CN108084037B - A kind of preparation method of methyl triethyl ammonium chloride - Google Patents
A kind of preparation method of methyl triethyl ammonium chloride Download PDFInfo
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- CN108084037B CN108084037B CN201711456261.4A CN201711456261A CN108084037B CN 108084037 B CN108084037 B CN 108084037B CN 201711456261 A CN201711456261 A CN 201711456261A CN 108084037 B CN108084037 B CN 108084037B
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- glyphosate
- ammonium chloride
- preparation
- triethyl ammonium
- mother liquor
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- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000005562 Glyphosate Substances 0.000 claims abstract description 128
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 128
- 229940097068 glyphosate Drugs 0.000 claims abstract description 128
- 239000010413 mother solution Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000012452 mother liquor Substances 0.000 claims abstract description 45
- 238000000605 extraction Methods 0.000 claims abstract description 39
- 238000002425 crystallisation Methods 0.000 claims abstract description 32
- 230000008025 crystallization Effects 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 46
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 33
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000004471 Glycine Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- -1 alkyl phosphite Chemical compound 0.000 claims description 7
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 235000009508 confectionery Nutrition 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 27
- 239000002699 waste material Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 206010054949 Metaplasia Diseases 0.000 abstract description 5
- 230000015689 metaplastic ossification Effects 0.000 abstract description 5
- 238000001704 evaporation Methods 0.000 description 22
- 230000008020 evaporation Effects 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 238000012545 processing Methods 0.000 description 13
- 238000004064 recycling Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 11
- 229960002449 glycine Drugs 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 7
- 238000010612 desalination reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- QUBBAXISAHIDNM-UHFFFAOYSA-N ethyldimethylbenzene Natural products CCC1=CC=CC(C)=C1C QUBBAXISAHIDNM-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000000513 principal component analysis Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- XORXDJBDZJBCOC-UHFFFAOYSA-N azanium;acetonitrile;acetate Chemical compound [NH4+].CC#N.CC([O-])=O XORXDJBDZJBCOC-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- DLQDGVZAEYZNTG-UHFFFAOYSA-N dimethyl hydrogen phosphite Chemical compound COP(O)OC DLQDGVZAEYZNTG-UHFFFAOYSA-N 0.000 description 1
- 239000013070 direct material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 238000000105 evaporative light scattering detection Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, comprising the following steps: glyphosate mother solution a) is evaporated concentration, obtains glyphosate concentrated mother liquor；B) the glyphosate concentrated mother liquor is extracted with extractant, obtains extract；C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.The present invention carries out separation and Extraction as raw material using glyphosate mother solution and obtains methyl triethyl ammonium chloride, it is produced using the production waste material in glyphosate industry as raw material, greatly reduce production cost, glyphosate production waste material is re-used, waste entrainment has not only been reduced but also realizes the rational utilization of resource；And separation and Extraction is only needed in producing process, without harsh chemical reaction, operating process is simple and easy, and has good purity and yield, is conducive to the production of market scale metaplasia.
Description
Technical field
The present invention relates to chemical technology field, in particular to a kind of preparation method of methyl triethyl ammonium chloride.
Background technique
Methyl triethyl ammonium chloride is a kind of quaternary ammonium salt, and molecular weight 151.68, fusing point is 282~284 DEG C, and appearance is white
Color powder or crystallization can be used as surfactant, phase transfer catalyst, metal extraction agent etc., can also be modified to it
To the series of products of more high added value.Therefore, methyl triethyl ammonium chloride is a kind of important fine chemicals in chemical field,
Its demand also increasingly increases.
In the prior art, the preparation method of methyl triethyl ammonium chloride be usually using quaternary ammonium base and ammonium chloride as raw material,
Certain reaction condition issues biochemical reaction and is made.However, this chemical reaction preparation method condition is harsh, operation difficulty
Greatly, using chemicals as raw material, preparation cost is higher, cannot carry out marketability large-scale production well.Therefore, exploitation simply has
The preparation method of the methyl triethyl ammonium chloride of effect has a very important significance.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of methyl triethyl ammonium chloride, preparation provided by the invention
Method greatly reduces production cost, and separation and Extraction is only needed in producing process, without harsh chemical reaction, preparation letter
It is single easy, while there is good yield and purity, be conducive to the production of market scale metaplasia.
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, comprising the following steps:
A) glyphosate mother solution is evaporated concentration, obtains glyphosate concentrated mother liquor；
B) the glyphosate concentrated mother liquor is extracted with extractant, obtains extract；
C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.
Preferably, in the step a), the mass ratio of glyphosate concentrated mother liquor and glyphosate mother solution is 1:(5~11).
Preferably, in the step b), the mass ratio of the glyphosate concentrated mother liquor and extractant is 1: (0.1~50).
Preferably, in the step b), extractant includes main extractant and auxiliary extraction agent；
The main extractant includes one or more of methanol, ethyl alcohol, isoamyl alcohol, butanol and acetonitrile；
The auxiliary extraction agent includes one of acetone, ether, ethyl acetate, Ethyl formate, benzene, toluene and dimethylbenzene
Or it is several.
Preferably, the main extractant and the mass ratio of auxiliary extraction agent are 1: (0.01~0.9).
Preferably, in the step c), evaporative crystallization is that crystallization is evaporated under reduced pressure.
Preferably, the temperature that crystallization is evaporated under reduced pressure is 20~200 DEG C, and pressure is 0.01~0.1MPa.
It preferably, further include separation of solid and liquid and drying after the evaporative crystallization in the step c).
Preferably, the glyphosate mother solution is after preparing glyphosate by glycin method to be formed by original nut liquid recycling triethylamine
Obtained mother liquor.
Preferably, the sweet ammonia process is prepared using paraformaldehyde, glycine and alkyl phosphite as raw material in glyphosate, and three
Ethamine is catalyst.
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, comprising the following steps: a) by glyphosate mother
Liquid is evaporated concentration, obtains glyphosate concentrated mother liquor；B) the glyphosate concentrated mother liquor is extracted with extractant, is extracted
Object；C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.The present invention divides by raw material of glyphosate mother solution
Methyl triethyl ammonium chloride is obtained from extracting, is produced, is greatly reduced as raw material using the production waste material in glyphosate industry
Production cost, re-uses glyphosate production waste material, has not only reduced waste entrainment but also has realized the reasonable of resource
Change and utilizes；And separation and Extraction is only needed in producing process, without harsh chemical reaction, operating process is simple and easy, and has
There are good purity and yield, is conducive to the production of market scale metaplasia.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the mass spectrogram of principal component analysis in oil slick；
Fig. 2 produces flow chart for inventive embodiments 1；
Fig. 3 is the liquid-phase chromatographic analysis test chart of 1 products obtained therefrom of the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, comprising the following steps:
A) glyphosate mother solution is evaporated concentration, obtains glyphosate concentrated mother liquor；
B) the glyphosate concentrated mother liquor is extracted with extractant, obtains extract；
C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.
Present invention firstly provides using glyphosate mother solution as raw material carry out separation and Extraction obtain methyl triethyl ammonium chloride, with
Production waste material in glyphosate industry is waste, greatly reduces production cost, is able to glyphosate production waste material
It re-uses, had not only reduced waste entrainment but also realized the rational utilization of resource；And it only needs to separate in producing process to mention
It takes, without harsh chemical reaction, operating process is simple and easy, and has good purity and yield, is conducive to market scale
Metaplasia produces.
Glyphosate is the advantage pesticide species in the maximum herbicide products of current global yield and China.It is domestic at present
Glyphosate production technique have two: first is that IDA method technique prepares intermediate pmida using diethanol amine as primary raw material,
Then it is aoxidized to obtain glyphosate again；Second is that glycine method technique, mainly with glycine, paraformaldehyde, dimethylphosphite
For raw material, methanol is solvent, triethylamine is catalyst.In two production process routes of glyphosate, amino acetic acid in China method technique
The production capacity of glyphosate accounts for 70%, is the glyphosate production technique of current mainstream.
Glyphosate mother solution is generated simultaneously in glyphosate by using glycine production process, one ton of glyphosate of every production about generates 5 tons
Glyphosate mother solution.And inorganic salts, high organic content in glyphosate mother solution, belong to high intractable organism P wastewater.State at present
It has inside succeeded in developing and has realized that the glyphosate mother solution treatment process of industrialization mainly has two lines, be catalytic wet oxidation work respectively
Skill and high temperature orient conversion process, and two glyphosate mother solution processing routes are able to achieve to the elements such as sodium, phosphorus in glyphosate mother solution
Recycling, not only saved valuable phosphate rock resource, but also solve the problem of outlet of glyphosate mother solution substantially.
However, the method for processing mother solution of glyphosate succeeded in developing at present is only right due to glyphosate mother solution complicated component
The elements such as the phosphorus in mother liquor are recycled, the recycling without paying close attention to the other compositions in mother liquor.Glyphosate is female
Liquid obtains high phosphorous glyphosate concentrated mother liquor, substantially increases the calorific value of mother liquor, be very suitable to height after being concentrated by evaporation desalination
Temperature orientation conversion reaction.But there are laminations, i.e. mother liquor in placement process after being concentrated by evaporation desalination for glyphosate mother solution mother liquor
The lighter oil slick of upper layer specific gravity and next specific gravity biggish glyphosate concentrated mother liquor can be converted into during storage tank.Glyphosate is dense
Contracting mother liquor directly goes orientation conversion production phosphate product technology very mature, but upper layer oil slick is fresh attracts attention less.By
It is difficult to enter subsequent phosphorus recovery system with glyphosate concentrated mother liquor in oil slick, thus oil slick is caused the more to accumulate the more more, seriously
Affect the normal production of glyphosate mother solution processing.
Applicant analyzes oil slick property, as the result is shown: appearance is brown, and specific gravity is 1.02~1.06, PH 7.5
~9, Cl content are that 10%~12%, COD is 20%~30%, and moisture is 40%~50%, can when temperature is 500 DEG C or more
Vigorous combustion simultaneously generates a large amount of smog.As it can be seen that oil slick is a kind of organic matter containing chlorine.
Through applicants have found that, include methyl triethyl ammonium chloride and moisture, and three second of methyl in the upper layer oil slick
The content of ammonium chloride is up to 40% or more, and moisture is up to 40%~50%.Test is analyzed by mass spectrometry to oil slick, as a result as schemed
Shown in 1, Fig. 1 is the mass spectrogram of principal component analysis in oil slick, it can be seen that ionized molecule amount is 116.1 under mass spectrum holotype, is changed
Structure is (CH3CH2)3N+CH3Cl-.Element is carried out to methyl triethyl ammonium chloride test article resulting after separating-purifying oil slick
Analysis is tested and is compared with the theoretical value of each element in methyl triethyl ammonium chloride, and the results are shown in Table 1, it can be seen that is surveyed
Each element content distribution and theoretical value are very close in test product, wherein C, H, Cl constituent content are slightly lower, and H content is slightly higher, be due to
Methyl triethyl ammonium chloride easy to absorb moisture, absorbs during the test caused by the moisture in air.
The elemental analysis test result of 1 methyl triethyl ammonium chloride test article of table
| Element | N | C | H | CL |
| Test value, wt% | 9.06 | 53.62 | 12.63 | 21.02 |
| Theoretical value, wt% | 9.24 | 55.45 | 11.88 | 23.43 |
It is analyzed by mass spectral analysis and element test, it was demonstrated that the main component of oil slick is methyl triethyl ammonium chloride.Through Shen
It asks someone to explore, formation basic theory of the methyl triethyl ammonium chloride in glyphosate mother solution may be as shown in following formula (1) or formula (2):
N(C2H5)3+CH3Cl=CH3N(C2H5)3·Cl (1)；
N(C2H5)3·HCl+CH3OH=CH3N(C2H5)3·Cl+H2O (2)。
Since methyl triethyl ammonium chloride is soluble easily in water, in oil slick in addition to methyl triethyl ammonium chloride, also containing 40%~
50% moisture, the two are combined in the form of hydrogen bond etc., very securely, it is difficult to recycle methyl three by common methods such as evaporative crystallizations
Ethyl ammonium chloride product, and the present invention has carried out a series of specially treateds to glyphosate mother solution to obtain methyl triethyl group chlorination
Ammonium.
As described above, at present before discharging glyphosate mother solution, it can be first to side product chlorinated sodium, the chloromethane in glyphosate mother solution
Alkane and dimethoxym ethane are recycled, and realize the recycling of resource, carry out discharge or sewage again after recycling above-mentioned useful by-product
Processing.However, the present invention but produces this fine chemicals of methyl triethyl ammonium chloride as raw material using glyphosate mother solution, this
It is to be difficult to it is contemplated that both at home and abroad also there is not yet related side in open source information in routine techniques processing in the prior art or in industry
The report in face, the present invention are to be put forward for the first time using glyphosate mother solution as raw material to extract methyl triethyl ammonium chloride.
It tests and finds through applicant, the content of methyl triethyl ammonium chloride is 0.5%~1.0% in glyphosate mother solution, state
In interior annual 600000 tons of glyphosate yield, glyphosate by using glycine yield is based on annual 350000 tons, then the glyphosate mother solution that generates
In the methyl triethyl ammonium chloride that contains reach as high as nearly 30,000 tons, market value may be up to 9000 Yu Wanyuan.As it can be seen that sweet with grass
Phosphine mother liquor is direct material, can not only produce the methyl triethyl ammonium chloride with high added value, saves valuable resource, and
And glyphosate mother solution subsequent processing difficulty can be reduced, thus the present invention handles skill to the recycling mother solution for pushing glyphosate industry
Art promotion is of great significance.
According to the present invention, glyphosate mother solution is first evaporated concentration, obtains glyphosate concentrated mother liquor.
In the present invention, preparing glyphosate by glycin method is preferably formed by original nut liquid recycling three by the glyphosate mother solution
The mother liquor obtained after ethamine.In the technique of preparing glyphosate by glycin method, catalyst of triethylamine is main during acid hydrolysis
To exist in the form of triethylamine hydrochloride, after glyphosate products are prepared, glyphosate original nut liquid, triethylamine salt can be generated
Hydrochlorate then stays in the glyphosate original nut liquid.Since catalyst of triethylamine dosage is larger, and price is higher, therefore, is making
After obtaining glyphosate, the usual processing mode of this field is that the triethylamine hydrochloride in the glyphosate original nut liquid that will be generated is used by force
Alkali replaces the preparation that catalyst is re-used as to recycle triethylamine for glyphosate.Wherein, triethylamine hydrochloride is set with highly basic
Shown in the principle such as reaction equation (3) for gaining receipts:
N(C2H5)3HCl+NaOH=N (C2H5)3+NaCl+H2O (3)；
After the triethylamine hydrochloride being dissolved in glyphosate original nut liquid is reacted with alkali, the triethylamine of formation is due to being insoluble in water
Layering, most of triethylamine are recycled by quantizer, are entrained in the triethylamine in glyphosate mother solution on a small quantity using rectifying column process
It is recycled, distillation residual liquid is glyphosate mother solution.
In the present invention, the glycine method is preferably alkyl ester process, i.e., with paraformaldehyde, glycine and phosphorous acid
Arrcostab is raw material, and triethylamine is the preparation method of catalyst.In the present invention, the type of the alkyl phosphite is not special
Limitation, to prepare conventional alkyl phosphite in glyphosate technique, including dimethylphosphite, phosphorous acid three in this field
Methyl esters or diethyl phosphite；Preferably phosphorous acid two more commonly used in alkyl ester process industrial production glyphosate route
Methyl esters.When alkyl phosphite method prepares glyphosate, depolymerization, addition and hydrolysis occur under the action of catalyst for raw material, raw
At glyphosate products, to obtaining glyphosate mother solution after devil liquor recovery triethylamine.
The present invention is first evaporated concentration to glyphosate mother solution, come remove inorganic salts (such as sodium chloride) impurity and moisture,
Improve mother liquid concentration.In the present invention, the mass ratio being preferably concentrated by evaporation to gained glyphosate concentrated mother liquor and glyphosate mother solution is
1:(5~11).It can guarantee sufficiently to remove the impurity such as inorganic salts within the scope of the concentrating degree, and can guarantee that mother liquor has
Good rheological characteristic is convenient for subsequent processing, is evaporated concentration to glyphosate mother solution and improves methyl triethyl group chlorine
Change relative concentration of the ammonium in glyphosate mother solution, reach hypersaturated state, more conducively subsequent methyl triethyl ammonium chloride with
The separation of glyphosate mother solution.
In the present invention, for small batch glyphosate mother solution, to improve evaporation efficiency and reducing temperature of charge, the evaporation is dense
Concentration is preferably evaporated under reduced pressure in contracting；The temperature and pressure of the reduction vaporization is not particularly limited, and is steamed according to depressurizing in this field
The normal condition for sending out material executes, and if pressure can be 0.01~0.1MPa, temperature can be 20~200 DEG C.Subtract described
After pressure is concentrated by evaporation, preferably also it is centrifuged.For the processing convenient for high-volume glyphosate mother solution, the side of the evaporation and concentration
Formula is preferably that single effect evaporation concentration, multiple-effect evaporation concentration or MVR are concentrated by evaporation, and can be steamed by means respectively of single effect evaporator, multiple-effect
It sends out device or MVR evaporator is realized.After the evaporation and concentration, glyphosate concentrated mother liquor is obtained.
According to the present invention, after obtaining glyphosate concentrated mother liquor, the glyphosate concentrated mother liquor is extracted with extractant, is obtained
Extract.
The mass ratio of the glyphosate concentrated mother liquor and extractant is preferably 1: (0.1~50), more preferably 1: (1~5).
In the present invention, due to the particularity of glyphosate concentrated mother liquor, it is difficult to it finds suitable single extractant and is extracted, institute of the present invention
It states extractant and preferably includes main extractant and auxiliary extraction agent；Wherein, the main extractant preferably includes methanol, ethyl alcohol, isoamyl
One or more of alcohol, butanol and acetonitrile；The auxiliary extraction agent preferably includes acetone, ether, ethyl acetate, formic acid second
One or more of ester, benzene, toluene and dimethylbenzene.Through applicants have found that, can be filled using said combination formula extractant
Divide extraction glyphosate concentrated mother liquor, is sufficiently separated the ingredients such as methyl triethyl ammonium chloride ingredient and other organic matter salt.At this
In one embodiment of invention, main extractant is methanol, and auxiliary extraction agent is acetone, ethyl acetate and toluene.Of the invention
In another embodiment, main extractant is ethyl alcohol and isoamyl alcohol, and auxiliary extraction agent is acetone, Ethyl formate and dimethylbenzene.At this
In the other embodiments of invention, the other combinations of main extractant and auxiliary extraction agent selected from above-mentioned listed type.
In the present invention, the mass ratio of main extractant and auxiliary extraction agent is preferably 1: (0.01~0.9).Of the invention one
In a embodiment, main extractant is methanol, and auxiliary extraction agent is acetone, ethyl acetate and toluene, main extractant and auxiliary extraction
The mass ratio of agent is 1:0.82.In another embodiment of the present invention, main extractant is ethyl alcohol and isoamyl alcohol, auxiliary extraction agent
For acetone, Ethyl formate and dimethylbenzene, the mass ratio of main extractant and auxiliary extraction agent is 1:0.54.The present invention uses extractant
Extract glyphosate concentrated mother liquor, gained raffinate phase mainly includes glyphosate, increases the organic matters salt such as sweet phosphorus, can be used for recycling phosphorus member
Element includes methyl triethyl ammonium chloride in gained extract.
According to the present invention, after obtaining extract, by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained.
The extractant in extract is evaporated off by evaporative crystallization by the present invention, to improve evaporative crystallization efficiency, the evaporation
Crystallization is preferably evaporated under reduced pressure in crystallization.In the present invention, the temperature that crystallization is evaporated under reduced pressure is preferably 20~150 DEG C；Decompression is steamed
The pressure of hair crystallization is preferably 0.07~0.1MPa.It can be selected out of described temperature and pressure according to the selection of above-mentioned extractant
Select evaporative crystallization parameter.
In the present invention, after being evaporated crystallization, preferably also it is separated by solid-liquid separation and is dried.The separation of solid and liquid is preferably
Centrifuge separation.The temperature of the drying is preferably 100~280 DEG C, and more preferably 150~200 DEG C, in the temperature range both
It can guarantee drying effect again and can be avoided the decomposition of methyl triethyl ammonium chloride, and then obtain the higher methyl triethyl group chlorine of content
Change ammonium product.
The present invention provides a kind of preparation methods of methyl triethyl ammonium chloride, carry out a system by raw material of glyphosate mother solution
The separation and Extraction of column is to obtain methyl triethyl ammonium chloride, on the one hand, using the production waste material in glyphosate industry as raw material system
It takes, greatly reduces production cost, re-use glyphosate production waste material, both reduced waste entrainment, reduced
The processing difficulty of glyphosate waste liquid, and realize the rational utilization of resource；Meanwhile it only needing to separate in producing process to mention
It takes, without harsh chemical reaction, operating process is simple and easy, is conducive to the production of market scale metaplasia；Moreover, the preparation method energy
Good purity and yield are enough obtained, can satisfy production and practical application request.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.In following embodiment, glyphosate mother solution used is that glycine method phosphorous acid dimethyl ester method is prepared glyphosate to be formed
The glyphosate mother solution obtained after glyphosate original nut liquid recycling triethylamine.It following embodiment glyphosate mother liquor raw material and produced
The component distributing of the extract and product that are formed in journey is tested by liquid-phase chromatographic analysis and is obtained.
Embodiment 1
It with processing capacity is 100kg/h's by 5000kg glyphosate mother solution (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；Be added 571.44kg extractant into
Row extraction, extractant composition are as follows: methanol 55wt%, acetone 25wt%, ethyl acetate 18wt%, toluene 2wt%, extraction terminate
Afterwards, raffinate phase 478.5kg, extract 569.14kg are obtained (methyl triethyl ammonium chloride content is 8.15%).Extract is existed
50~100 DEG C are centrifuged after 5 hours with reduction vaporization crystallization under 0.095MPa pressure, dry, obtain at 180 DEG C later
To methyl triethyl ammonium chloride product 45.70kg, methyl triethyl ammonium chloride content is 98.2%, overall recovery 93.49%.
Evaporative crystallization recycles extractant 520.12kg, can be applied to extraction process recycling.
Referring to fig. 2, Fig. 2 produces flow chart for the embodiment of the present invention 1 to above-mentioned producing process.
Liquid-phase chromatographic analysis test is carried out to products obtained therefrom, test condition is as follows:
Reagent: methyl triethyl ammonium chloride standard items 98%, acetonitrile (HPLC grades), ammonium acetate (analysis is pure), acetic acid (analysis
It is pure), water (ultrapure water), to test sample (i.e. above-mentioned preparation method products obtained therefrom)；
Instrument: waters HPLC2695, evaporative light-scattering device (ELSP2424)；
Chromatographic column: Dikmaspuile C 18-EP, 5 μm, 250mm × 4.6mm；
Mobile phase: A phase: acetic acid aqueous solution (mass concentration 0.1%), B phase: (mass concentration is ammonium acetate acetonitrile solution
0.08%)；A phase: phase=40 B: 60 (volume ratios)；
Flow velocity: 0.3mL/min.
Test results are shown in figure 3 for liquid-phase chromatographic analysis, and Fig. 3 is that the liquid-phase chromatographic analysis of the present embodiment products obtained therefrom is tested
Figure, the results show that it is methyl triethyl ammonium chloride.
Embodiment 2
It with processing capacity is 100kg/h's by 5000kg glyphosate mother solution (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；Be added 571.44kg extractant into
Row extraction, extractant composition are as follows: ethyl alcohol 50wt%, acetone 25wt%, isoamyl alcohol 15wt%, Ethyl formate 5wt%, dimethylbenzene
5wt% after extraction, obtains raffinate phase 477.2kg, and (methyl triethyl ammonium chloride content is extract 570.44kg
8.08%).It is centrifuged after extract being evaporated under reduced pressure to crystallization under 80 DEG C and 0.090 pressure 8 hours, later in 200
It is dried at DEG C, obtains methyl triethyl ammonium chloride product 46.15kg, methyl triethyl ammonium chloride content is 98.1%, total to recycle
Rate is 94.32%.Evaporative crystallization recycles extractant 523.50kg, can be applied to extraction process recycling.
Embodiment 3
It with processing capacity is 100kg/h's by 5000kg glyphosate mother solution (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；Be added 1428.6kg extractant into
Row extraction, extractant composition are as follows: ethyl alcohol 50wt%, acetone 30wt%, isoamyl alcohol 5wt%, Ethyl formate 5wt%, dimethylbenzene
5wt% after extraction, obtains raffinate phase 478.9kg, and (methyl triethyl ammonium chloride content is extraction phase 1425.9kg
3.22%).It is centrifuged after extract is evaporated under reduced pressure crystallization 10 hours under 85 DEG C and 0.92MPa pressure, Zhi Houyu
It is dried at 190 DEG C, obtains methyl triethyl ammonium chloride product 46.88kg, methyl triethyl ammonium chloride content is 98.5%, total to return
Yield is 96.21%.Evaporative crystallization recycles extractant 1405.7kg, can be applied to extraction process recycling.
Comparative example 1
It with processing capacity is 100kg/h's by 5000kg glyphosate mother solution (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；Be added 23.81kg extractant into
Row extraction, extractant composition are as follows: ethyl alcohol 50wt%, acetone 30wt%, isoamyl alcohol 5wt%, Ethyl formate 5wt%, dimethylbenzene
5wt% after extraction, obtains raffinate phase 481.56kg, and (methyl triethyl ammonium chloride content is extract 18.45kg
20.5%).It is centrifuged after extract is evaporated under reduced pressure crystallization 2.5 hours under 60 DEG C and 0.096MPa pressure, later
It is dried at 180 DEG C, obtains methyl triethyl ammonium chloride product 3.87kg, methyl triethyl ammonium chloride content is 97.8%, always
The rate of recovery is 7.89%.Evaporative crystallization recycles extractant 17.6kg, can be applied to extraction process recycling.
Comparative example 2
It with processing capacity is 100kg/h's by 5000kg glyphosate mother solution (methyl triethyl ammonium chloride content be 0.96%)
After triple-effect evaporation plant carries out continuous evaporation desalination, glyphosate concentrated mother liquor 476.2kg is obtained；The extraction of 571.44kg ethyl alcohol is added
Agent is extracted, and since ethyl alcohol mixes and can not be layered with concentrated mother liquor, thus extraction test fails, and can not obtain methyl triethyl group
Ammonium chloride.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention, including best mode, and but also this field is appointed
What technical staff can practice the present invention, including any device or system of manufacture and use, and implement the method for any combination.
It should be pointed out that for those skilled in the art, it without departing from the principle of the present invention, can also be right
Some improvement and modification can also be carried out by the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.This hair
The range of bright patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other implementations
Example.If these other embodiments, which have, is similar to the structural element of claim character express, or if they include with
Equivalent structural elements of the character express of claim without essence difference, are wanted then these other embodiments should also be included in right
In the range of asking.
Claims (8)
1. a kind of preparation method of methyl triethyl ammonium chloride, which comprises the following steps:
A) glyphosate mother solution is evaporated concentration, obtains glyphosate concentrated mother liquor；
B) the glyphosate concentrated mother liquor is extracted with extractant, obtains extract；
C) by the extract evaporative crystallization, methyl triethyl ammonium chloride is obtained；
The glyphosate mother solution is that preparing glyphosate by glycin method is formed by original nut liquid to recycle the mother liquor obtained after triethylamine；
The glycine method is alkyl ester process；
When the alkyl phosphite method prepares glyphosate, depolymerization, addition and hydrolysis occur under the action of catalyst for raw material,
Glyphosate products are generated, to obtaining glyphosate mother solution after devil liquor recovery triethylamine；
The extractant includes main extractant and auxiliary extraction agent；
The main extractant includes one or more of methanol, ethyl alcohol, isoamyl alcohol, butanol and acetonitrile；
The auxiliary extraction agent includes one of acetone, ether, ethyl acetate, Ethyl formate, benzene, toluene and dimethylbenzene or several
Kind.
2. preparation method according to claim 1, which is characterized in that in the step a), glyphosate concentrated mother liquor and grass
The mass ratio of sweet phosphine mother liquor is 1:(5~11).
3. preparation method according to claim 1, which is characterized in that in the step b), the glyphosate concentrated mother liquor
Mass ratio with extractant is 1: (0.1~50).
4. preparation method according to claim 1, which is characterized in that the mass ratio of the main extractant and auxiliary extraction agent
It is 1: (0.01~0.9).
5. preparation method according to claim 1, which is characterized in that in the step c), evaporative crystallization is to be evaporated under reduced pressure
Crystallization.
6. preparation method according to claim 5, which is characterized in that the temperature that crystallization is evaporated under reduced pressure is 20~200
DEG C, pressure is 0.01~0.1MPa.
7. preparation method according to claim 1, which is characterized in that in the step c), after the evaporative crystallization also
Including being separated by solid-liquid separation and drying.
8. preparation method according to claim 1, which is characterized in that the sweet ammonia process is prepared in glyphosate with poly first
Aldehyde, glycine and alkyl phosphite are raw material, and triethylamine is catalyst.
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