)=O IHBBREPROWBPRG-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000002274 desiccant Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000000658 coextraction Methods 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical group CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 238000012805 post-processing Methods 0.000 abstract description 2
- -1 salt compounds Chemical class 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 238000004807 desolvation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001465977 Coccoidea Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 241001347978 Major minor Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000488583 Panonychus ulmi Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000062793 Sorghum vulgare Species 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a kind of improvement technique for synthesizing omethoate, this method is the thick crude oil of the omethoate of preparation to be first dried, then precipitation during preparing omethoate using rear amine-decomposing, and omethoate crude oil is made.The present invention improves reaction environment to the full extent, the process for improving main reaction, reduces hydrolysis, improve reaction yield, and keep the post-processing containing salt compounds more convenient by the improvement to multiple techniques.Using technique of the invention, oxy-thiophosphate essence ester yield be can be improved to 86% or more, and purity is also improved to 90% or more；And purity of ammonia chloride can be sold up to 99% or more directly as by-product primes, omethoate crude oil total recovery can be improved to 79% or more；Crude oil purity also increases, and integrated artistic is substantially improved, and social and economic benefits are huge.
Description
Technical field
The present invention relates to a kind of improvement techniques for synthesizing omethoate, belong to organic synthesis technical field.
Background technique
Organic synthesis is a kind of common reaction, but due to the autoreactivity of organic synthesis, organic synthesis
It will appear some problems in journey.Such as there are many side reactions in solid-liquid organic synthesis, one of the most common is exactly to generate
By-product containing salt, and the generation of side reaction all more or less constitutes certain influence to main reaction, for example: influencing main reaction
Process, influence content, yield of principal product etc..As the content that hydrolyze can to product occurs for organic compound, yield has not
Benefit influences.
Omethoate is a kind of efficient absorbability insecticidal/acaricidal agent, is widely used in rice, cotton, fruit tree, wheat, height
The crops such as fine strain of millet, sugarcane, for preventing and treating sucking pest, to red spider, aphid, cotten aphid, aleyrodid, coccid etc. with drug resistance
There is special efficacy.The country mostly uses greatly rear amine-decomposing to prepare omethoate at present, but there is also some problems in omethoate synthesis process.
As by-product ammonium chloride can be generated in oxy-thiophosphate reaction in omethoate synthesis.It is needed in the conventional procedure of the reaction plus water, and
It is reacted under the conditions of 65 DEG C, entire process environments are particularly conducive to chloride leach in thick ester system, therefore cause system and put
Heat is big, employee is to temperature operating difficulties, and increases the progress of side reaction, increases the meeting of major-minor product to a greater extent
Chance, reduce the yield of the step.If the thick crude oil of omethoate needs to carry out precipitation, and water can occur for omethoate during being somebody's turn to do
Solution, causes the reduction of omethoate crude yield and content.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of improvement technique for synthesizing omethoate, the techniques
Temperature control it is more convenient, product purity is high, high income.
To achieve the goals above, the technical scheme adopted by the invention is that:
A kind of improvement technique synthesizing omethoate: during preparing omethoate using rear amine-decomposing, by the oxygen of preparation
The thick crude oil of Rogor is first dried, then precipitation, and omethoate crude oil is made.
Dry is three-stage drying.
The improvement technique of omethoate mainly comprises the steps that the preparation of the thick ester of (1) oxy-thiophosphate；(2) oxy-thiophosphate essence
The preparation of ester；(3) preparation of the thick crude oil of omethoate；(4) extraction of the thick crude oil of omethoate；(5) drying of omethoate crude oil；(6)
The preparation of omethoate essence crude oil.
The thick ester of step (1) oxy-thiophosphate is prepared as anhydrous system, and reaction temperature is 45-55 DEG C, time 2-4h.
The thick ester preparation of step (1) oxy-thiophosphate method particularly includes: 800-1200kg chloroethene is successively put into reaction kettle
Sour methyl esters, 500-900L ammonium sulphate phosphate salt, 2-5kg catalyst open stirring, steam valve, close and steam when temperature rises to 45-55 DEG C
Steam valve, 45-55 DEG C of heat preservation 2-4h open cooling penstock and carry out material cooling, when temperature is down to 20-40 DEG C after heat preservation
Discharging, material carry out the centrifuge separation of ammonium chloride, and the filtrate thrown away is the thick ester of oxy-thiophosphate；The ammonium chloride being centrifuged out is through drying
By-product sale is carried out after dry.
The preparation of step (2) oxy-thiophosphate essence ester method particularly includes: first the thick ester of oxy-thiophosphate is dried, then precipitation,
Oxy-thiophosphate essence ester is made.
The thick crude oil preparation of step (3) omethoate method particularly includes: 500-600kg oxy-thiophosphate essence ester is put into and is synthesized
Pot starts the monomethylamine aqueous solution that 170-230kg mass fraction 40% is added dropwise, control drop when synthesizing pot temperature and dropping to -25 DEG C
Added-time temperature is at -9 to -12 DEG C；After being added dropwise, -8 to -12 DEG C of heat preservation 20-40min add hydrochloric acid tune pH=5- after heat preservation
7, temperature is controlled at 0 DEG C, adds 300-600kg chloroform, feed liquid is squeezed into sub-material tank after adding, carry out subsequent extraction.
Dry desiccant used is 3A molecular sieve, and molecular sieve is 1:2 with the weight ratio for needing dry matter；Catalyst is three fourths
Amine, triethylamine, TEBA, mixing one or more of in hexadecyltrimethylammonium chloride；The temperature of precipitation is controlled in 70-90
DEG C, vacuum control is below -0.095MPa.
The synthetic method of omethoate, comprising the following steps:
(1) preparation of the thick ester of oxy-thiophosphate
800-1200kg methyl chloroacetate, 500-900L ammonium sulphate phosphate salt, 2-5kg catalyst are successively put into reaction kettle,
Stirring, steam valve, the steam off valve when temperature rises to 45-55 DEG C are opened, 45-55 DEG C of heat preservation 2-4h is opened after heat preservation
The penstock that cools down carries out material cooling, discharging when temperature is down to 20-40 DEG C, and material carries out the centrifuge separation of ammonium chloride, throws away
Filtrate be the thick ester of oxy-thiophosphate；The ammonium chloride being centrifuged out carries out by-product sale after drying；
(2) preparation of oxy-thiophosphate essence ester
The thick ester of oxy-thiophosphate is subjected to three-stage drying using molecular sieve, the thick ester of oxy-thiophosphate after drying is put into precipitation pot
Precipitation is carried out, the control of precipitation temperature is at 100-130 DEG C, and vacuum control is in -0.095MPa hereinafter, removal methyl chloroacetate, obtains
Oxy-thiophosphate essence ester；
(3) preparation of the thick crude oil of omethoate
500-600kg oxy-thiophosphate essence ester is put into synthesis pot, starts that 170- is added dropwise when synthesizing pot temperature and dropping to -25 DEG C
The monomethylamine aqueous solution of 230kg mass fraction 40%, temperature is at -9 to -12 DEG C when control is added dropwise；After being added dropwise, -8 to -12
DEG C heat preservation 20-40min, after heat preservation plus hydrochloric acid tune pH=5-7, temperature is controlled at 0 DEG C, is added 300-600kg chloroform, is added
Feed liquid is squeezed into sub-material tank afterwards；
(4) extraction of the thick crude oil of omethoate
After feed liquid stands 20-40min in sub-material filling, for lower layered material point to thick crude oil stock tank, upper layer then carries out chloroform extraction,
Three times, lower layered material extracted is all divided into thick crude oil stock tank for coextraction；
(5) drying of the thick crude oil of omethoate
Three-stage drying is carried out to the thick crude oil of omethoate using molecular sieve；
(6) preparation of omethoate essence crude oil
The thick crude oil of omethoate after drying is squeezed into precipitation kettle and carries out precipitation, the control of precipitation temperature is at 70-90 DEG C, vacuum control
System is in -0.095MPa hereinafter, pulling vacuum 20min or more can discharge to obtain omethoate essence crude oil.
Ammonium sulphate phosphate salt the preparation method comprises the following steps: by 600-900L dimethylphosphite be pumped into reaction kettle, put into 80-150kg sulphur
Sulphur powder starts logical ammonia when temperature of reaction kettle reaches 5 DEG C or less, leads to ammonia temperature and is not more than 12 DEG C, is 6-7.5 to reaction material liquid pH
When, stop logical ammonia, control 0-10 DEG C of temperature, keeps the temperature 45-60min, discharging.
The invention has the advantages that:
1, the present invention by exploring omethoate synthesis technology has found that certain journey can occur in omethoate desolvation process
The hydrolysis of degree, to influence the purity and yield of omethoate.Therefore the present invention is determined in reaction system by a series of experiment
The content of water is maximum to omethoate desolvation process Hydrolysis.For the hydrolysis that organic compound desolvation process is effectively reduced, this hair
It is bright to needing the thick crude oil of the omethoate for carrying out precipitation that water removal is dried, keep whole system anhydrous.The present invention has liquid simultaneously
The desiccant of machine compound has carried out repeated screening: usually liquid is added in desiccant by (1) drying of liquid organic compound
In organic compound, with the organic compound chemistry or catalytic action must not occur for desiccant used.(2) desiccant should not
It is dissolved in the liquid organic compound.(3) when selecting in conjunction with water the desiccant for generating hydrate, it is necessary to consider desiccant
Water absorption capacity and dry efficiency.Therefore final choice 3A molecular sieve of the present invention does the thick crude oil of omethoate as desiccant
Dry, after which carries out, omethoate crude oil total recovery be can be improved to 79% or more；Crude oil purity also increases, integrated artistic
It is substantially improved.
2, the present invention is dried the thick ester of oxy-thiophosphate using molecular sieve equally in oxy-thiophosphate essence ester preparation process,
Also achieve preferable effect, after thick ester water removal, oxy-thiophosphate essence ester yield be can be improved to 86% or more, purity also improve to
90% or more；And purity of ammonia chloride can be sold up to 99% or more directly as by-product primes.Compared to tradition
Technique, integrated artistic of the present invention are substantially improved.
3, the present invention has developed a kind of anhydrous response according to the characteristic (meeting water dissolution, low temperature is precipitated) of ammonium chloride, that is, exists
In the solid-liquid organic reaction that side reaction has ammonium chloride to generate, forbids the entrance of water, whole system is made to be in a kind of anhydrous reaction
State.Reaction system does not have water once, and ammonium chloride will be present in system with a kind of solid state, further in accordance with following three aspect
Process modification, integrated artistic is with the obvious advantage:
(1) increase quantity of solvent.Invention increases the proportions of solvent (methyl chloroacetate), to increase hot melt, operator
Member can preferably control reaction temperature, to improve the reaction rate of reactant, increase the generation of principal product, reduce by-product
With the molecular collision chance of principal product, reduces side reaction and generate.
(2) reaction temperature is reduced.Because system does not have water, reaction temperature is compared to greenhouse cooling when having water reaction, to reduce
Reaction condition.In addition, the reduction of reaction temperature not only can be reduced the generation of side reaction, principal product content and entire can be more improved
The yield of reaction.
(3) increase centrifugation, drying equipment.Ammonium chloride is collected it by being centrifuged, drying after being precipitated, and filtrate is as molten
Agent carries out recovery, and the ammonium chloride after drying can be sold.Water is not added in system, reduces the discharge of waste water, promotes public affairs
Clean manufacturing is taken charge of, while increasing by-product income to company again, is achieved many things at one stroke.
4, the present invention improves reaction environment to the full extent, improves main reaction by the improvement to multiple techniques
Process reduces hydrolysis, improves reaction yield, and keep the post-processing containing salt compounds more convenient, social and economic benefits are huge
Greatly.
Specific embodiment
Specific embodiments of the present invention will be described in further detail with reference to embodiments.
Ammonium sulphate phosphate salt the preparation method comprises the following steps: by 700L dimethylphosphite be pumped into reaction kettle, put into 100kg sulphur powder, to
Temperature of reaction kettle starts logical ammonia when reaching 3 DEG C or less, reactor temperature is not more than 12 DEG C when leading to ammonia, is to reaction material liquid pH
When 7.2, stop logical ammonia, control 5 DEG C of temperature, keeps the temperature 50min, discharging.
Embodiment 1
A kind of improvement technique synthesizing omethoate, comprising the following steps:
(1) preparation of the thick ester of oxy-thiophosphate
Successively put into 900kg methyl chloroacetate, 500L ammonium sulphate phosphate salt, 2.5kg triethylamine into reaction kettle, open stirring,
Steam valve, the steam off valve when temperature rises to 45 DEG C, 45 DEG C of heat preservation 3h open cooling penstock and carry out material after heat preservation
Cooling, discharging when temperature is down to 30 DEG C, material carry out the centrifuge separation of ammonium chloride, and the filtrate thrown away is that oxy-thiophosphate is thick
Ester；The ammonium chloride being centrifuged out carries out by-product sale after drying；
(2) preparation of oxy-thiophosphate essence ester
The thick ester of oxy-thiophosphate is subjected to three-stage drying using 3A molecular sieve, the weight ratio of molecular sieve and the thick ester of oxy-thiophosphate is
The thick ester investment precipitation pot of oxy-thiophosphate after drying is carried out precipitation by 1:2, the control of precipitation temperature at 110 DEG C, vacuum control-
0.095MPa obtains oxy-thiophosphate essence ester hereinafter, removal methyl chloroacetate；
(3) preparation of the thick crude oil of omethoate
500kg oxy-thiophosphate essence ester is put into synthesis pot, starts that 190kg matter is added dropwise when synthesizing pot temperature and dropping to -25 DEG C
The monomethylamine aqueous solution of score 40% is measured, temperature is at -10 DEG C when control is added dropwise；After being added dropwise, -10 DEG C of heat preservation 30min, heat preservation
After plus hydrochloric acid tune pH=6, temperature control at 0 DEG C, add 300kg chloroform, feed liquid squeezed into sub-material tank after adding；
(4) extraction of the thick crude oil of omethoate
After feed liquid stands 30min in sub-material filling, for lower layered material point to thick crude oil stock tank, upper layer then carries out chloroform extraction, altogether
Three times, lower layered material extracted is all divided into thick crude oil stock tank for extraction；
(5) drying of the thick crude oil of omethoate
Three-stage drying is carried out to the thick crude oil of omethoate using 3A molecular sieve, the weight ratio of molecular sieve and the thick crude oil of omethoate is
1:2；
(6) preparation of omethoate essence crude oil
The thick crude oil of omethoate after drying is squeezed into precipitation kettle and carries out precipitation, the control of precipitation temperature is at 80 DEG C, vacuum control
In -0.095MPa hereinafter, pulling vacuum 30min or more, discharging obtain omethoate crude oil.
The purity of oxy-thiophosphate essence ester obtained by the present embodiment is 89.78%, and the purity of yield 85.89%, ammonium chloride is
99.07%, the purity of omethoate crude oil (essence) is 84.27%, total recovery 78.49%.
Embodiment 2
A kind of improvement technique synthesizing omethoate, comprising the following steps:
(1) preparation of the thick ester of oxy-thiophosphate
Successively put into 1200kg methyl chloroacetate, 900L ammonium sulphate phosphate salt, 3.5kg triethylamine into reaction kettle, open stirring,
Steam valve, the steam off valve when temperature rises to 55 DEG C, 55 DEG C of heat preservation 3h open cooling penstock and carry out material after heat preservation
Cooling, discharging when temperature is down to 30 DEG C, material carry out the centrifuge separation of ammonium chloride, and the filtrate thrown away is that oxy-thiophosphate is thick
Ester；The ammonium chloride being centrifuged out carries out by-product sale after drying；
(2) preparation of oxy-thiophosphate essence ester
The thick ester of oxy-thiophosphate is subjected to three-stage drying using 3A molecular sieve, the weight ratio of molecular sieve and the thick ester of oxy-thiophosphate is
The thick ester investment precipitation pot of oxy-thiophosphate after drying is carried out precipitation by 1:2, the control of precipitation temperature at 130 DEG C, vacuum control-
0.095MPa obtains oxy-thiophosphate essence ester hereinafter, removal methyl chloroacetate；
(3) preparation of the thick crude oil of omethoate
580kg oxy-thiophosphate essence ester is put into synthesis pot, starts that 210kg matter is added dropwise when synthesizing pot temperature and dropping to -25 DEG C
The monomethylamine aqueous solution of score 40% is measured, temperature is at -10 DEG C when control is added dropwise；After being added dropwise, -10 DEG C of heat preservation 30min, heat preservation
After plus hydrochloric acid tune pH=6, temperature control at 0 DEG C, add 600kg chloroform, feed liquid squeezed into sub-material tank after adding；
(4) extraction of the thick crude oil of omethoate
After feed liquid stands 30min in sub-material filling, for lower layered material point to thick crude oil stock tank, upper layer then carries out chloroform extraction, altogether
Three times, lower layered material extracted is all divided into thick crude oil stock tank for extraction；
(5) drying of the thick crude oil of omethoate
Three-stage drying is carried out to the thick crude oil of omethoate using 3A molecular sieve, the weight ratio of molecular sieve and the thick crude oil of omethoate is
1:2；
(6) preparation of omethoate essence crude oil
The thick crude oil of omethoate after drying is squeezed into precipitation kettle and carries out precipitation, the control of precipitation temperature is at 85 DEG C, vacuum control
In -0.095MPa hereinafter, pulling vacuum 40min or more, discharging obtain omethoate crude oil.
The purity of oxy-thiophosphate essence ester obtained by the present embodiment is 89.91%, and the purity of yield 86.08%, ammonium chloride is
99.17%, the purity of omethoate crude oil is 84.75%, total recovery 78.93%.
Embodiment 3
A kind of improvement technique synthesizing omethoate, comprising the following steps:
(1) preparation of the thick ester of oxy-thiophosphate
1000kg methyl chloroacetate, 700L ammonium sulphate phosphate salt, 4kg triethylamine are successively put into reaction kettle, are opened stirring, are steamed
Steam valve, the steam off valve when temperature rises to 50 DEG C, 50 DEG C of heat preservation 3h open cooling penstock and carry out material drop after heat preservation
Temperature, discharging when temperature is down to 30 DEG C, material carry out the centrifuge separation of ammonium chloride, and the filtrate thrown away is the thick ester of oxy-thiophosphate；
The ammonium chloride being centrifuged out carries out by-product sale after drying；
(2) preparation of oxy-thiophosphate essence ester
The thick ester of oxy-thiophosphate is subjected to three-stage drying using 3A molecular sieve, the weight ratio of molecular sieve and the thick ester of oxy-thiophosphate is
The thick ester investment precipitation pot of oxy-thiophosphate after drying is carried out precipitation by 1:2, the control of precipitation temperature at 120 DEG C, vacuum control-
0.095MPa obtains oxy-thiophosphate essence ester hereinafter, removal methyl chloroacetate；
(3) preparation of the thick crude oil of omethoate
580kg oxy-thiophosphate essence ester is put into synthesis pot, starts that 230kg matter is added dropwise when synthesizing pot temperature and dropping to -25 DEG C
The monomethylamine aqueous solution of score 40% is measured, temperature is at -12 DEG C when control is added dropwise；After being added dropwise, -10 DEG C of heat preservation 30min, heat preservation
After plus hydrochloric acid tune pH=6, temperature control at 0 DEG C, add 500kg chloroform, feed liquid squeezed into sub-material tank after adding；
(4) extraction of the thick crude oil of omethoate
After feed liquid stands 30min in sub-material filling, for lower layered material point to thick crude oil stock tank, upper layer then carries out chloroform extraction, altogether
Three times, lower layered material extracted is all divided into thick crude oil stock tank for extraction；
(5) drying of the thick crude oil of omethoate
Three-stage drying is carried out to the thick crude oil of omethoate using 3A molecular sieve, the weight ratio of molecular sieve and the thick crude oil of omethoate is
1:2；
(6) preparation of omethoate essence crude oil
The thick crude oil of omethoate after drying is squeezed into precipitation kettle and carries out precipitation, the control of precipitation temperature is at 75 DEG C, vacuum control
In -0.095MPa hereinafter, pulling vacuum 20min or more, discharging obtain omethoate crude oil.
The purity of oxy-thiophosphate essence ester obtained by the present embodiment is 90.14%, and the purity of yield 86.28%, ammonium chloride is
99.26%, the purity of omethoate crude oil is 84.67%, total recovery 79.09%.
Comparative example
The technique of existing synthesis omethoate, comprising the following steps:
(1) preparation of the thick ester of oxy-thiophosphate
600kg methyl chloroacetate, 700L ammonium sulphate phosphate salt, 300kg water, 4kg triethylamine are successively put into reaction kettle, are opened
Stirring, steam valve, the steam off valve when temperature rises to 65 DEG C, 65 DEG C of heat preservation 3h stand 3h into water distributing can after heat preservation,
By lower layer's crude product be divided into measuring tank by filtering after carry out precipitation, obtain oxy-thiophosphate；
(2) preparation of oxy-thiophosphate essence ester
Oxy-thiophosphate thick ester investment precipitation pot is subjected to precipitation, the control of precipitation temperature at 120 DEG C, vacuum control-
0.095MPa obtains oxy-thiophosphate essence ester hereinafter, removal methyl chloroacetate；
(3) preparation of the thick crude oil of omethoate
580kg oxy-thiophosphate essence ester is put into synthesis pot, starts that 230kg matter is added dropwise when synthesizing pot temperature and dropping to -25 DEG C
The monomethylamine aqueous solution of score 40% is measured, controls dropping temperature at -12 DEG C；After being added dropwise, -10 DEG C of heat preservation 30min, heat preservation knot
Shu Houjia hydrochloric acid tune pH=6, temperature control at 0 DEG C, add 500kg chloroform, feed liquid is squeezed into sub-material tank after adding；
(4) extraction of the thick crude oil of omethoate
After feed liquid stands 30min in sub-material filling, for lower layered material point to thick crude oil stock tank, upper layer then carries out chloroform extraction, altogether
Three times, lower layered material extracted is all divided into thick crude oil stock tank for extraction；
(5) preparation of omethoate essence crude oil
The thick crude oil of omethoate is squeezed into precipitation kettle and carries out precipitation, the control of precipitation temperature at 75 DEG C, vacuum control-
0.095MPa is hereinafter, pulling vacuum 20min or more, discharging obtain omethoate crude oil.
The purity of oxy-thiophosphate essence ester obtained by comparative example is 87.56%, and the purity of yield 83.76%, ammonium chloride is
96.64%, the purity of omethoate crude oil is 83.24%, total recovery 75.60%.
The foregoing is merely the optimal embodiments of the present invention, and for those skilled in the art, the present invention can have
Various modifications and variations.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on, should all
It is included within protection scope of the present invention.
Claims (10)
1. a kind of improvement technique for synthesizing omethoate, which is characterized in that, will during preparing omethoate using rear amine-decomposing
The thick crude oil of the omethoate of preparation is first dried, then precipitation, and omethoate crude oil is made.
2. improvement technique according to claim 1, which is characterized in that dry is three-stage drying.
3. improvement technique according to claim 1, which is characterized in that the improvement technique of omethoate mainly includes following step
It is rapid: (1) preparation of the thick ester of oxy-thiophosphate；(2) preparation of oxy-thiophosphate essence ester；(3) preparation of the thick crude oil of omethoate；(4) oxygen is happy
The extraction of the thick crude oil of fruit；(5) drying of omethoate crude oil；(6) preparation of omethoate essence crude oil.
4. improvement technique according to claim 3, which is characterized in that being prepared as the thick ester of step (1) oxy-thiophosphate is anhydrous
System, reaction temperature are 45-55 DEG C, time 2-4h.
5. improvement technique according to claim 4, which is characterized in that the specific side of the thick ester preparation of step (1) oxy-thiophosphate
Method are as follows: successively put into 800-1200kg methyl chloroacetate, 500-900L ammonium sulphate phosphate salt, 2-5kg catalyst into reaction kettle, open
Stirring, steam valve, the steam off valve when temperature rises to 45-55 DEG C, 45-55 DEG C of heat preservation 2-4h open cooling after heat preservation
Penstock carries out material cooling, discharging when temperature is down to 20-40 DEG C, and material carries out the centrifuge separation of ammonium chloride, the filter thrown away
Liquid is the thick ester of oxy-thiophosphate；The ammonium chloride being centrifuged out carries out by-product sale after drying.
6. improvement technique according to claim 3, which is characterized in that the specific side of step (2) oxy-thiophosphate essence ester preparation
Method are as follows: first the thick ester of oxy-thiophosphate is dried, then precipitation, oxy-thiophosphate essence ester is made.
7. improvement technique according to claim 3, which is characterized in that the specific side of the thick crude oil preparation of step (3) omethoate
Method are as follows: 500-600kg oxy-thiophosphate essence ester is put into synthesis pot, starts that 170- is added dropwise when synthesizing pot temperature and dropping to -25 DEG C
The monomethylamine aqueous solution of 230kg mass fraction 40%, temperature is at -9 to -12 DEG C when control is added dropwise；After being added dropwise, -8 to -12
DEG C heat preservation 20-40min, after heat preservation plus hydrochloric acid tune pH=5-7, temperature is controlled at 0 DEG C, is added 300-600kg chloroform, is added
Feed liquid is squeezed into sub-material tank afterwards, carries out subsequent extraction.
8. improvement technique according to claim 1-7, which is characterized in that dry desiccant used is 3A molecule
Sieve, molecular sieve are 1:2 with the weight ratio for needing dry matter；Catalyst is tri-n-butylamine, triethylamine, TEBA, cetyl trimethyl
One or more of mixing in ammonium chloride；The temperature of precipitation is controlled at 70-90 DEG C, and vacuum control is below -0.095MPa.
9. any one of -7 improvement technique according to claim 1, which is characterized in that the synthetic method of omethoate, including it is following
Step:
(1) preparation of the thick ester of oxy-thiophosphate
800-1200kg methyl chloroacetate, 500-900L ammonium sulphate phosphate salt, 2-5kg catalyst are successively put into reaction kettle, are opened
Stirring, steam valve, the steam off valve when temperature rises to 45-55 DEG C, 45-55 DEG C of heat preservation 2-4h open cooling after heat preservation
Penstock carries out material cooling, discharging when temperature is down to 20-40 DEG C, and material carries out the centrifuge separation of ammonium chloride, the filter thrown away
Liquid is the thick ester of oxy-thiophosphate；The ammonium chloride being centrifuged out carries out by-product sale after drying；
(2) preparation of oxy-thiophosphate essence ester
The thick ester of oxy-thiophosphate is subjected to three-stage drying using molecular sieve, the thick ester investment precipitation pot of oxy-thiophosphate after drying is carried out
Precipitation, the control of precipitation temperature is at 100-130 DEG C, and vacuum control is in -0.095MPa hereinafter, removal methyl chloroacetate, obtains oxygen sulphur
Phosphide essence ester；
(3) preparation of the thick crude oil of omethoate
500-600kg oxy-thiophosphate essence ester is put into synthesis pot, starts that 170- is added dropwise when synthesizing pot temperature and dropping to -25 DEG C
The monomethylamine aqueous solution of 230kg mass fraction 40%, temperature is at -9 to -12 DEG C when control is added dropwise；After being added dropwise, -8 to -12
DEG C heat preservation 20-40min, after heat preservation plus hydrochloric acid tune pH=5-7, temperature is controlled at 0 DEG C, is added 300-600kg chloroform, is added
Feed liquid is squeezed into sub-material tank afterwards；
(4) extraction of the thick crude oil of omethoate
After feed liquid stands 20-40min in sub-material filling, for lower layered material point to thick crude oil stock tank, upper layer then carries out chloroform extraction, co-extraction
It takes three times, lower layered material extracted is all divided into thick crude oil stock tank；
(5) drying of the thick crude oil of omethoate
Three-stage drying is carried out to the thick crude oil of omethoate using molecular sieve；
(6) preparation of omethoate essence crude oil
The thick crude oil of omethoate after drying is squeezed into precipitation kettle and carries out precipitation, the control of precipitation temperature is at 70-90 DEG C, vacuum control
In -0.095MPa hereinafter, pulling vacuum 20min or more can discharge to obtain omethoate essence crude oil.
10. improvement technique according to claim 9, which is characterized in that ammonium sulphate phosphate salt the preparation method comprises the following steps: by 600-900L
Dimethylphosphite is pumped into reaction kettle, puts into 80-150kg sulphur powder, starts logical ammonia when temperature of reaction kettle reaches 5 DEG C or less,
Logical ammonia temperature is not more than 12 DEG C, when reaction material liquid pH is 6-7.5, stops logical ammonia, controls 0-10 DEG C of temperature, keep the temperature 45-
60min, discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810886441.4A CN108997418B (en) | 2018-08-06 | 2018-08-06 | Improved technology for synthesizing omethoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810886441.4A CN108997418B (en) | 2018-08-06 | 2018-08-06 | Improved technology for synthesizing omethoate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108997418A true CN108997418A (en) | 2018-12-14 |
| CN108997418B CN108997418B (en) | 2021-06-18 |
Family
ID=64595926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810886441.4A Active CN108997418B (en) | 2018-08-06 | 2018-08-06 | Improved technology for synthesizing omethoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108997418B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651432A (en) * | 2019-01-17 | 2019-04-19 | 河南省化工研究所有限责任公司 | It is a kind of to prepare O, the method for O- dimethyl-S- (N- methylcarbamoyl methyl) thiophosphate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122810A (en) * | 1994-11-08 | 1996-05-22 | 清华紫光(集团)总公司 | Process for prodn. of oxy-thiophosphate |
| CN1122809A (en) * | 1994-11-08 | 1996-05-22 | 清化紫光(集团)总公司 | Process for prodn. of omethoate |
| CN1165825A (en) * | 1996-05-16 | 1997-11-26 | 北京清华紫光英力化工技术有限责任公司 | Compounded phase transfering catalyst used for catalyzing omethoate intermediate synthesis and its prepn. |
| CN1702074A (en) * | 2004-05-24 | 2005-11-30 | 姚文刚 | Process for synthesizing dimethoate |
| CN104610346A (en) * | 2013-11-05 | 2015-05-13 | 青岛好利特生物农药有限公司 | Persistent omethoate stock solution |
| CN107955034A (en) * | 2017-10-25 | 2018-04-24 | 江苏腾龙生物药业有限公司 | A kind of preparation process of Rogor active compound |
-
2018
- 2018-08-06 CN CN201810886441.4A patent/CN108997418B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122810A (en) * | 1994-11-08 | 1996-05-22 | 清华紫光(集团)总公司 | Process for prodn. of oxy-thiophosphate |
| CN1122809A (en) * | 1994-11-08 | 1996-05-22 | 清化紫光(集团)总公司 | Process for prodn. of omethoate |
| CN1165825A (en) * | 1996-05-16 | 1997-11-26 | 北京清华紫光英力化工技术有限责任公司 | Compounded phase transfering catalyst used for catalyzing omethoate intermediate synthesis and its prepn. |
| CN1702074A (en) * | 2004-05-24 | 2005-11-30 | 姚文刚 | Process for synthesizing dimethoate |
| CN104610346A (en) * | 2013-11-05 | 2015-05-13 | 青岛好利特生物农药有限公司 | Persistent omethoate stock solution |
| CN107955034A (en) * | 2017-10-25 | 2018-04-24 | 江苏腾龙生物药业有限公司 | A kind of preparation process of Rogor active compound |
Non-Patent Citations (1)
| Title |
|---|
| 李书安: ""催化剂在氧乐果全合成中应用的研究"", 《河南化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651432A (en) * | 2019-01-17 | 2019-04-19 | 河南省化工研究所有限责任公司 | It is a kind of to prepare O, the method for O- dimethyl-S- (N- methylcarbamoyl methyl) thiophosphate |
| CN109651432B (en) * | 2019-01-17 | 2021-04-09 | 河南省化工研究所有限责任公司 | Method for preparing O, O-dimethyl-S- (N-methyl carbamoylmethyl) thiophosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108997418B (en) | 2021-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107293695A (en) | A kind of method of pair of kettle Fast back-projection algorithm ternary anode material of lithium battery presoma | |
| CN103497260B (en) | A kind of β-oligomerization acid, its preparation method and application | |
| CN108997418A (en) | A kind of improvement technique synthesizing omethoate | |
| CN102897795A (en) | Production method of large granular ammonium sulfate crystal | |
| CN101993455A (en) | Glyphosate synthesis process | |
| CN106589017B (en) | The preparation method of 3 ', 4 ', 7- troxerutin | |
| CN111518154A (en) | Preparation method of 24-epibrassinol intermediate | |
| CN103664881A (en) | Dabigatran etexilate of crystallized variant form B as well as preparation method thereof and application | |
| CN106478438A (en) | A kind of preparation method of magnesium glycinate chelate | |
| CN107417794B (en) | Photochromic cellulose and preparation method thereof | |
| CN106435186B (en) | Cobalt scrap acid hydrolyzation and preparing the application in cobaltosic oxide high-purity cobalt liquid | |
| CN108675933A (en) | N, N- diethyl -2- (2- methoxyl group -5- nitro-phenoxies)-ethamine and its preparation method and application | |
| CN110183351A (en) | The method of continuous extraction synthesis ACA | |
| CN102321068A (en) | Method for preparing strontium ranelate | |
| CN106809887A (en) | A kind of method for preparing chloro-iridic acid | |
| CN108864187A (en) | A kind of new process synthesizing omethoate important intermediate oxy-thiophosphate | |
| CN110282638A (en) | The method and device of sodium bicarbonate is produced in a kind of double decomposition | |
| CN109942568A (en) | A kind of thiamine mononitrate preparation method | |
| CN108947870A (en) | A kind of preparation method of bromo sartanbiphenyl | |
| CN107698471A (en) | It is a kind of to MSM benzaldehyde preparation method | |
| CN1212962A (en) | Method for producing calcium hydrogen phosphate by recovery and using waste water containing phosphate of quinacridineone serial pigment | |
| CN107383066A (en) | A kind of method of latamoxef acid deprotection base | |
| CN110128412A (en) | The preparation method of dextrorotation Iprazole sylvite mother liquor, dextrorotation Iprazole and preparation method thereof | |
| CN101955497A (en) | Process technology for producing high content phosethyl-Al original drug | |
| CN109776441A (en) | Unformed Valsartan Sha Kuba song sodium compound |
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 |