CN208562200U - A kind of system that methylisothiouronium methylphosphite ester is prepared using throwing disc reaction kettle - Google Patents
A kind of system that methylisothiouronium methylphosphite ester is prepared using throwing disc reaction kettle Download PDFInfo
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Abstract
The utility model provides a kind of system for preparing methylisothiouronium methylphosphite ester using throwing disc reaction kettle, and the system comprises sequentially connected throwing disc reaction kettle, de- by-product unit and product separative units；Wherein, the material outlet of the throwing disc reaction kettle is connected with the material inlet of de- by-product unit.The utility model combines the equipment such as rectifying column using throwing disc reaction kettle as the reactor of methyl dichloro phosphorus and alcohol, passes through the processes such as mixing synthesis, depickling and rectifying, continuous synthesizing methyl phosphite ester product, process recovery ratio is high, easy to operate, basic no three wastes generates, and is not necessarily to solvent, environmentally protective.
Description
Technical field
The utility model belongs to organic chemical synthesis field, is related to a kind of system for preparing methylisothiouronium methylphosphite ester, especially relates to
And a kind of system that methylisothiouronium methylphosphite ester is continuously generated with throwing disc reaction kettle.
Background technique
Methylisothiouronium methylphosphite ester is a kind of important industrial chemicals intermediate, can be widely used in and prepare fire retardant and remove
Careless agent.Methylisothiouronium methylphosphite ester structure is as follows:
CH3P(OR)n(OH)2-n
Wherein, group R is alkyl of the C atomicity 1~4, and n is 1 or 2.Such substance use is extensive, can be used for fire-retardant
Agent synthesis and pesticide synthesis etc..
When R is methyl, and n is 2, as methyl dimethyl phosphite, molecular formula C3H9O3P, molecular weight 124.08, outside
Seeing is colourless liquid, and fusing point is less than -50 DEG C, and boiling point is 181 DEG C (0.1005MPa), density 1.16g/cm3.It is mainly used for ring
In the high molecular materials such as additive flame retardant, polyurethane foam plastics, unsaturated polyester (UP) resin and the epoxy resin of oxygen resin class,
Also act as the intermediate of organic synthesis, rare metal extractant etc..
When R is ethyl, and n is 2, as diethyl methyl-phosphonite, molecular formula C5H13O2P, molecular weight 136.13,
Appearance is colourless liquid, and boiling point is 124.5 DEG C, and flash-point is 26.5 DEG C, density 0.9g/cm3.Diethyl methyl-phosphonite is to close
At the key intermediate of herbicide glufosinate-ammonium.
When R is normal-butyl, and n is 1, as methylisothiouronium methylphosphite list N-butyl, colourless liquid are mainly used for plastic flame and add
Add agent.
When R is normal-butyl, and n is 2, as methylisothiouronium methylphosphite dibutyl ester, molecular weight 208.23, boiling point are 264.5 DEG C,
Density is 0.973g/cm3。
CN 103319529A discloses a kind of preparation method of diethyl methyl-phosphonite, use diethyl phosphite,
Chloromethanes is raw material, and diethyl phosphite is first passed through with chloromethanes reaction, generation methyl acid phosphate diethylester, methylphosphonic acid diethylester again
It crosses reduction reaction and obtains diethyl methyl-phosphonite, key reaction step is methylation reaction, two step of reduction reaction.
CN 103374030A discloses the preparation method of a kind of glufosinate-ammonium and its intermediate, wherein methyl phosphonous acid diethyl
The preparation method of ester is that phosphorus trichloride and triethyl phosphite react to obtain chloro phosphite ester；Magnesium and chloromethanes react to obtain first
Base magnesium chloride；Chloro phosphite ester reacts to obtain diethyl methyl-phosphonite again with methyl-magnesium-chloride.
CN 105524109A discloses a kind of synthetic method of methylisothiouronium methylphosphite ester, is that starting is former with phosphorus pentoxide
First catalytic hydrogenation obtains chloro phosphite ester to material after vulcanization reaction, chlorination reaction, washing, distilation, then through grignard reaction
Obtain methylisothiouronium methylphosphite ester.Reactions steps of this method is more, complex process, and yield is low.
CN 105131034A discloses a kind of method for synthesizing and purifying of methylisothiouronium methylphosphite ester type compound, specially lazy
In property solvent, salt water, isolated first is added under low temperature in the solution of Xiang Hanyou methylisothiouronium methylphosphite dialkyl and magnesium chloride mixture
Base dialkylphosphites or methylisothiouronium methylphosphite list alkyl ester.This method main function is to purify and is with methylisothiouronium methylphosphite dialkyl
Material synthesis methylisothiouronium methylphosphite list alkyl ester.
CN 104892670A discloses a kind of preparation method of glufosinate-ammonium and the like, wherein devising methyl phosphorous
The synthesis of acid esters, method reacts synthesizing methyl phosphite ester using methyl dichloro phosphorus and alcohol as raw material, it is characterized in that used
Alcohol be C4 or more positive alcohol or different alcohol, reaction product is methylisothiouronium methylphosphite monoesters.This method is by the way of intermittently operated, instead
Process is answered to need to use n,N-Dimethylformamide etc. as acid binding agent, Atom economy is poor.
CN 106046051A discloses a kind of preparation method of methylisothiouronium methylphosphite diethylester, uses methyl dichloro phosphorus
It (MDP) is raw material, in tubular reactor and ethyl alcohol gas phase reaction, generation diethyl methyl-phosphonite focus on tubular type
Reactor.This method carries out in tubular reactor, but lacks the aftertreatment technologies such as depickling, rectifying, cause conversion rate of products and
Content is lower.
CN 105949239A discloses a kind of preparation method of methylisothiouronium methylphosphite dialkyl, and 10 uncle is greater than using pKa
Amine makees acid binding agent, and methyl dichloro phosphorus reacts in a solvent with alcohol, obtains methylisothiouronium methylphosphite dialkyl.The reaction needs acid binding agent
Reaction is participated in, and is to be reacted in a solvent, complex process is big to environmental protection pressure；It is unable to continuous production, utilization rate of equipment and installations
It is low.
CN 106674275A discloses the preparation process and corresponding preparation facilities and system of a kind of methyl phosphinate
Preparation Method, by under -0.095MPa~-0.001MPa condition of negative pressure and reaction temperature is 35 DEG C~90 DEG C of condition
Under, methyl phosphinate is made in the reaction that methyl dichloro phosphorus and alcohol roh are carried out in packed tower.Although this method is without addition
It acid binding agent and can be continuously produced, but packed tower is larger for the opereating specification of starting charge, is not easy to reaction controlling.
Domestic also some researchs for diethyl phosphite synthesis, basic line focuses mostly on is being with phosphorus trichloride
Raw material first carries out esterification and obtains chloro phosphite ester, then carries out methylation reaction again, obtain methyl phosphonous acid two with alcohol
Ethyl ester." diethyl methyl-phosphonite synthesising process research ", " fine chemistry industry delivered such as " Zhejiang Polytechnical University's journal " Ding Chengrong
" synthesising process research of diethyl methyl-phosphonite ", " the 11st whole nation that intermediate " the 2nd phase Wang Hong-Liang of volume 35 delivers
Pesticide Science section teaching and scientific research seminar " collection of thesis Du Chun grey hair table " glufosinate-ammonium and its intermediate diethyl methyl-phosphonite
Synthesising process research " all concentrate this synthetic route of research.
In addition there are reports, and MDP to be added dropwise into ethyl alcohol using reaction kettle, using triethylamine or pyridine or ammonia as acid binding agent, but
Due to the limitation of reaction kettle structure, reaction needs carry out under solvent condition, additionally due to MDP is unstable, easily with addition
Alkaline matter reacts under optimum conditions, and one side consumption of raw materials is big, and cost of material increases, another aspect product yield
Low, side reaction increases, and increases product cost for purification.
Utility model content
For the prior art can not serialization prepare methylisothiouronium methylphosphite ester, need additionally to add solvent or acid binding agent etc. addition
The problems such as agent, product yield is low, and side reaction increases, and product cost for purification is high, the utility model provide a kind of anti-using throwing disc
The system for answering kettle to prepare methylisothiouronium methylphosphite ester.The utility model is using throwing disc reaction kettle as the reaction of methyl dichloro phosphorus and alcohol
Device, and combine the equipment such as rectifying column, by processes such as mixing synthesis, depickling and rectifying, continuous synthesizing methyl phosphite ester product,
Process recovery ratio is high, easy to operate, and basic no three wastes generates, and is not necessarily to solvent, environmentally protective.
For this purpose, the utility model uses following technical scheme:
The utility model provides a kind of system for preparing methylisothiouronium methylphosphite ester, and the system comprises sequentially connected throwing discs
Reaction kettle, de- by-product unit and product separative unit；Wherein, the object of the material outlet of the throwing disc reaction kettle and de- by-product unit
Expect that entrance is connected.
The utility model provides a kind of system for continuously preparing methylisothiouronium methylphosphite ester, is with methyl dichloro phosphorus and alcohol
Raw material, the two carry out hybrid reaction in throwing disc reaction kettle, and reaction raw materials methyl dichloro phosphorus and alcohol are introduced into throwing disc reaction kettle
In throwing disc, be evenly distributed over by throwing disc on reaction kettle inner wall, then carry out continuous hybrid reaction.The utility model can be with
Reaction raw materials are made continuously uniformly to be mixed and be reacted, more existing conventional reactor, tubular reactor and packed tower
Equal devices lamps structure is simple, the good feature with subsequent depickling and rectifier unit matching.Meanwhile material can be effectively prevent heated
Unevenness is partially formed channel or without liquid stream, under throwing disc effect in reaction medium on wall homogeneous film formation, in evaporation process still
The reaction was continued with ethyl alcohol for unreacted dichloromethylphosphine, further improves the yield and production effect of methylisothiouronium methylphosphite ester product
Rate.
In the utility model, the by-products such as hydrogen chloride HCl that methyl dichloro phosphorus and alcohol generate during being reacted
It needs further to be separated by subsequent de- by-product unit and product separative unit, to obtain the higher methyl phosphorous of purity
Acid ester product.
It is used as the preferred technical solution of the utility model below, but not as the limit of technical solution provided by the utility model
System, by the following technical programs, can preferably reach and realize the technical purpose and beneficial effect of the utility model.
As the preferred technical solution of the utility model, the throwing disc reaction kettle built-in throwing disc in a kettle, throwing disc with
Liquid material entrance is connected.
In the utility model, built-in throwing disc is that this field has device feature, therefore no longer goes to live in the household of one's in-laws on getting married in the throwing disc reaction kettle
It states.
As the preferred technical solution of the utility model, the liquid material entrance includes methyl dichloro phosphorus mild and mellow
Entrance, methyl dichloro phosphorus entrance connect methyl dichloro phosphorus transfer pipeline；The alcohol inlet connects alcohol transfer pipeline.
As the preferred technical solution of the utility model, the de- by-product unit includes deacidifying device；Throwing disc reaction kettle
Material outlet is connected with the material inlet of deacidifying device；Deacidifying device is to appoint in reaction kettle, falling film evaporator or tower reactor
It anticipates a kind of or at least two combinations, the combination typical case but non-limiting example has: the combination of reaction kettle and falling film evaporator,
The combination of falling film evaporator and tower reactor, reaction kettle, falling film evaporator and combination of tower reactor etc..
As the preferred technical solution of the utility model, the deacidifying device include sequentially connected level-one deacidifying device and
Second level deacidifying device；The level-one deacidifying device and second level deacidifying device independently are reaction kettle, falling film evaporator or tower
Any one in reactor or at least two combination, the combination is typical but non-limiting example has: reaction kettle and falling liquid film steam
Send out the combination of device, the combination of falling film evaporator and tower reactor, the combination of reaction kettle, falling film evaporator and tower reactor
Deng.
It is anti-into continuing in deacidifying device after methyl dichloro phosphorus and alcohol progress hybrid reaction in the utility model
Should and it remove by-product hydrogen chloride；Further, methyl dichloro phosphorus and alcohol enter level-one deacidifying device after carrying out hybrid reaction
The reaction was continued and tentatively removes by-product hydrogen chloride, enters back into second level deacidifying device and thoroughly removes byproduct hydrogen chloride, removing
Hydrogen chloride prepares hydrochloric acid with water recycling.
As the preferred technical solution of the utility model, the product separative unit includes at least one rectifying column, but not
It is limited to a rectifying column, so that rectifying column is used alternatingly, can guarantees the company of whole system with 2,3,4 or 5 or more
Reforwarding row；The product exit of the de- by-product unit is connected with the material inlet of rectifying column.
Wherein, taking off by-product unit includes product exit and byproduct discharge, the material inlet of product exit and rectifying column
It is connected.
As the preferred technical solution of the utility model, described the top of the distillation column sets condenser, the condensate liquid point of condenser
Two-way returns to rectifying column all the way, connects storage tank all the way.
As the preferred technical solution of the utility model, the rectifying tower bottom sets reboiler, and the discharging of reboiler is divided to two
Road returns to rectifying column all the way, connects storage tank all the way.
As the preferred technical solution of the utility model, the system comprises sequentially connected throwing disc reaction kettle, level-one are de-
Sour device, second level deacidifying device and rectifying column；
Wherein, the material outlet of the throwing disc reaction kettle is connected with the material inlet of level-one deacidifying device, and the throwing disc is anti-
Answering kettle, built-in throwing disc, throwing disc are connected with liquid material entrance in a kettle；Liquid material entrance includes that methyl dichloro phosphorus enters
Mouth and alcohol inlet, the methyl dichloro phosphorus entrance connect methyl dichloro phosphorus transfer pipeline, the alcohol inlet connection alcohol conveying
Pipeline；The product exit of second level deacidifying device is connected with the material inlet of rectifying column, and the top of the distillation column sets condenser, condenser
Condensate liquid divides two-way, returns to rectifying column all the way, connects storage tank all the way；Rectifying tower bottom sets reboiler, and the discharging of reboiler is divided to two
Road returns to rectifying column all the way, connects storage tank all the way.
The preparation method of the above-mentioned system for preparing methylisothiouronium methylphosphite ester the following steps are included:
Raw material methyl dichloro phosphorus and alcohol are reacted in throwing disc reaction kettle, and reacting rear material is successively through depickling and essence
It evaporates, obtains methylisothiouronium methylphosphite ester product.
More specifically, the above-mentioned system for preparing methylisothiouronium methylphosphite ester preparation method the following steps are included:
(a) raw material methyl dichloro phosphorus and alcohol are 1:(0.5~10 in molar ratio) it is reacted in throwing disc reaction kettle, instead
Answering temperature is 10 DEG C~40 DEG C, and reaction pressure is -0.05MPa~-0.095MPa, and the slewing rate of throwing disc is in throwing disc reaction kettle
10r/min~200r/min obtains reacting rear material；
(b) step (a) reacting rear material sequentially enters in level-one deacidifying device and second level deacidifying device is in temperature
40 DEG C~80 DEG C, pressure carries out depickling under conditions of being -0.05MPa~-0.095MPa, removes byproduct hydrogen chloride；
(c) material after step (b) depickling, which enters, carries out rectifying in rectifying column, the temperature of rectifying is 80 DEG C~160 DEG C, pressure
Power is -0.05MPa~-0.095MPa, obtains methylisothiouronium methylphosphite ester product.
Compared with prior art, the utility model has the following beneficial effects:
(1) system described in the utility model is the production system of serialization, using methyl dichloro phosphorus and alcohol as raw material, is first existed
Hybrid reaction in throwing disc reaction kettle, then methyl phosphinate is obtained through depickling and rectifying, continuous reaction simplifies technological operation
Process greatly improves the effective rate of utilization of equipment, reduces cost of labor, saves production cost；
(2) the utility model uses throwing disc reaction kettle, the reactions such as opposite tubular reactor, conventional reactor and packed tower
For device, react it is more abundant, the yield of product can be greatlyd improve, make methyl phosphinate receive reach 90% with
On, and reaction condition is mild, only can be carried out under cryogenic；
(3) the utility model reduces the processes such as subsequent distillation without additives such as solvent and acid binding agents in reacting,
Energy consumption is reduced, resource has been saved, waste is seldom generated in reaction process, processing is convenient, environmentally friendly.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that the system of methylisothiouronium methylphosphite ester is prepared described in the utility model embodiment 1；
Fig. 2 is the structural schematic diagram that the system of methylisothiouronium methylphosphite ester is prepared described in the utility model embodiment 2；
Wherein, 1- throwing disc reaction kettle, 2- deacidifying device, 21- level-one deacidifying device, 22- second level deacidifying device, 3- rectifying
Tower, 4- condenser, 5- reboiler.
Specific embodiment
For the utility model is better described, it is easy to understand the technical solution of the utility model, below to the utility model
It is further described.But following embodiments is only the simple example of the utility model, does not represent or limits and is originally practical
Novel rights protection scope, scope of protection of the utility model are subject to claims.
Specific embodiment of the present invention part, which provides, a kind of prepares methylisothiouronium methylphosphite ester using throwing disc reaction kettle
System and preparation method, the system comprises sequentially connected throwing disc reaction kettle 1, de- by-product unit and product separative units；Its
In, 1 material outlet of throwing disc reaction kettle is connected with the material inlet of de- by-product unit.
Preparation method the following steps are included:
Raw material methyl dichloro phosphorus and alcohol are reacted in throwing disc reaction kettle 1, and reacting rear material is successively through depickling and essence
It evaporates, obtains methylisothiouronium methylphosphite ester product.
The typical but non-limiting embodiment the following are the utility model:
Embodiment 1:
A kind of system for preparing methylisothiouronium methylphosphite ester is present embodiments provided, as shown in Figure 1, the system comprises successively connect
Throwing disc reaction kettle 1, deacidifying device 2 and the rectifying column 3 connect；
Wherein, the material outlet of the throwing disc reaction kettle 1 is connected with the material inlet of deacidifying device 2, and throwing disc reaction kettle 1 exists
Built-in throwing disc, throwing disc are connected with liquid material entrance in reaction kettle, and liquid material entrance includes methyl dichloro phosphorus mild and mellow
Entrance, methyl dichloro phosphorus entrance connect methyl dichloro phosphorus transfer pipeline, and alcohol inlet connects alcohol transfer pipeline；Deacidifying device 2
Material inlet for reaction kettle, the product exit rectifying column 3 of deacidifying device 2 is connected, and 3 tower top of rectifying column sets condenser 4, condensation
The condensate liquid of device 4 divides two-way, returns to rectifying column 3 all the way, connects storage tank all the way；3 tower bottom of rectifying column sets reboiler 5, reboiler 5
Discharging divides two-way, returns to rectifying column 3 all the way, connects storage tank all the way.
Embodiment 2:
A kind of system for preparing methylisothiouronium methylphosphite ester is present embodiments provided, as shown in Fig. 2, the system structure is referring to real
Apply example 1, difference is only that: deacidifying device 2 includes sequentially connected level-one deacidifying device 21 and second level deacidifying device 22, and level-one is de-
Sour device 21 is falling film evaporator, and second level deacidifying device 22 is tower reactor.
Embodiment 3:
A kind of system for preparing methylisothiouronium methylphosphite ester is present embodiments provided, the system structure is referring to embodiment 1, area
Be not only that: deacidifying device 2 includes sequentially connected level-one deacidifying device 21 and second level deacidifying device 22, level-one deacidifying device
21 be reaction kettle, and second level deacidifying device 22 is falling film evaporator.
Embodiment 4:
A kind of system for preparing methylisothiouronium methylphosphite ester is present embodiments provided, the system structure is referring to embodiment 1, area
Be not only that: deacidifying device 2 includes sequentially connected level-one deacidifying device 21 and second level deacidifying device 22, level-one deacidifying device
21 and second level deacidifying device 22 be falling film evaporator.
Embodiment 5:
A kind of system for preparing methylisothiouronium methylphosphite ester is present embodiments provided, the system structure is referring to embodiment 1, area
Be not only that: deacidifying device 2 includes sequentially connected level-one deacidifying device 21 and second level deacidifying device 22, level-one deacidifying device
21 and second level deacidifying device 22 be tower reactor.
Embodiment 6:
A kind of preparation method of diethyl methyl-phosphonite is present embodiments provided, the method, which uses in embodiment 2, is
It is prepared by system, specifically includes the following steps:
(a) raw material methyl dichloro phosphorus (purity 98wt%) presses 1000kg/h, and ethyl alcohol (purity 99wt%) presses 760kg/h
It is passed through in throwing disc reaction kettle 1, carries out hybrid reaction, control reaction temperature is 25 DEG C~35 DEG C, and reaction pressure≤- 0.08MPa is got rid of
The revolving speed of throwing disc is 10~20r/min in disk reaction kettle 1, obtains reacting rear material；
(b) reacting rear material is introduced into level-one deacidifying device 21 and continues reaction and preliminary removing in step (a)
By-product hydrogen chloride, the feed rate 0.4m of level-one deacidifying device 213/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging
Flow is 0.4m3/ h~4m3/ h, 35 DEG C~65 DEG C of the temperature of level-one deacidifying device 21, the pressure of level-one deacidifying device 21 is negative
Pressure, vacuum degree≤- 0.085MPa；Material after 21 depickling of level-one deacidifying device, which enters, carries out depickling in second level deacidifying device 22,
Thoroughly removing by-product hydrogen chloride, the feed rate 0.4m of second level deacidifying device 223/ h~4m3/ h, regurgitant volume 0.4m3/ h~
1.5m3/ h, discharging flow 0.4m3/ h~4m3/ h, temperature 60 C~80 DEG C of second level deacidifying device 22, second level deacidifying device
22 pressure≤- 0.085MPa
(c) material after step (b) depickling, which enters, carries out rectifying in rectifying column 3, control 3 tower top pressure of rectifying column be-
0.07Mpa~-0.095MPa, column bottom temperature≤165 DEG C, rectifying column feed rate 0.4m3/ h~4m3/ h, discharging flow
0.4m3/ h~4m3/ h after waiting 3 temperature of rectifying columns to reach 165 DEG C, switches rectifying column 3, and original rectifying column 3 stops charging, out once
By-product is high boiling, finally obtains diethyl methyl-phosphonite product.
In the present embodiment, after rectifying the purity of diethyl methyl-phosphonite product up to 98wt% or more, product yield with
Methyl dichloro phosphorus meter is about 94%.
Embodiment 7:
A kind of preparation method of methyl phosphonous acid mono ethyl ester is present embodiments provided, the method, which uses in embodiment 3, is
It is prepared by system, specifically includes the following steps:
(a) raw material methyl dichloro phosphorus (purity 98wt%) presses 1000kg/h, and ethyl alcohol (purity 99wt%) presses 370kg/h
It is passed through in throwing disc reaction kettle 1, carries out hybrid reaction, control reaction temperature is 30 DEG C~40 DEG C, and reaction pressure≤- 0.06MPa is got rid of
The revolving speed of throwing disc is 30~40r/min in disk reaction kettle 1, obtains reacting rear material；
(b) reacting rear material is introduced into level-one deacidifying device 21 and continues reaction and preliminary removing in step (a)
By-product hydrogen chloride, the feed rate 0.4m of level-one deacidifying device 213/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging
Flow is 0.4m3/ h~4m3/ h, 40 DEG C~65 DEG C of the temperature of level-one deacidifying device 21, the pressure of level-one deacidifying device 21≤-
0.07MPa；Material after 21 depickling of level-one deacidifying device, which enters, carries out depickling in second level deacidifying device 22, thoroughly remove by-product chlorine
Change hydrogen, the feed rate 0.4m of second level deacidifying device 223/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging flow
For 0.4m3/ h~4m3/ h, temperature 60 C~80 DEG C of second level deacidifying device 22, the pressure of second level deacidifying device 22≤-
0.08MPa；
(c) material after step (b) depickling, which enters, carries out rectifying in rectifying column 3, control 3 tower top pressure of rectifying column be-
0.08Mpa~-0.095MPa, temperature≤150 DEG C, rectifying column feed rate 0.4m3/ h~4m3/ h, discharging flow 0.4m3/ h~
4m3/ h after waiting 3 temperature of rectifying columns to reach 150 DEG C, switches rectifying column 3, and original rectifying column 3 stops charging, out a by-product height
Boiling, finally obtains methyl phosphonous acid mono ethyl ester product.
In the present embodiment, after rectifying the purity of methyl phosphonous acid mono ethyl ester product up to 98wt% or more, product yield with
Methyl dichloro phosphorus meter is about 92%.
Embodiment 8:
A kind of preparation method of methyl dimethyl phosphite is present embodiments provided, the method, which uses in embodiment 4, is
It is prepared by system, specifically includes the following steps:
(a) raw material methyl dichloro phosphorus (purity 98wt%) presses 1000kg/h, and methanol (purity 99wt%) presses 570kg/h
It is passed through in throwing disc reaction kettle 1, carries out hybrid reaction, control reaction temperature is 20~30 DEG C, reaction pressure≤- 0.05MPa, throwing disc
The revolving speed of throwing disc is 20~30r/min in reaction kettle 1, obtains reacting rear material；
(b) reacting rear material is introduced into level-one deacidifying device 21 and continues reaction and preliminary removing in step (a)
By-product hydrogen chloride, the feed rate 0.4m of level-one deacidifying device 213/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging
Flow is 0.4m3/ h~4m3/ h, 30 DEG C~50 DEG C of the temperature of level-one deacidifying device 21, the pressure of level-one deacidifying device 21≤-
0.06MPa；Material after 21 depickling of level-one deacidifying device, which enters, carries out depickling in second level deacidifying device 22, thoroughly remove by-product chlorine
Change hydrogen, the feed rate 0.4m of second level deacidifying device 223/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging flow
For 0.4m3/ h~4m3/ h, temperature 50 C~70 DEG C of second level deacidifying device 22, the pressure of second level deacidifying device 22 are negative pressure, very
Reciprocal of duty cycle≤- 0.07MPa；
(c) material after step (b) depickling, which enters, carries out rectifying in rectifying column 3, control 3 tower top pressure of rectifying column be-
0.06Mpa~-0.085MPa, temperature≤155 DEG C, rectifying column feed rate 0.4m3/ h~4m3/ h, discharging flow 0.4m3/ h~
4m3/ h after waiting 3 temperature of rectifying columns to reach 155 DEG C, switches rectifying column 3, and original rectifying column 3 stops charging, out a by-product height
Boiling, finally obtains methyl dimethyl phosphite product.
In the present embodiment, after rectifying the purity of methyl dimethyl phosphite product up to 98wt% or more, product yield with
Methyl dichloro phosphorus meter is about 95%.
Embodiment 9:
A kind of preparation method of methyl phosphonous acid mono-methyl is present embodiments provided, the method, which uses in embodiment 4, is
It is prepared by system, specifically includes the following steps:
(a) raw material methyl dichloro phosphorus (purity 98wt%) presses 1000kg/h, and methanol (purity 99wt%) presses 265kg/h
It is passed through in throwing disc reaction kettle 1, carries out hybrid reaction, control reaction temperature is 30 DEG C~40 DEG C, and reaction pressure≤- 0.06MPa obtains
To reacting rear material；
(b) reacting rear material is introduced into level-one deacidifying device 21 and continues reaction and preliminary removing in step (a)
By-product hydrogen chloride, the feed rate 0.4m of level-one deacidifying device 213/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging
Flow is 0.4m3/ h~4m3/ h, 40 DEG C~65 DEG C of the temperature of level-one deacidifying device 21, the pressure of level-one deacidifying device 21≤-
0.07MPa；Material after 21 depickling of level-one deacidifying device, which enters, carries out depickling in second level deacidifying device 22, thoroughly remove by-product chlorine
Change hydrogen, the feed rate 0.4m of second level deacidifying device 223/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging flow
For 0.4m3/ h~4m3/ h, temperature 60 C~80 DEG C of second level deacidifying device 22, the pressure of second level deacidifying device 22≤-
0.08MPa；
(c) material after step (b) depickling, which enters, carries out rectifying in rectifying column 3, control 3 tower top pressure of rectifying column be-
0.07Mpa~-0.095MPa, temperature≤150 DEG C, rectifying column feed rate 0.4m3/ h~4m3/ h, discharging flow 0.4m3/ h~
4m3/ h after waiting 3 temperature of rectifying columns to reach 150 DEG C, switches rectifying column 3, and original rectifying column 3 stops charging, out a by-product height
Boiling, finally obtains methyl phosphonous acid mono-methyl product.
In the present embodiment, after rectifying the purity of methyl phosphonous acid mono-methyl product up to 98wt% or more, product yield with
Methyl dichloro phosphorus meter is about 93%.
Embodiment 10:
A kind of preparation method of methyl phosphonous acid dipropyl is present embodiments provided, the method, which uses in embodiment 4, is
It is prepared by system, specifically includes the following steps:
(a) raw material methyl dichloro phosphorus (purity 98wt%) presses 1000kg/h, and propyl alcohol (purity 99wt%) presses 990kg/h
It is passed through in throwing disc reaction kettle 1, carries out hybrid reaction, control reaction temperature is 15 DEG C~25 DEG C, and reaction pressure≤- 0.07MPa is got rid of
The revolving speed of throwing disc is 60~70r/min in disk reaction kettle 1, obtains reacting rear material；
(b) reacting rear material is introduced into level-one deacidifying device 21 and continues reaction and preliminary removing in step (a)
By-product hydrogen chloride, the feed rate 0.4m of level-one deacidifying device 213/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging
Flow is 0.4m3/ h~4m3/ h, 25 DEG C~60 DEG C of the temperature of level-one deacidifying device 21, the pressure of level-one deacidifying device 21≤-
0.08MPa；Material after 21 depickling of level-one deacidifying device, which enters, carries out depickling in second level deacidifying device 22, thoroughly remove by-product chlorine
Change hydrogen, the feed rate 0.4m of second level deacidifying device 223/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging flow
For 0.4m3/ h~4m3/ h, temperature 60 C~80 DEG C of second level deacidifying device 22, the pressure of second level deacidifying device 22≤-
0.08MPa；
(c) material after step (b) depickling, which enters, carries out rectifying in rectifying column 3, control 3 tower top pressure of rectifying column be-
0.05Mpa~-0.07MPa, temperature≤175 DEG C, rectifying column feed rate 0.4m3/ h~4m3/ h, discharging flow 0.4m3/ h~
4m3/ h after waiting 3 temperature of rectifying columns to reach 175 DEG C, switches rectifying column 3, and original rectifying column 3 stops charging, out a by-product height
Boiling, finally obtains methyl phosphonous acid mono-methyl product.
In the present embodiment, after rectifying the purity of methyl phosphonous acid dipropyl product up to 98wt% or more, product yield with
Methyl dichloro phosphorus meter is about 93%.
Embodiment 11:
A kind of preparation method of methyl phosphonous acid list propyl ester is present embodiments provided, the method, which uses in embodiment 5, is
It is prepared by system, specifically includes the following steps:
(a) raw material methyl dichloro phosphorus (purity 98wt%) presses 1000kg/h, and propyl alcohol (purity 99wt%) presses 540kg/h
It is passed through in throwing disc reaction kettle 1, carries out hybrid reaction, control reaction temperature is 10 DEG C~20 DEG C, and reaction pressure≤- 0.06MPa is got rid of
The revolving speed of throwing disc is 90~100r/min in disk reaction kettle 1, obtains reacting rear material；
(b) reacting rear material is introduced into level-one deacidifying device 21 and continues reaction and preliminary removing in step (a)
By-product hydrogen chloride, the feed rate 0.4m of level-one deacidifying device 213/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging
Flow is 0.4m3/ h~4m3/ h, 20 DEG C~50 DEG C of the temperature of level-one deacidifying device 21, the pressure of level-one deacidifying device 21≤-
0.07MPa；Material after 21 depickling of level-one deacidifying device, which enters, carries out depickling in second level deacidifying device 22, thoroughly remove by-product chlorine
Change hydrogen, the feed rate 0.4m of second level deacidifying device 223/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging flow
For 0.4m3/ h~4m3/ h, temperature 50 C~80 DEG C of second level deacidifying device 22, the pressure of second level deacidifying device 22≤-
0.08MPa；
(c) material after step (b) depickling, which enters, carries out rectifying in rectifying column 3, control 3 tower top pressure of rectifying column be-
0.07Mpa~-0.095MPa, temperature≤165 DEG C, rectifying column feed rate 0.4m3/ h~4m3/ h, discharging flow 0.4m3/ h~
4m3/ h after waiting 3 temperature of rectifying columns to reach 165 DEG C, switches rectifying column 3, and original rectifying column 3 stops charging, out a by-product height
Boiling, finally obtains methyl phosphonous acid list propyl ester product.
In the present embodiment, after rectifying the purity of methyl phosphonous acid list propyl ester product up to 98wt% or more, product yield with
Methyl dichloro phosphorus meter is about 95%.
Embodiment 12:
A kind of preparation method of methyl phosphonous acid di-n-butyl is present embodiments provided, the method is using in embodiment 2
It is prepared by system, specifically includes the following steps:
(a) raw material methyl dichloro phosphorus (purity 98wt%) presses 1000kg/h, and n-butanol (purity 99wt%) is pressed
1170kg/h is passed through in throwing disc reaction kettle 1, carries out hybrid reaction, and control reaction temperature is 20 DEG C~30 DEG C, and reaction pressure≤-
0.07MPa, the revolving speed of throwing disc is 120~130r/min in throwing disc reaction kettle 1, obtains reacting rear material；
(b) reacting rear material is introduced into level-one deacidifying device 21 and continues reaction and preliminary removing in step (a)
By-product hydrogen chloride, the feed rate 0.4m of level-one deacidifying device 213/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging
Flow is 0.4m3/ h~4m3/ h, 30 DEG C~65 DEG C of the temperature of level-one deacidifying device 21, the pressure of level-one deacidifying device 21≤-
0.08MPa；Material after 21 depickling of level-one deacidifying device, which enters, carries out depickling in second level deacidifying device 22, thoroughly remove by-product chlorine
Change hydrogen, the feed rate 0.4m of second level deacidifying device 223/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging flow
For 0.4m3/ h~4m3/ h, temperature 60 C~80 DEG C of second level deacidifying device 22, the pressure of second level deacidifying device 22≤-
0.08MPa；
(c) material after step (b) depickling, which enters, carries out rectifying in rectifying column 3, control 3 tower top pressure of rectifying column be-
0.07Mpa~-0.095MPa, temperature≤175 DEG C, rectifying column feed rate 0.4m3/ h~4m3/ h, discharging flow 0.4m3/ h~
4m3/ h after waiting 3 temperature of rectifying columns to reach 175 DEG C, switches rectifying column 3, and original rectifying column 3 stops charging, out a by-product height
Boiling, finally obtains methyl phosphonous acid di-n-butyl product.
In the present embodiment, the purity of methyl phosphonous acid di-n-butyl product is up to 98wt% or more, product yield after rectifying
It is about 91% in terms of methyl dichloro phosphorus.
Embodiment 13:
A kind of preparation method of methyl phosphonous acid diisobutyl ester is present embodiments provided, the method is using in embodiment 2
It is prepared by system, specifically includes the following steps:
(a) raw material methyl dichloro phosphorus (purity 98wt%) presses 1000kg/h, and isobutanol (purity 99wt%) is pressed
1150kg/h is passed through in throwing disc reaction kettle 1, carries out hybrid reaction, and control reaction temperature is 20 DEG C~30 DEG C, and reaction pressure≤-
0.07MPa, the revolving speed of throwing disc is 190~200r/min in throwing disc reaction kettle 1, obtains reacting rear material；
(b) reacting rear material is introduced into level-one deacidifying device 21 and continues reaction and preliminary removing in step (a)
By-product hydrogen chloride, the feed rate 0.4m of level-one deacidifying device 213/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging
Flow is 0.4m3/ h~4m3/ h, 30 DEG C~65 DEG C of the temperature of level-one deacidifying device 21, the pressure of level-one deacidifying device 21≤-
0.08MPa；Material after 21 depickling of level-one deacidifying device, which enters, carries out depickling in second level deacidifying device 22, thoroughly remove by-product chlorine
Change hydrogen, the feed rate 0.4m of second level deacidifying device 223/ h~4m3/ h, regurgitant volume 0.4m3/ h~1.5m3/ h, discharging flow
For 0.4m3/ h~4m3/ h, temperature 60 C~80 DEG C of second level deacidifying device 22, the pressure of second level deacidifying device 22≤-
0.08MPa；
(c) material after step (b) depickling, which enters, carries out rectifying in rectifying column 3, control 3 tower top pressure of rectifying column be-
0.07Mpa~-0.095MPa, temperature≤175 DEG C, rectifying column feed rate 0.4m3/ h~4m3/ h, discharging flow 0.4m3/ h~
4m3/ h after waiting 3 temperature of rectifying columns to reach 175 DEG C, switches rectifying column 3, and original rectifying column 3 stops charging, out a by-product height
Boiling, finally obtains methyl phosphonous acid diisobutyl ester product.
In the present embodiment, the purity of methyl phosphonous acid diisobutyl ester product is up to 98wt% or more, product yield after rectifying
It is about 90% in terms of methyl dichloro phosphorus.
Comparative example 1:
This comparative example provides the preparation system and method for a kind of diethyl methyl-phosphonite, the structure reference of the system
Structure in embodiment 2, difference are only that: reaction unit used is tubular reactor.
The preparation method is referring to method in embodiment 6.
In this comparative example, the purity of diethyl methyl-phosphonite product is only 94% after rectifying, and product yield is with methyl two
Phosphorus chloride meter is only 80%.
Comparative example 2:
This comparative example provides the preparation system and method for a kind of diethyl methyl-phosphonite, the structure reference of the system
Structure in embodiment 2, difference are only that: reaction unit used is conventional reactor.
The preparation method is referring to method in embodiment 6.
In this comparative example, the purity of diethyl methyl-phosphonite product is only 93% after rectifying, and product yield is with methyl two
Phosphorus chloride meter is only 75%.
Comparative example 3:
This comparative example provides the preparation system and method for a kind of diethyl methyl-phosphonite, the structure reference of the system
Structure in embodiment 2, difference are only that: reaction unit used is packed tower.
The preparation method is referring to method in embodiment 6.
In this comparative example, the purity of diethyl methyl-phosphonite product is only 94% after rectifying, and product yield is with methyl two
Phosphorus chloride meter is only 78%.
It can be seen that the production that system and method described in the utility model are serializations with comparative example based on the above embodiments
System and method, using methyl dichloro phosphorus and alcohol as raw material, the first hybrid reaction in throwing disc reaction kettle, then obtained through depickling and rectifying
To methyl phosphinate, continuous reaction simplifies operational process of craft, greatly improves the effective rate of utilization of equipment, drop
Low cost of labor, saves production cost；
Meanwhile the utility model uses throwing disc reaction kettle, opposite tubular reactor, conventional reactor and packed tower etc. are anti-
For answering device, react it is more abundant, the yield of product can be greatlyd improve, make the yield of methyl phosphinate reach 90% with
On, and reaction condition is mild, only can be carried out under cryogenic；
Also, the utility model, without additives such as solvent and acid binding agents, reduces subsequent distillation and waited in reacting
Journey reduces energy consumption, has saved resource, waste is seldom generated in reaction process, processing is convenient, environmentally friendly.
Applicant's statement, the utility model illustrate the detailed applications method of the utility model through the foregoing embodiment, but
The utility model is not limited to above-mentioned detailed applications method, that is, does not mean that the utility model must rely on above-mentioned method detailed
It could implement.It should be clear to those skilled in the art, any improvement to the utility model, produces to the utility model
The equivalence replacement of product raw material and addition, concrete operations condition and the selection of mode of auxiliary element etc., all fall within the utility model
Protection scope and the open scope within.
Claims (9)
1. a kind of system for preparing methylisothiouronium methylphosphite ester using throwing disc reaction kettle, which is characterized in that the system comprises successively connect
Throwing disc reaction kettle (1), de- by-product unit and the product separative unit connect；Wherein, throwing disc reaction kettle (1) material outlet and de-
The material inlet of by-product unit is connected.
2. system according to claim 1, which is characterized in that the throwing disc reaction kettle (1) built-in throwing disc in a kettle,
Throwing disc is connected with liquid material entrance.
3. system according to claim 2, which is characterized in that the liquid material entrance includes methyl dichloro phosphorus entrance
And alcohol inlet, methyl dichloro phosphorus entrance connect methyl dichloro phosphorus transfer pipeline；The alcohol inlet connects alcohol transfer pipeline.
4. system according to claim 1, which is characterized in that the de- by-product unit includes deacidifying device (2)；Throwing disc is anti-
The material outlet of kettle (1) and the material inlet of deacidifying device (2) is answered to be connected；Deacidifying device (2) be reaction kettle, falling film evaporator or
Any one in tower reactor or at least two combination.
5. system according to claim 4, which is characterized in that the deacidifying device (2) includes that sequentially connected level-one is de-
Sour device (21) and second level deacidifying device (22)；The level-one deacidifying device (21) and second level deacidifying device (22) independently are
Any one in reaction kettle, falling film evaporator or tower reactor or at least two combination.
6. system according to claim 1, which is characterized in that the product separative unit includes at least one rectifying column
(3), product is gone out at the top of rectifying column (3), bottom goes out by-product；The product exit of the de- by-product unit and the material of rectifying column (3)
Entrance is connected.
7. system according to claim 6, which is characterized in that rectifying column (3) tower top sets condenser (4), condenser
(4) condensate liquid divides two-way, returns to rectifying column (3) all the way, connects storage tank all the way.
8. system according to claim 6, which is characterized in that rectifying column (3) tower bottom sets reboiler (5), reboiler
(5) discharging divides two-way, returns to rectifying column (3) all the way, connects storage tank all the way.
9. system according to claim 1, which is characterized in that the system comprises sequentially connected throwing disc reaction kettle (1),
Level-one deacidifying device (21), second level deacidifying device (22) and rectifying column (3)；
Wherein, the material outlet of the throwing disc reaction kettle (1) is connected with the material inlet of level-one deacidifying device (21), the throwing disc
Built-in throwing disc, throwing disc are connected reaction kettle (1) with liquid material entrance in a kettle；Liquid material entrance includes methyl dichloro
Phosphorus mild and mellow entrance, the methyl dichloro phosphorus entrance connect methyl dichloro phosphorus transfer pipeline, and the alcohol inlet connects alcohol
Transfer pipeline；The product exit of second level deacidifying device (22) is connected with the material inlet of rectifying column (3), and rectifying column (3) tower top is set
The condensate liquid of condenser (4), condenser (4) divides two-way, returns to rectifying column (3) all the way, connects storage tank all the way；Rectifying column (3) tower
Bottom is set reboiler (5), and the discharging of reboiler (5) divides two-way, is returned to rectifying column (3) all the way, is connected storage tank all the way.
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| CN201820370711.1U CN208562200U (en) | 2018-03-19 | 2018-03-19 | A kind of system that methylisothiouronium methylphosphite ester is prepared using throwing disc reaction kettle |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574561A (en) * | 2020-06-17 | 2020-08-25 | 浙江新安化工集团股份有限公司 | Synthesis method and synthesis device of diethyl methylphosphonite |
| CN112791680A (en) * | 2020-12-24 | 2021-05-14 | 华阳新材料科技集团有限公司 | A nickel phosphorus complex synthesis system for adiponitrile production |
-
2018
- 2018-03-19 CN CN201820370711.1U patent/CN208562200U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574561A (en) * | 2020-06-17 | 2020-08-25 | 浙江新安化工集团股份有限公司 | Synthesis method and synthesis device of diethyl methylphosphonite |
| CN112791680A (en) * | 2020-12-24 | 2021-05-14 | 华阳新材料科技集团有限公司 | A nickel phosphorus complex synthesis system for adiponitrile production |
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