CN110003269A - The method of low energy consumption production glufosinate-ammonium - Google Patents
The method of low energy consumption production glufosinate-ammonium Download PDFInfo
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- CN110003269A CN110003269A CN201910355084.3A CN201910355084A CN110003269A CN 110003269 A CN110003269 A CN 110003269A CN 201910355084 A CN201910355084 A CN 201910355084A CN 110003269 A CN110003269 A CN 110003269A
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- energy consumption
- glufosinate
- ammonium
- low energy
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- 238000000034 method Methods 0.000 title claims abstract description 47
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000005265 energy consumption Methods 0.000 title claims abstract description 27
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 14
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 13
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004176 ammonification Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 4
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 claims description 32
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000005336 cracking Methods 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- -1 methoxyl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000007792 gaseous phase Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- JJPBKCZJVYSKGV-UHFFFAOYSA-N diethoxyphosphane Chemical compound CCOPOCC JJPBKCZJVYSKGV-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- ZFJMTDFOGDGPTF-UHFFFAOYSA-N phosphanium;chloride;hydrochloride Chemical compound P.Cl.Cl ZFJMTDFOGDGPTF-UHFFFAOYSA-N 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 241000209504 Poaceae Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 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 2
- 241000234653 Cyperus Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the methods of low energy consumption production glufosinate-ammonium, belong to herbicide glufosinate-ammonium production technical field.Present invention solves the technical problem that being that the existing method energy consumption for producing glufosinate-ammonium is high, at high cost.The invention discloses the methods of low energy consumption production glufosinate-ammonium, it is trapped using Pintsch process material of the trapping agent to methane, phosphorus trichloride, obtained trapping solution is isolated into most phosphorus trichlorides through rectifying, then the diethyl methyl-phosphonite trapping agent solution containing a small amount of triethyl phosphite is obtained with ethanol synthesis, rectifying separates de- heavy constituent triethyl phosphite, then acetal is prepared with acrolein reaction, most obtains glufosinate-ammonium through cyanogen ammonification, hydrolysis afterwards.The present invention is enough to be condensed at a relatively high temperature, and distillation process does not need high theoretical cam curve, big reflux ratio, has the characteristics that low energy consumption, reduces production run expense.
Description
Technical field
The invention belongs to herbicide glufosinate-ammonium production technical fields, and in particular to the method for low energy consumption production glufosinate-ammonium.
Background technique
The structural formula of glufosinate-ammonium are as follows:It (is now belonged to by German Hoechst company earliest
Beyer Co., Ltd) it succeeds in developing, belong to non-selective contact weedicide.Currently, glufosinate-ammonium can be used in orchard, vineyard, it is non-plough
In the environment such as ground, potato fields, to prevent and treat annual and perennial dicotyledonous and gramineae weed, perennial gramineae weed
And nutgrass flatsedge, there is preferable effect, be the excellent substitute of paraquat, the resolution ability of quick-acting and antagonism weeds is again excellent
In glyphosate.
Zhuan Jianyuan and Hu laugh at shape and review the industry of glufosinate-ammonium in " discussion and inspiration of glufosinate-ammonium foreign countries industrialized route "
The method of being combined to includes: Strecker method process route, the methyl-phosphinic acid using diethyl methyl-phosphonite as key intermediate
Ester (MPE) and acrolein cyanohydrin acetic acid esters (ACA) are the Michael additive process process route of key intermediate.Most domestic
Enterprise uses Strecker method, wherein key intermediate diethyl methyl-phosphonite can pass through Grignard and dichloromethylphosphine
Method obtains.Grignard Atom economy is not high, yield is not high, quantity of three wastes big (magnesium chloride), high production cost.In contrast, first
Raw material is cheap and easy to get, Atom economy is high, quantity of three wastes is small needed for base dichloride phosphine method.However, being obtained by dichloromethylphosphine method
Pintsch process reaction, -55 DEG C of cooling materials of low temperature depth and two boiling points for taking the process of glufosinate-ammonium to be related to 500 DEG C or more
The separation of poor only 7 DEG C of dichloromethylphosphine and phosphorus trichloride causes operation energy consumption high, and comprehensive production cost is high.Cause
This, research high efficiency, low cost manufactures dichloromethylphosphine, and then obtains glufosinate-ammonium, is increasingly valued by people.
It is the technology path of high-temperature cracking method diethyl methyl-phosphonite production glufosinate-ammonium below:
CH4+PCl3→CH3PCl2+HCl
CH3PCl2+2EtOH+2NH3→CH3P(OEt)2+2NH4Cl
Currently, preparing dichloromethylphosphine technology, methyl two in 500 DEG C or more of Pintsch process by methane and phosphorus trichloride
The isolation technics of phosphonium chloride and phosphorus trichloride is the core technology of Bayer, and Bayer patent US4104304 reports methyl dichloro
Phosphine synthetic technology and reaction unit, the conversion ratio 20% or so of raw material, high temperature gaseous phase materials -55 DEG C of cryogenic condensations of use.However,-
55 DEG C of low temperature energy consumption in industrial processes is very high, is not easy to produce and use on a large scale.In addition, phosphorus trichloride and first
Base dichloride phosphine boiling point differs 7 DEG C, and it is very big that dichloromethylphosphine difficulty is separated from a large amount of phosphorus trichloride.US4104299
In disclose a kind of method and device for isolating and purifying dichloromethylphosphine, in order to realize separation phosphorus trichloride purity reach
99%, phosphorus trichloride theoretical number of plates of rectifying tower is 130 pieces, and reflux ratio 15:1, big reflux ratio causes in industrial processes
Middle energy consumption is very high, is also not susceptible to produce and use on a large scale.
Cracking process prepares dichloromethylphosphine and separates dichloromethylphosphine from phosphorus trichloride, very fastidious engineering
Level, only Bayer realizes industrialization at present.For this purpose, there is an urgent need to a kind of preparations of the Pintsch process of low energy consumption, low operating cost
Dichloromethylphosphine intermediate and then the method for producing glufosinate-ammonium, to meet the current high-efficiency low-toxicity type pesticide chemical development in China
It needs.
Summary of the invention
Present invention solves the technical problem that being method energy consumption height, the operating cost height of existing production glufosinate-ammonium.
Technical proposal that the invention solves the above-mentioned problems is to provide the method for low energy consumption production glufosinate-ammonium, including walks as follows
It is rapid: condensing trapping to be carried out using Pintsch process material of the trapping agent to methane, phosphorus trichloride, by obtained trapping solution through rectifying point
Most phosphorus trichlorides are separated out, then obtain catching containing the diethyl methyl-phosphonite of a small amount of triethyl phosphite with ethanol synthesis
Collect agent solution, rectifying separates de- heavy constituent triethyl phosphite, then prepares acetal with acrolein reaction, depressurizes and steam from acetal
Recycling trapping agent is evaporated, most obtains glufosinate-ammonium through cyanogen ammonification, hydrolysis afterwards.
Wherein, trapping agent is compoundOr in which two or more mixtures, wherein R1、R2、R3、
R4、R5、R6It is each independently selected from hydrogen, methyl, ethyl, methoxyl group, ethyoxyl, halogen.
Wherein, trapping agent is preferably at least one of toluene, ethylbenzene, paraxylene.
Wherein, condensation equilibrium temperature is 0~30 DEG C.
Wherein, rectifying, tower are carried out to the mixed material containing dichloromethylphosphine, phosphorus trichloride, trapping agent using rectifying column
Top extraction phosphorus trichloride, directly set are used as cracking stock, and tower bottom produces the dichloromethylphosphine containing a small amount of phosphorus trichloride and catches
Collect the mixed liquor of agent.
Wherein, rectifying column is plate column or packed tower, and theoretical cam curve is 50~100, and mixture feed entrance point is the
At 25~50 blocks of column plates, the tower top temperature for distilling out phosphorus trichloride is 73 DEG C~76 DEG C, overhead reflux ratio 1:1~5:1, tower bottom temperature
Degree is 90 DEG C~120 DEG C.
Wherein, the dichloromethylphosphine trapping agent solution containing a small amount of phosphorus trichloride and ethyl alcohol esterification obtain phosphorous acid three
Ethyl ester and diethyl methyl-phosphonite, using rectifying column to esterification products carry out rectifying, overhead extraction diethyl methyl-phosphonite,
The mixture of trapping agent, directly as lower step aldolisation raw material, tower bottom produces triethyl phosphite.
Wherein, rectifying column is plate column or packed tower, and theoretical cam curve is 30~60, and mixture feed entrance point is the 15th
At~30 blocks of column plates, the tower top temperature for distilling out diethyl methyl-phosphonite is 70 DEG C~75 DEG C, overhead reflux ratio 1:1~5:1,
Tower top pressure -80KPa, column bottom temperature are 90 DEG C~120 DEG C.
Wherein, using vacuum distillation equipment recycling trapping agent recycled in the condensing trapping of cracking gaseous phase materials.
Beneficial effects of the present invention:
The present invention introduces trapping agent in the condensation process of high-temperature split product, and phosphorus trichloride and methyl dichloro can be effectively reduced
Change phosphine gas phase vapour pressure, changes the relative volatility of phosphorus trichloride and dichloromethylphosphine, so as in relatively high temperature
It being condensed under degree, condensation equilibrium temperature is 0~30 DEG C, it is easier to the collection and separation of dichloromethylphosphine reduce energy consumption, from
And reduce production cost；The present invention does not need the low-temperature deep using -55 DEG C compared with the conventional method that Bayer is reported, and not
High theoretical cam curve, big reflux ratio rectifying separation dichloromethylphosphine are needed, therefore has the characteristics that low energy consumption, reduces production
Operating cost has better prospects for commercial application.
Specific embodiment
The present invention provide low energy consumption production glufosinate-ammonium method, specifically comprise the following steps: using methane, phosphorus trichloride as
Pintsch process raw material carries out condensing trapping to Pintsch process material using trapping agent, and trapping solution is through the rectifying separation overwhelming majority three
After phosphorus chloride, the dichloromethylphosphine trapping agent solution containing a small amount of phosphorus trichloride, the methyl dichloro containing a small amount of phosphorus trichloride are obtained
Change the solution of phosphine and trapping agent and then and ethanol synthesis obtains diethyl methyl-phosphonite and the trapping agent of triethyl phosphite is molten
Liquid, after rectifying separates de- heavy constituent triethyl phosphite, by trapping agent solution and methacrylaldehyde containing diethyl methyl-phosphonite
Reaction prepares acetal, and vacuum distillation recycling trapping agent, realizes the recycling of trapping agent from acetal, acetal most afterwards through cyanogen ammonification,
Hydrolysis obtains glufosinate-ammonium.
Wherein, trapping agent is compoundOr in which two or more mixtures, wherein R1、R2、R3、
R4、R5、R6It is each independently selected from hydrogen, methyl, ethyl, methoxyl group, ethyoxyl, halogen.
Wherein, trapping agent is preferably at least one of toluene, ethylbenzene, paraxylene.
Wherein, the present invention condenses equilibrium temperature and can be controlled in 0~30 DEG C.Methane, phosphorus trichloride high-temperature split product go out
Temperature meets with the lower trapping agent of temperature in product trapping system about at 500~600 DEG C and carries out condensing trapping, split after coming
Solution product is dissolved in trapping agent, can increase trapping agent temperature, and last entirety condensation temperature balance is at 0~30 DEG C.
Wherein, rectifying, tower are carried out to the mixed material containing dichloromethylphosphine, phosphorus trichloride, trapping agent using rectifying column
Top extraction phosphorus trichloride, directly set are used as cracking stock, and tower bottom produces the dichloromethylphosphine containing a small amount of phosphorus trichloride and catches
Collect the mixed liquor of agent.
Wherein, rectifying column is plate column or packed tower, and theoretical cam curve is 50~100, and mixture feed entrance point is the
At 25~50 blocks of column plates, the tower top temperature for distilling out phosphorus trichloride is 73 DEG C~76 DEG C, overhead reflux ratio 1:1~5:1, tower bottom temperature
Degree is 90 DEG C~120 DEG C.
Wherein, the dichloromethylphosphine trapping agent solution containing a small amount of phosphorus trichloride and ethyl alcohol esterification obtain phosphorous acid three
Ethyl ester and diethyl methyl-phosphonite, using rectifying column to esterification products carry out rectifying, overhead extraction diethyl methyl-phosphonite,
The mixture of trapping agent, directly as lower step aldolisation raw material, tower bottom produces triethyl phosphite.
Wherein, rectifying column is plate column or packed tower, and theoretical cam curve is 30~60, and mixture feed entrance point is the 15th
At~30 blocks of column plates, the tower top temperature for distilling out diethyl methyl-phosphonite is 70 DEG C~75 DEG C, overhead reflux ratio 1:1~5:1,
Tower top pressure -80KPa, column bottom temperature are 90 DEG C~120 DEG C.
In order to realize the recycling of trapping agent, the present invention can be after aldolisation first using vacuum distillation equipment to trapping agent
It is recycled, then recycled obtains glufosinate-ammonium to the ammonification of acetal cyanogen, hydrolysis again in the condensing trapping of cracking gaseous phase materials.
The present invention will be further explained by the following examples and explanation.
Embodiment 1
Experiment is using a DN32, the Hastelloy pipe of long 800mm, electric heating as cracking reaction device, methane feed amount
For 1 cube/h, phosphorus trichloride (carbon tetrachloride containing 4.5%) inlet amount 1.2kg/h, 600 DEG C of reaction temperature, obtains cracking and produce
Object, -10 DEG C of diformazan benzene input is 1kg/h in product trapping system, with high-temperature gas fair current, collects pyrolysis product
2.15kg/h, analysis detection each component content are as follows: 8.1% dichloromethylphosphine, 44.5% phosphorus trichloride, 46.5% pair of diformazan
Benzene, 0.5% carbon tetrachloride；
Glass rectifying column of the experiment using a set of Φ 30mm, built-in θ ring filler, 3 meters of tower height (theoretical cam curve 70~75),
Condensing trapping liquid feed entrance point containing pyrolysis product is to control reflux ratio 1:1 at 1.5 meters of tower heights, 110 DEG C of column bottom temperature, tower
74 DEG C of temperature of top, tower top obtain the phosphorus trichloride that purity is 99%, and tower bottom obtains the dichloromethylphosphine containing a small amount of phosphorus trichloride
With the mixture of paraxylene, analysis detection each component content are as follows: 13.3% dichloromethylphosphine, 1.5% phosphorus trichloride, 85%
Paraxylene；
The mixture and ethyl alcohol, ammonia for the dichloromethylphosphine and paraxylene containing a small amount of phosphorus trichloride that upper step is obtained
Reaction obtains the paraxylene solution of diethyl methyl-phosphonite, and using the glass rectifying column of a set of Φ 30mm, built-in θ ring is filled out
Material, 1.5 meters of tower height, control reflux ratio is 1:1, and 73 DEG C~76 DEG C of tower top temperature obtain the paraxylene of diethyl methyl-phosphonite
Solution, 120 DEG C of tower bottom obtain triethyl phosphite, content 98%；
The xylene solution of diethyl methyl-phosphonite is added dropwise to the mixture of methacrylaldehyde and acetic anhydride in 25 DEG C -30 DEG C,
Vacuum distillation recycling paraxylene, paraxylene content 99.1% after having reacted；
It is the prior art, the method that can refer to CN1267305A announcement that acetal, which obtains glufosinate-ammonium through cyanogen ammonification, hydrolysis,.
Embodiment 2
Same as Example 1, trapping agent is adjusted to toluene, detection cracking product compositions content are as follows: 8.2% methyl dichloro
Change phosphine, 44.7% phosphorus trichloride, 46.5% toluene, 0.5% carbon tetrachloride；
Phosphorus trichloride rectifying separation process reflux ratio replaces with 2:1, and 74 DEG C of tower top temperature, resulting phosphorus trichloride purity is
98%, the mixture each component content of dichloromethylphosphine and toluene of the tower bottom gained containing a small amount of phosphorus trichloride are as follows: 14.7% first
Base dichloride phosphine, 1.5% phosphorus trichloride, 83.5% toluene；
The triethyl phosphite content 98% obtained with rectifying after ethanol synthesis recycles first through vacuum distillation after aldolisation
Benzene content 99.2%；
It is the prior art, the method that can refer to CN1267305A announcement that acetal, which obtains glufosinate-ammonium through cyanogen ammonification, hydrolysis,.
The invention is not limited to specific embodiments above-mentioned.The present invention, which expands to, any in the present specification to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (11)
1. the method for low energy consumption production glufosinate-ammonium, it is characterised in that include the following steps: using trapping agent to methane, phosphorus trichloride
Pintsch process material carry out condensing trapping, obtained trapping solution is isolated into most phosphorus trichlorides through rectifying and is obtained containing few
The dichloromethylphosphine for measuring phosphorus trichloride traps agent solution, and the methyl containing a small amount of triethyl phosphite is then obtained with ethanol synthesis
Phosphonous acid diethylester traps agent solution, and rectifying separates de- heavy constituent triethyl phosphite, then prepares acetal with acrolein reaction,
Most glufosinate-ammonium is obtained through cyanogen ammonification, hydrolysis afterwards.
2. the method for low energy consumption production glufosinate-ammonium according to claim 1, it is characterised in that: the trapping agent is compoundOr in which two or more mixtures, wherein R1、R2、R3、R4、R5、R6It is each independently hydrogen, methyl, second
Base, methoxyl group, ethyoxyl, halogen.
3. the method for low energy consumption production glufosinate-ammonium according to claim 1 or 2, it is characterised in that: the trapping agent is first
At least one of benzene, ethylbenzene, paraxylene.
4. the method for described in any item low energy consumption production glufosinate-ammoniums according to claim 1~3, it is characterised in that: the condensation
Equilibrium temperature is 0~30 DEG C.
5. the method for low energy consumption production glufosinate-ammonium according to any one of claims 1 to 4, it is characterised in that: use rectifying
Tower carries out rectifying to the mixed material containing dichloromethylphosphine, phosphorus trichloride, trapping agent, and overhead extraction phosphorus trichloride directly covers
It is used as cracking stock, tower bottom produces the mixed liquor of dichloromethylphosphine and trapping agent containing a small amount of phosphorus trichloride.
6. the method for low energy consumption production glufosinate-ammonium according to claim 5, it is characterised in that: the rectifying column is plate column
Or packed tower, overhead reflux ratio 1:1~5:1.
7. the method for low energy consumption production glufosinate-ammonium according to claim 5 or 6, it is characterised in that: the rectifying column is theoretical
The number of plates is 50~100, and mixture feed entrance point is that the tower top temperature of phosphorus trichloride is distilled out at the 25th~50 block of column plate is 73
DEG C~76 DEG C, column bottom temperature is 90 DEG C~120 DEG C.
8. the method for described in any item low energy consumption production glufosinate-ammoniums according to claim 1~7, it is characterised in that: described containing few
The dichloromethylphosphine trapping agent solution and ethyl alcohol esterification of amount phosphorus trichloride obtain triethyl phosphite and methyl phosphonous acid
Diethylester, using rectifying column to esterification products carry out rectifying, the mixture of overhead extraction diethyl methyl-phosphonite, trapping agent,
Directly as lower step aldolisation raw material, tower bottom produces triethyl phosphite.
9. the method for low energy consumption production glufosinate-ammonium according to claim 8, it is characterised in that: the rectifying column is plate column
Or packed tower, overhead reflux ratio 1:1~5:1.
10. the method for low energy consumption production glufosinate-ammonium according to claim 8 or claim 9, it is characterised in that: the theoretical cam curve
It is 30~60, mixture feed entrance point is at the 15th~30 block of column plate, and the tower top temperature for distilling out diethyl methyl-phosphonite is
70 DEG C~75 DEG C, tower top pressure -80KPa, column bottom temperature is 90 DEG C~120 DEG C.
11. the method for described in any item low energy consumption production glufosinate-ammoniums according to claim 1~10, it is characterised in that: acetal is anti-
It should be afterwards using vacuum distillation equipment recycling trapping agent recycled in the condensing trapping of cracking gaseous phase materials.
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