CN1288118C - Clean reclaiming process for byproduct chloromethane of glyphosate acid - Google Patents
Clean reclaiming process for byproduct chloromethane of glyphosate acid Download PDFInfo
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- CN1288118C CN1288118C CN 200410097716 CN200410097716A CN1288118C CN 1288118 C CN1288118 C CN 1288118C CN 200410097716 CN200410097716 CN 200410097716 CN 200410097716 A CN200410097716 A CN 200410097716A CN 1288118 C CN1288118 C CN 1288118C
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- methyl chloride
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- methylal
- methyl
- impurity
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- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000002253 acid Substances 0.000 title claims abstract description 39
- 239000005562 Glyphosate Substances 0.000 title abstract description 16
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title abstract description 16
- 229940097068 glyphosate Drugs 0.000 title abstract description 16
- 239000006227 byproduct Substances 0.000 title description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 139
- 229940050176 methyl chloride Drugs 0.000 claims abstract description 61
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005516 engineering process Methods 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000012530 fluid Substances 0.000 claims abstract description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 13
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 6
- -1 alkyl phosphite Chemical compound 0.000 claims description 6
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 3
- DLQDGVZAEYZNTG-UHFFFAOYSA-N dimethyl hydrogen phosphite Chemical compound COP(O)OC DLQDGVZAEYZNTG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 238000005406 washing Methods 0.000 description 21
- 238000011084 recovery Methods 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002203 pretreatment Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- BSIJOEMKOZVYPS-UHFFFAOYSA-N dimethoxymethane;hydrate Chemical compound O.COCOC BSIJOEMKOZVYPS-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 244000037671 genetically modified crops Species 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- YWICANUUQPYHOW-UHFFFAOYSA-M sodium;2-(phosphonomethylamino)acetate Chemical compound [Na+].OP(O)(=O)CNCC([O-])=O YWICANUUQPYHOW-UHFFFAOYSA-M 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Abstract
Tail gas is exhausted in the production process of glyphosate acid by using a phosphorous acid alkyl acid method, and the tail gas contains 20 to 90% of methyl chloride and impurities of methanol, methylal, water, hydrogen chloride, etc. Impurities are absorbed by solvent and are condensed, or part of the impurities, such as the methanol and the methylal, are added in fluid containing the hydrogen chloride and are converted into methyl chloride, and thus, methyl chloride with high purity is prepared. The technology not only solves the problem of environment pollution in the production process of the glyphosate acid, but also greatly reduces the production cost of the glyphosate acid.
Description
The application is to be on July 23rd, 2002, open day to be that October 8, application number in 2003 are dividing an application of 02125282.3 Chinese patent application the applying date.
Technical field
The present invention relates to the method for purifying and recovering of hydrolysis tail gas in the glyphosphonic acid building-up process, more particular words is to produce the high yield recovery by product methyl chloride the tail gas that discharges from glyphosphonic acid, and this process does not produce secondary pollution.
Background technology
Glyphosate is the maximum and the fastest steriland herbicide of rate of growth of sales volume in the world, whole world glyphosate technicals ultimate production reaches 260,000 tons, and along with the succeeding in developing and promoting the use of of the genetically modified crops of resistance glyphosate, for the continuation development of glyphosate provides new opportunity.The two kinds of methods that mainly contain are produced in whole world glyphosate industrialization: the one, and the IDA method promptly is starting raw material with the diethanolamine, U.S. Meng Shan waits offshore company generally to adopt this technology; Another kind method is an alkyl esterification method, domestic big multiple enterprises adopts this technology, alkyl esterification method glyphosate preparation method is open at document DEOLSNO.P 2942898.6, method commonly used is with Paraformaldehyde 96 or formaldehyde in containing the methanol solvate of triethylamine heating for dissolving 5-15 minute, again glycine is added heating for dissolving in this solution, add dimethylphosphite after 30 minutes, under 60-70 ℃, carry out condensation reaction, finish through 30-120 minute afterreaction, adding hydrochloric acid then is hydrolyzed (being called hydrolyzing process), generate the hydrochloride of glyphosphonic acid, the glyphosphonic acid crystallization was separated out after underpressure distillation removed solvent methanol and excessive hydrochloric acid again, filter after scouring, filter cake is glyphosphonic acid, the glyphosate that contains triethylamine hydrochloride and minimal amounts of dissolved in mother liquor and the washing lotion is used to prepare 10% sodium glyphosate aqua in liquid caustic soda and after reclaiming triethylamine.With the solution rectifying (being called the solvent recuperation operation) that underpressure distillation steams, isolate wherein solvent methanol and by product methylal, raffinate carries out biochemical treatment.If produce glyphosphonic acid with trimethyl phosphite, technology is similar.
Employing is in the production of alkyl phosphite technology (comprising with the phosphorus trichloride being raw material synthesizing phosphorous acid dimethyl ester operation) synthesizing glyphosate acid of starting raw material with dimethylphosphite or trimethyl phosphite, produce a large amount of tail gas that contains methyl chloride at dimethylphosphite synthesis procedure and the synthetic hydrolyzing process of glyphosphonic acid, can be used as the production of products such as carboxymethyl cellulose, chloroprene rubber behind the methyl chloride reclaiming clean wherein.Patent of invention 99119970.7 (franchise the applicant) discloses a kind of industrial method that reclaims the methyl chloride that produces in the alkyl phosphite method glyphosphonic acid building-up process, adopt be hydrolysis tail gas through washing, alkali cleaning, dry tertiary treatment, the storage of recompression condensation liquefaction.But this technology comes with some shortcomings in the rate of recovery and environmental protection: 1. the rate of recovery is low.Owing to contain saturated or oversaturated methylal and methyl alcohol under the normal pressure in this tail gas, if can not when washing, be removed, bring dehumidification system into after, can cause the consumption of siccative higher, and the quality of methyl chloride is reclaimed in influence.But be subjected to the influence of methylal and methyl alcohol solubleness and rate of mass transfer in water, in order to guarantee to reclaim the quality of methyl chloride, need to wash with a large amount of water (6 tons of/ton methyl chloride), and there is certain solubility (0.38 grams per liter) in methyl chloride in water, the washing water yield causes that greatly the solution loss of methyl chloride in water increases, and influenced the rate of recovery; 2. contaminate environment.Though this technology can be with the most of recovery of the methyl chloride in the discharging tail gas, reduced the pollution of glyphosphonic acid production to environment, but making, the defective of this technology itself can not thoroughly solve environmental issue, organic compound such as the methylal in the tail gas, methyl alcohol, methyl chloride have been dissolved in a large amount of bath wateies, and these materials of low levels can't adopt economic method to reclaim, can only carry out biochemical treatment or discharging, cause pollution environment; If carry out biochemical treatment, because methylal is embarrassed biochemical substances with methyl chloride, it is higher that it is carried out processing cost.3. it is not good to reclaim the methyl chloride quality.The impurity (moisture content, methylal, methyl alcohol) that also contains in the byproduct chloromethane of glyphosate acid that adopts the described tertiary treatment technology of this technology to reclaim is too high, in methyl chlorosilane is synthetic, can form polymkeric substance or thermo-cracking at catalyst surface coking, knot charcoal with the target product reaction, thus influence production.
Summary of the invention
The objective of the invention is to for solving the above-mentioned problem that exists, a kind of novel method of alkyl phosphite method glyphosphonic acid hydrolysis tail gas clean-up is provided, and whole recovery technology is environmental protection, can realize cleaner production, thoroughly solves the influence of glyphosphonic acid suitability for industrialized production discharging tail gas to environment.
Main contents of the present invention are that (1) collects discharge tail gas in the glyphosate production process; (2) adopt the method that transforms impurity to handle collected tail gas, methyl chloride content is wherein increased.Wherein the method for this conversion impurity is: the collected tail gas that contains methyl chloride is fed in the solution that contains hydrogenchloride or with hydrogenchloride be mixed into reactor, wherein methyl alcohol and methylal partly or entirely changed into methyl chloride.
The methyl chloride weight content that reclaims is 20-99.99%, wherein contains feature impurity methylal, and weight content is 0.1ppm-80%; Further, the methyl chloride weight content of recovery is 99-99.99%, and the weight content of feature impurity methylal is 0.1-100ppm.
Glyphosphonic acid of the present invention is that to adopt dimethylphosphite or trimethyl phosphite be that the alkyl phosphite method of one of main raw material is produced.
Glyphosphonic acid production technique described in the present invention comprises phosphorus trichloride synthesizing phosphorous acid dimethyl ester or trimethyl phosphite as one of glyphosphonic acid synthesis procedure.
The present invention can further include behind method for transformation, will contain the pressurized with fluid of methyl chloride or cooling or pressurization and cooling and make methyl chloride, methyl alcohol, methylal and water in the fluid liquefy fully or partial liquefaction; Further comprise will liquefy fully or partial liquefaction after the method for the fluid that contains methyl chloride by solvent absorbing, the content of impurity methyl alcohol contained in the described fluid, methylal, water, hydrogenchloride and salt acid mist is descended.Described solvent is the water or the aqueous solution that contains alkaline matter, perhaps is the vitriol oil.Can also comprise that further the fluid that will contain methyl chloride adopts the method for absorption to make the wherein aqueous content decline of institute by the solid adsorbent that can absorb water.
The present invention comprises that also after described method for transformation, the fluid that will contain methyl chloride adopts the method that absorbs that the methyl chloride in the described fluid is changed in the solvent by organic solvent; Comprise that further the absorption liquid that will contain methyl chloride and other impurity composition separates through desorb.Described organic solvent is that carbonatoms is the hydrocarbon of halohydrocarbon, ketone, alcohol or the carbonatoms 4-16 of 1-10.Can also comprise that further the fluid that will contain methyl chloride adopts the method for absorption to make the wherein aqueous content decline of institute by the solid adsorbent that can absorb water.
Described solid adsorbent is oxide compound or the anhydrous metal salt that water sorption is arranged.
In addition, the tail gas of the recovery phlegma that contains methyl alcohol or methylal material after separating methyl chloride returns the solvent recuperation operation of glyphosphonic acid in producing.
Glyphosphonic acid production discharging tail gas consists of:
| Methyl chloride | Air | Methyl alcohol | Methylal | Water | Hydrogenchloride | Other |
| 20-90 | 8-20 | 2-15 | 4-20 | 2-10 | 1-5 | 1-5 |
Methyl alcohol wherein, methylal are in saturated or hypersaturated state, the boiling point of methyl alcohol, methylal, methyl chloride is respectively 64.5 ℃ under normal pressure, 42.3 ℃,-23.73 ℃, the emergent pressure of methyl alcohol, methylal is 240 ℃, 215 ℃, far above 143 ℃ of methyl chloride, the method that therefore can adopt compression is with methyl alcohol in the gas phase and the most of condensation of methylal, thereby the absorption that can reduce subsequent handling is significantly loaded.Methyl chloride saturated vapor pressure at normal temperatures is 506.63kpa (absolute pressure), therefore tail gas can be compressed to 0.11-1Mpa (absolute pressure), for guaranteeing that methyl alcohol separates with the most economical of methyl chloride with methylal, preferred pressure is 0.45-0.55Mpa (absolute pressure), the separation that is liquefied of methyl alcohol more than 80% and methylal will be arranged this moment, this phlegma mainly contains methyl alcohol and methylal, can return the solvent recuperation operation in the glyphosphonic acid production, separate the 60-95% methylal, can be used as commodity selling, 〉=98% methyl alcohol can be as the solvent of synthesizing glyphosate acid.
To wash the methyl chloride solution loss that is caused with water or reduce contained organic substance influence problem of environment in the washing water that cause therefrom in order to reduce, also having a kind of technical scheme is that the tail gas that will contain methyl chloride makes its almost completely condensation except that contained non-condensable gasess such as air by pressurization and refrigerative method, this moment, pressure can be 0.4-2Mpa (absolute pressure), and temperature is-50-40 ℃ (technical professional can also adopt the combination of multiple pressure and temperature to reach same effect certainly).Components such as contained methyl chloride, methyl alcohol, methylal are separated from phlegma by the method for rectifying again, because the boiling point of methyl chloride is minimum, can at first obtain from cat head, bottom product is the mixture of components such as methyl alcohol, methylal, and this mixture is again through separating methyl alcohol and the methylal to obtain higher concentration.
Because most methyl alcohol and methylal separated (being called pre-treatment), can significantly reduce the consumption of washing water, in order to strengthen rate of mass transfer and to improve the content of methyl alcohol and methylal in the washing water, adopt the circulation absorption technique, single tower can be adopted according to tolerance in the absorption tower, perhaps multitower serial or parallel connection, working pressure is 0.08-0.3Mpa (absolute pressure).Contain methyl alcohol and methylal that weight concentration is 10-30% in the washing water, the solvent recuperation operation that also can return in the glyphosphonic acid production is separated.
Still contain carbonic acid gas, hydrogenchloride or vaporific hydrochloric acid in the gas after washing, can also be that potassium hydroxide, carbonate (sodium, the potassium) aqueous solution etc. of 10-40% absorbs with weight concentration except that the liquid caustic soda of patent of invention 99119970.7 disclosed 30% weight concentrations, factor preferred weight concentration such as comprehensive cost be the aqueous sodium hydroxide solution of 25-35%.
The water that still contains the 100-20000ppm that has an appointment in the gas after above-mentioned processing, still do not meet the requirement of industry standard, patent of invention 99119970.7 adopts the vitriol oil to carry out drying, but only use this method, still contain the water that is about 30ppm in the methyl chloride after the processing, though meet the industry standard of methyl chloride, very harsh to the requirement of the used methyl chloride of synthesizing methyl-chloro-silane, water content is low more favourable more to synthesizing methyl-chloro-silane.It is considered herein that and can also adopt other method that can remove micro-moisture, simple to operate, effective as adopting the solid matter that can absorb moisture to absorb moisture.Therefore can adopt behind vitriol oil drying process again with or the solid adsorbent that directly can absorb moisture with copper sulfate, calcium sulfate, calcium chloride, yellow soda ash, water glass, Vanadium Pentoxide in FLAKES, calcium oxide, 3A aluminum oxide molecular sieve etc. dewater, moisture content can be reduced to below the 15ppm after this art breading.
Also the tail gas of tail gas or treated mistake can be absorbed methyl chloride by organic solvent, method by stripping or rectifying obtains comparatively purified methyl chloride again, used organic solvent can be halogenated hydrocarbons, as first chlorination carbon, ethylene dichloride chlorinated aliphatic hydrocarbon, chlorination aromatic hydrocarbons such as mono chloro benzene, dichlorobenzene, m-chlorotoluene; Alcohols is as methyl alcohol, ethanol etc.; Ketone such as acetone, butanone etc.Require solvent for use higher boiling point concerning methyl chloride has higher solubleness and relative methyl chloride, can think that tetracol phenixin is to select preferably.
Contain impurity such as more methyl alcohol, methylal in the synthetic discharging of the glyphosphonic acid tail gas, and the purpose product is high-load methyl chloride, except that the method for above-mentioned separating impurity, the method of another efficient and cost-effective is by chemical reaction impurity conversion to be become the purpose product, huge separating device can be save on the one hand, more purpose product can also be obtained on the other hand.Methylal can be converted into methyl chloride, formaldehyde and water in the presence of hydrogenchloride; Methyl alcohol also can be converted into methyl chloride in the presence of the zinc chloride in hydrochloric acid or hydrogen chloride gas.Therefore carry out other handle before earlier with described tail gas by containing zine ion hydrochloric acid soln or mix laggard promoting the circulation of qi solid catalysis reaction with hydrogenchloride methyl alcohol and methylal are converted into methyl chloride also be a kind of method preferably, used catalyzer is the particulate alumina that contains zinc chloride.
Embodiment
It is considered herein that easily the technical scheme of industrializing implementation is: (1) pre-treatment: after described hydrolysis tail gas is sent into the gas holder buffering, with compressor compresses and cooling, the control compressor delivery pressure does not liquefy with methyl chloride and is advisable, be generally 0.1-1Mpa (absolute pressure), methylal and methyl alcohol in the hydrolysis tail gas are liquefied because of being in hypersaturated state, separate with the methylal and the methyl alcohol of separator, get pre-treatment gas liquefaction.The present invention is preferably 0.35-0.4Mpa (absolute pressure), and the washing hydration of isolated methylal and methyl alcohol and a step operation is also handled.(2) circulation washing: pre-treatment gas is removed the not methylal and the methyl alcohol of liquefaction in the pre-treatment gas by single-stage washing or plural serial stage washing, must wash gas.The washing of should pressurizeing of this step to improve methylal and the solubleness of methyl alcohol in water, reduces washing water consumption (can reduce to 1-2 ton/ton), and working pressure is 0.08-0.3Mpa (absolute pressure), is preferably 0.15-0.2Mpa (absolute pressure).Methylal and methanol content are higher in the washing water after the absorption, can with send methanol recovery system to separate purification after the methylal of pre-treatment discharging and methyl alcohol merge with rectifying tower, the methyl alcohol of recovery is used for the synthetic of glyphosphonic acid, methylal is as commodity selling.(3) alkali lye absorbs: with the liquid caustic soda washing of above-mentioned gas by 10-40%, remove acidic substance, used absorption agent also can for the hydrogen of 10-40% according to yellow soda ash or the salt of wormwood of changing potassium or 10-40%, from considering economically, the present invention is preferably sodium hydroxide, and concentration is 25-35%.(4) drying: will handle that back gas passes through vitriol oil plural serial stage drying after molecular sieve adsorption or anhydrous metal salt drying through the last step, compressed again condensation promptly gets the methyl chloride finished product.
Characteristics of the present invention are the methyl chloride rate of recovery height in the glyphosphonic acid tail gas, quality better, and methyl alcohol in the tail gas and methylal can be made full use of.
The method that is used for removing the impurity component of the synthetic discharging of glyphosphonic acid tail gas described in the invention can be carried out multiple combination, do not do the limit explanation in the present invention, should be included within the present invention yet even the combination of the processing scheme of being done on basis of the present invention is different from the described scheme of embodiment.
Embodiment: it is 4M that the exhaust emissions point from glyphosphonic acid and dimethylphosphite production respectively draws pipeline to a volume
3Surge tank through spinner-type flowmeter, adopts down routine scheme to handle methyl chloride and methylal weight content in the usefulness gas spectrum analysis exit gas of back respectively, in each experimentation from surge tank sampling analysis methyl chloride content wherein.
Embodiment 1: adopt patent of invention 99119970.7 described tertiary treatment, both earlier through big water gaging spray washing, washing is to be 89mm at four groups of diameters, high 1000mm, in fill out in the packing tower of glass rectangular saddle ring and carry out, washing gas absorbs through 30% liquid caustic soda, 85% vitriol oil again.
Embodiment 2: be compressed to 0.3Mpa (absolute pressure) earlier, be cooled to 15 ℃ through condenser, gas phase washes with water through two groups of above-mentioned packing towers again, and washing gas absorbs through 35% liquid caustic soda, 90% vitriol oil again, keeps system pressure and is not less than 0.2Mpa (absolute pressure).
Embodiment 3: be compressed to 5Mpa (absolute pressure) earlier, be cooled to-5 ℃ with chilled brine, get rid of the experiment of again phlegma being introduced through being incubated processing behind the non-condensable gases and use in the distillation tower, keep tower still temperature and be no more than 5 ℃, the tower internal pressure is 0.2Mpa (absolute pressure), analyzes the overhead gas phase composite.
Embodiment 4: is the stainless steel tube of 25mm with exsiccant with the aluminium sesquioxide granular solids filling diameter that zinc chloride soaks, adopt the electric heating type of heating, gas is mixed the back feed this reactor with the hydrogenchloride that parses from hydrochloric acid, and to keep temperature of reaction be 120-180 ℃, adopts the method for embodiment 1 to handle exit gas again.
Embodiment 5: pass through the anhydrous cupric sulfate drying again after embodiment 2 handles.
Embodiment 6: adopt embodiment 1 described packing tower, replace water to absorb with tetracol phenixin, temperature is controlled at 20-30 ℃, pressure 0.6-1Mpa (absolute pressure).Through embodiment 3 described distillation tower distillations, the control tower internal pressure is 0.05Mpa (absolute pressure) to absorption liquid again, and cat head is controlled at 0-10 ℃ with chilled brine, adopts the method for embodiment 1 to handle exit gas again.
The experimental result tabulation
| Sequence number | Methyl chloride weight content (%) | Impurity weight content ppm | ||
| Surge tank | Outlet | Methylal | Water | |
| 1 | 62.2 | 99.5 | 35 | 40 |
| 2 | 64.5 | 99.8 | 28 | 32 |
| 3 | 62.3 | 98.1 | 80 | 68 |
| 4 | 63.7 | 99.7 | 30 | 35 |
| 5 | 62.8 | 99.9 | 26 | 10 |
| 6 | 62.0 | 99.7 | 30 | 27 |
Claims (13)
1. technology that reclaims the methyl chloride that produces in the glyphosphonic acid production process is characterized in that:
(1) collects discharge tail gas in the glyphosphonic acid production process;
(2) adopt the method that transforms impurity to handle collected tail gas, methyl chloride content is wherein increased, wherein the method for this conversion impurity is: the collected tail gas that contains methyl chloride is fed in the solution that contains hydrogenchloride or with hydrogenchloride be mixed into reactor, wherein methyl alcohol and methylal partly or entirely changed into methyl chloride.
2. according to the technology of claim 1, being characterized as of the methyl chloride that is reclaimed wherein: 1. the weight content of methyl chloride is 20-99.99%; 2. contain feature impurity methylal, its weight content is 0.1ppm-80%.
3. according to the technology of claim 2, being characterized as of described methyl chloride: 1. the weight content of methyl chloride is 99-99.99%; 2. the weight content of feature impurity methylal is 0.1-100ppm.
4. according to the technology of claim 1, being characterized as of described glyphosphonic acid: adopting dimethylphosphite or trimethyl phosphite is that the alkyl phosphite method of one of main raw material is produced.
5. according to the technology of claim 4, described glyphosphonic acid production technique comprises phosphorus trichloride synthesizing phosphorous acid dimethyl ester or trimethyl phosphite as one of glyphosphonic acid synthesis procedure.
6. according to the technology of claim 1, it further comprises: after described method for transformation, to contain the pressurized with fluid of methyl chloride or cooling or pressurization and cooling liquefies or partial liquefaction wherein methyl chloride, methyl alcohol, methylal and water fully, it further comprises: with the method for the fluid that contains methyl chloride behind described liquefaction fully or the partial liquefaction by solvent absorbing, the content of impurity methyl alcohol contained in the described fluid, methylal, water, hydrogenchloride and salt acid mist is descended.
7. according to the technology of claim 6, being characterized as of wherein said solvent absorbing method: the solvent of employing is the water or the aqueous solution that contains alkaline matter, perhaps is the vitriol oil.
8. according to the technology of claim 1, it further comprises: after described method for transformation, the fluid that will contain methyl chloride adopts the method that absorbs that the methyl chloride in the described fluid is changed in the solvent by organic solvent.
9. technology according to Claim 8, wherein said organic solvent is that carbonatoms is the hydrocarbon of halohydrocarbon, ketone, alcohol or the carbonatoms 4-16 of 1-10.
10. technology according to Claim 8, it comprises that further the absorption liquid that will contain methyl chloride and other impurity component separates through desorb.
11. according to the technology of claim 6 or 8, it further comprises: the fluid that will contain methyl chloride adopts the method for absorption to make the wherein aqueous content decline of institute by the solid adsorbent that can absorb water.
12. according to the technology of claim 11, wherein said solid adsorbent is oxide compound or the anhydrous metal salt that water sorption is arranged.
13., wherein will separate the phlegma that contains methyl alcohol or methylal material behind the methyl chloride and return the solvent recuperation operation of glyphosphonic acid in producing according to the technology of claim 6.
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| CN 200410097716 CN1288118C (en) | 2002-07-23 | 2002-07-23 | Clean reclaiming process for byproduct chloromethane of glyphosate acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108047063A (en) * | 2017-12-28 | 2018-05-18 | 浙江新安化工集团股份有限公司 | A kind of preparation method of methyl triethyl ammonium chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104959002A (en) * | 2015-06-29 | 2015-10-07 | 江西金龙化工有限公司 | Method for removing hydrogen chloride by continuously recycling glyphosate hydrolyzed tail gas |
| CN105753901A (en) * | 2016-03-19 | 2016-07-13 | 安徽东至广信农化有限公司 | Technology for recovering chloromethane washing wastewater in glyphosate production |
| CN108084037B (en) * | 2017-12-28 | 2019-06-11 | 浙江新安化工集团股份有限公司 | A kind of preparation method of methyl triethyl ammonium chloride |
| CN110540487A (en) * | 2018-05-28 | 2019-12-06 | 无锡凯美工程技术有限公司 | System for purifying methyl chloride and method for treating organic matters in methyl chloride gas by substituted sulfuric acid adsorption |
| CN108586190A (en) * | 2018-07-31 | 2018-09-28 | 山东海昆化工技术有限公司 | A method of recycling chloromethanes from chloromethanes exhaust gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108047063A (en) * | 2017-12-28 | 2018-05-18 | 浙江新安化工集团股份有限公司 | A kind of preparation method of methyl triethyl ammonium chloride |
| CN108047063B (en) * | 2017-12-28 | 2019-06-11 | 浙江新安化工集团股份有限公司 | A kind of preparation method of methyl triethyl ammonium chloride |
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