CN103073595B - Hermetically sealedly clean the technique preparing methylpyridine phosphorus - Google Patents
Hermetically sealedly clean the technique preparing methylpyridine phosphorus Download PDFInfo
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- CN103073595B CN103073595B CN201210596238.6A CN201210596238A CN103073595B CN 103073595 B CN103073595 B CN 103073595B CN 201210596238 A CN201210596238 A CN 201210596238A CN 103073595 B CN103073595 B CN 103073595B
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Abstract
The invention provides and a kind ofly hermetically sealedly clean the technique preparing methylpyridine phosphorus, it comprises the steps: to provide a reaction unit; Prepare side chain chloro-product: in eddy flow still, pass into chlorine, described eddy flow still comprises the first noumenon, and described the first noumenon hollow arranges the first reaction chamber forming tool inverted cone structure; Mix and dispersed oxazole [4 with the first powder liquid mixing pump, 5-b] pyridine-2 (3H) ketone, N, described eddy flow still injected by the raw materials such as dinethylformamide, paraformaldehyde and sulfur oxychloride, makes described raw material at described first reaction response thus obtains side chain chloro-product.Thiophosphatephosphorothioate is prepared at the second reaction member.Methylpyridine phosphorus is prepared at the 3rd reaction member.The hermetically sealed technique preparing methylpyridine phosphorus that cleans provided by the invention can clean and prepares methylpyridine phosphorus under hermetically sealed environment.
Description
Technical field
The present invention relates to a kind of production technique of methylpyridine phosphorus, particularly a kind ofly hermetically sealedly can clean the technique preparing methylpyridine phosphorus.
Background technology
Methylpyridine phosphorus has another name called first base pyrrole Evil phosphorus, is a kind of excellent sterilant, and chemistry S-[the chloro-oxazole of 6-(4,5-b) pyridine-2 (3 hydrogen)-one base-methyl]-O, O-dimethyl sulphide substituted phosphate by name, molecular formula is C
9h
10clN
2o
5pS, molecular weight is in order to 324.68.Methylpyridine phosphorus is a kind of excellent miticide, have insecticidal activity concurrently, belong to and tagging and stomach toxicity medicament, long-lasting is good, insecticidal spectrum is wide, can be used for cotton, fruit tree, vegetables and livestock, public health and family, prevent and treat various mite class and stupid, aphid, leaf lice, small kernel-eating insect, colorado potato bug and fly, cockroach etc., this agent is to people and animals' low toxicity, belong to efficient, low toxicity, low residue resistant medicament, therefore methylpyridine phosphorus becomes the organic phosphorous insecticide of the World Health Organization (WHO) recommendation.Again because make emulsion, sprays, pulvis, wettable powder and sol particle in this methylpyridine phosphorus, be therefore specially adapted to the insects such as control fly.
Conventional methylpyridine phosphorus preparation technology mainly comprises three steps: step one, with oxazole [4,5-b] pyridine-2 (3H) ketone is raw material, then generates a kind of intermediate side chain chloro-product of methylpyridine phosphorus through nucleophilic chloro, methylolation; Step 2, with dimethylphosphite and sulfur reaction, under the effect of sodium methylate, generates the another kind of intermediate thiophosphatephosphorothioate of methylpyridine phosphorus; Step 3, finally by side chain chloro-product and thiophosphoric acid ester condensation reaction further synthesizing methyl pyridine phosphorus.Please refer to Fig. 1, is the module diagram of the device of the described methylpyridine phosphorus of existing preparation, and described device comprises the first reaction member 100, second reaction member 200, and the 3rd reaction member 300 be connected with first, second reaction member 100,200 described.At described first reaction member 100 for the preparation of intermediate product side chain chloro-product.Second reaction member 200 is for the preparation of intermediate product thiophosphatephosphorothioate.Above-mentioned two kinds of intermediate products and side chain chloro-product and thiophosphatephosphorothioate finally enter the 3rd reaction member 300, produce the finished product methylpyridine phosphorus.
Refer to Fig. 2, for the structural representation of traditional first reaction member 100, described first reaction member 100 comprises one first reactor 10, multiple the first storage tank, a gas-holder 30 and waste gas recovery tank 40 of communicating with this first reactor 10 and one first whipping appts 50.Described first storage tank comprises an oxazole [4,5-b] pyridine-2 (3H) ketone storage tank 21, DMF (DMF) storage tank 22, paraformaldehyde storage tank 23 and monochlor(in)ate sulfoxide storage tank 24.Described gas-holder 30 stores chlorine, when reacting, by a ventpipe (not shown), gas is imported the first reactor 10.40, described waste gas recovery tank reclaims by the recovery tube (not shown) extend in the first reactor 10 waste gas reacting and produce.Described first whipping appts 50 comprises the first stirring rod 51 extended in the first reactor 10.When reacting, the raw materials such as oxazole pyridone, DMF (DMF), paraformaldehyde and sulfur oxychloride being added the first reactor 10 according to a graded, and passes into chlorine, reacting while stirring.Referring to Fig. 3, is the structural representation of traditional second reaction member 200, and described second reaction member 200 comprises one second reactor 210, multiple the second storage tank of communicating with this second reactor 210 and one second whipping appts 230.Described second storage tank comprises sulphur storage tank 221, methyl alcohol storage tank 222, sodium methylate storage tank 223 and a dimethylphosphite storage tank 224.Described second whipping appts 230 comprises the second stirring rod 231 extended in the second reactor 210.When reacting, the raw materials such as sulphur storage tank 221, methyl alcohol storage tank 222, sodium methylate storage tank 223 and dimethylphosphite 224 being added the second reactor 210 according to a graded, reacts while stirring.When back has reacted, then add new raw material.
But during with traditional technique preparation preparation described side chain chloro-product, be difficult to accomplish to seal completely, easily there is the situations such as run, drip, leak in described first reaction member 100 in preparation process.And the gas (as hydrogenchloride) that described side chain chloro-product produces in preparation process all has stronger toxicity and corrodibility, leak out and easily affect production environment and human body health, be unfavorable for environment protection.Reason has two: the first, because described oxazole [4,5-b] pyridine-2 (3H) ketone is solid feed, when feeding in raw material at every turn, all need hand-fed, and hand-fed must open described first reactor 10, affect the sealing of described first reactor 10.Second, because described first reactor 10 has the first whipping appts 50, the raw material that seal point between first whipping appts 50 and the first reactor 10 easily suffers to prepare described side chain chloro-product as sulfur oxychloride and in the reaction the gas that produces as the corrosion of hydrogenchloride, affect the sealing of the first reactor 10, become the hidden danger point can not stopping poisonous gas leakage.
Summary of the invention
In view of this, be necessary to provide a kind of and hermetically sealedly clean the technique preparing methylpyridine phosphorus, to overcome above-mentioned deficiency.
The invention provides a kind of technique of hermetically sealed cleanly production methylpyridine phosphorus, it comprises the steps: to provide a reaction unit, it the 3rd reaction member comprising one first reaction member, one second reaction member and be communicated with respectively with first, second reaction member described, this first reaction member comprises an eddy flow still, one first powder liquid mixing pump, an oxazole [4,5-b] pyridine-2 (3H) ketone storage tank, a DMF storage tank, a paraformaldehyde storage tank, monochlor(in)ate sulfoxide storage tank, a gas-holder and a waste gas recovery tank; Described sulfur oxychloride storage tank is directly communicated with described eddy flow still, and described gas-holder and waste gas recovery tank are all communicated with described eddy flow still; Described first powder liquid mixing pump comprises one first import and one first outlet, described oxazole [4,5-b] pyridine-2 (3H) ketone storage tank, N, dinethylformamide storage tank and paraformaldehyde storage tank and described first inlet communication, described first outlet is communicated with described eddy flow still; Described eddy flow still comprises a first noumenon, and described the first noumenon hollow arranges formation one first reaction chamber, and described first reaction chamber is the conical structure of a handstand, and described sulfur oxychloride storage tank is arranged on the larger side of the round tangent plane diameter of described first reaction chamber; Described eddy flow still comprise be separately positioned on described the first noumenon sidewall on the first opening for feed and the first discharge port, this first opening for feed is near the larger side of the round tangent plane diameter of described first reaction chamber, and this first discharge port is near the less side of the round tangent plane diameter of described first reaction chamber; Described first opening for feed is a shower nozzle, and the direction that the diameter defining the round tangent plane of described first reaction chamber in axial direction reduces gradually is first direction, and the axial direction due of described shower nozzle and described first direction have an angle, and described angle is more than or equal to 45 degree; Prepare side chain chloro-product: make the chlorine in gas-holder be sent to described eddy flow still, oxazole [4 is sucked from the first import according to a definite sequence by described first powder liquid mixing pump, 5-b] pyridine-2 (3H) ketone, N, dinethylformamide, paraformaldehyde dispersed, raw material after dispersion is exported from the first outlet and injects described first reaction chamber via described shower nozzle, and along under the first noumenon inwall rotating fluid; Sulfur oxychloride is dripped at this first reaction chamber, make oxazole [4,5-b] pyridine-2 (3H) ketone, DMF, paraformaldehyde, sulfur oxychloride and chlorine completes nucleophilic chlorination, hydroxymethylation and side chain chlorination successively at the first reaction chamber thus obtains side chain chloro-product; Prepare thiophosphatephosphorothioate: in a kettle. with dimethylphosphite and sulfur reaction, under the effect of sodium methylate, obtain thiophosphatephosphorothioate.Prepare methylpyridine phosphorus: make described side chain chloro-product, thiophosphatephosphorothioate deliver to the 3rd reaction member from the first reaction member, the second reaction member respectively, and carry out condensation reaction at the 3rd reaction member and generate described methylpyridine phosphorus.
By raw material oxazole [4,5-b] pyridine-2 (3H) ketone and solvent N, dinethylformamide is from described oxazole [4,5-b] pyridine-2 (3H) ketone storage tank and N, dinethylformamide storage tank sucks the first powder liquid mixing pump and carries out mixing and dispersed, mixed solution after dispersion is injected eddy flow still by the first opening for feed, carries out nucleophilic chlorination with the chlorine in eddy flow still and obtain chloro-product.
Described hydroxymethylation comprise the steps: further by paraformaldehyde from paraformaldehyde storage tank suck the first powder liquid mixing pump dispersed after inject eddy flow still, in eddy flow still, obtain methylolation product with described chloro-product generation hydroxymethylation.
Solid-liquid two-phase raw material in eddy flow still is disperseed further from the first outlet material suction first powder liquid mixing pump, then injects eddy flow still by shower nozzle.
Described side chain chlorination comprises the steps: to add sulfur oxychloride by sulfur oxychloride storage tank toward eddy flow still further, makes this methylolation product and sulfur oxychloride carry out side chain chlorination and obtains described side chain chloro-product.
The axial direction due of described first discharge port overlaps with the axial direction due of the first reaction chamber.
The axial direction due of described shower nozzle and the angle of described first direction are 90 degree.
The axial direction due of described shower nozzle and the internal surface of described the first noumenon tangent.
Described shower nozzle is hollow tubular structure.
Described eddy flow still comprises a channel setting further at the sidewall of described the first noumenon and is communicated with described gas sampling tank, described passage near the larger side of the round tangent plane diameter of the first reaction chamber.
Compared to prior art, provided by the present inventionly hermetically sealedly clean the technique preparing methylpyridine phosphorus, by the first powder liquid mixing pump by oxazole [4,5-b] raw material such as two-phase such as solid-liquid such as pyridine-2 (3H) ketone, DMF etc. is dispersed utilizes the inwall along this eddy flow still in pressure directive eddy flow still to flow down afterwards, and nationality is arranged by the gradient of the first reaction chamber of described eddy flow still and the position of nozzle, described raw material helically can be declined at the inwall of this first reaction chamber, delay the time that described raw material flows down along the inwall of described first reaction chamber.Be appreciated that one is make the first reaction member without the need to hand-fed, and all reinforced processes all can be carried out in a sealed meter environment by introducing the first powder liquid mixing pump and having the eddy flow still of taper first reaction chamber; Two is by dispersed for the raw material of solid-liquid two-phase and make raw material spiral in the first reaction chamber stay by the first powder liquid mixing pump; increase the duration of contact between chlorine and raw material; raw material can be made to reach the effect of stirring; thus can accomplish in eddy flow still without whipping appts; fundamentally stop poisonous gas leakage, be conducive to environment protection.To sum up; the device preparing methylpyridine phosphorus provided by the present invention; because described side chain chloro-product can be prepared by the eddy flow still under hermetically sealed environment; therefore, described eddy flow still, when preparing described side chain chloro-product, can be accomplished to seal completely; there will not be the situations such as run, drip, leak in preparation process; the toxic gas produced also can not leak out, thus it is healthy to affect production environment and human body, is beneficial to cleaning of environment protection and whole production environment.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, embodiments of the invention are described, wherein:
Fig. 1 is the module diagram of a kind of device for the preparation of methylpyridine phosphorus provided by the invention.
Fig. 2 is the structural representation of the first reaction member in Fig. 1.
Fig. 3 is the structural representation of the second reaction member in Fig. 1.
Fig. 4 is the module diagram of a kind of reaction unit for the preparation of methylpyridine phosphorus provided by the invention.
Fig. 5 is the structural representation of the first reaction member in Fig. 4.
Fig. 6 is the structural representation of shower nozzle in Fig. 5 and the first noumenon.
Fig. 7 is the structural representation of the second reaction member in Fig. 4.
Embodiment
Based on accompanying drawing, specific embodiments of the invention are further elaborated below.Should be appreciated that specific embodiment described herein is as just embodiment, the protection domain be not intended to limit the present invention.
The hermetically sealed technique preparing methylpyridine phosphorus that cleans provided by the invention comprises the steps:
Step one, provides a reaction unit.
Referring to Fig. 4, is the module diagram of described reaction unit, and it comprises first reaction member 400, second reaction member 500, and the 3rd reaction member 600 that first, second reaction member 400,500 described in connects.
Refer to Fig. 5, described first reaction member 400 comprises an eddy flow still 410, multiple the first storage tank (scheming not indicate), gas-holder 430, waste gas recovery tank 440 and one first powder liquid mixing pump 450 communicated with this eddy flow still 410.
Described first storage tank synthesizes the various raw materials of described side chain chloro-product for laying in.Particularly, described first storage tank comprises an oxazole [4,5-b] pyridine-2 (3H) ketone storage tank 421, DMF (DMF) storage tank 422, paraformaldehyde storage tank 423 and monochlor(in)ate sulfoxide storage tank 424.Wherein, described oxazole [4,5-b] pyridine-2 (3H) ketone storage tank 421, DMF storage tank 422 and paraformaldehyde storage tank 423 are communicated with described eddy flow still 410 by described first powder liquid mixing pump 450.Described sulfur oxychloride storage tank 424 is directly communicated with described eddy flow still 410, to prevent described sulfur oxychloride from directly entering the first powder liquid mixing pump 450 described in the first powder liquid mixing pump 450 and then corrosion damage, also prevent various raw material from reacting in the first powder liquid mixing pump 450 simultaneously.In order to control described oxazole [4,5-b] switch of pyridine-2 (3H) ketone storage tank 421, DMF storage tank 422 and paraformaldehyde storage tank 423 and flow, the connecting pipe of this oxazole [4,5-b] pyridine-2 (3H) ketone storage tank 421, DMF storage tank 422 and paraformaldehyde storage tank 423 and the first powder liquid mixing pump 450 is provided with three control valves (scheming not indicate).Understandably, for controlling switch and the flow of sulfur oxychloride storage tank 424, this sulfur oxychloride storage tank 424 with the connecting pipe of eddy flow still 410 are also provided with a control valve (scheming not indicate).
Described gas-holder 430 stores chlorine, when reacting, by a ventpipe (figure does not indicate), gas is imported eddy flow still 410.For controlling switch and the flow of gas-holder 430, described ventpipe is provided with a control valve (figure does not indicate).440, described waste gas recovery tank reclaims by the recovery tube (figure does not indicate) extend in eddy flow still 410 waste gas reacting and produce.Described waste gas mainly comprises hydrogenchloride.It is emphasized that described waste gas recovery tank 440 means that all can collect the device of described waste gas, as recovery tower.
Described first powder liquid mixing pump 450 has takes out material, feeding, and mixing, the function of dispersed various raw material, for Solid raw materials or solid-liquid mixed-phase feed being carried out dispersed and being sent in eddy flow still 410 and reacting.Particularly, this first powder liquid mixing pump 450 comprises first import 451 and one first outlet 452.Described first import 451 is communicated with described oxazole [4,5-b] pyridine-2 (3H) ketone storage tank 421, DMF storage tank 422 and paraformaldehyde storage tank 423, and described first outlet 452 is communicated with eddy flow still 410.With by raw material (oxazole [4,5-b] pyridine-2 (3H) ketone, DMF and paraformaldehyde) from the first import 451 suck and through mixing, dispersed after, from first outlet 452 with certain pressure, well-mixed material is pressed to eddy flow still 410.Because the raw material of solid-liquid two-phase or solvent also can be carried out mixing press-in eddy flow still 410 automatically by automatic material-absorbing by described first powder liquid mixing pump 450, thus without the need to hand-stuff (as manually added oxazole [4,5-b] pyridine-2 (3H) ketone in solid phase).Namely automatically carry out filler (oxazole [4,5-b] pyridine-2 (3H) ketone in solid phase) by the first powder liquid mixing pump 450, can reaction efficiency be improved, be conducive to the optimization of the healthy of employee and reaction process.
Described eddy flow still 410 comprises a first noumenon 411, a taper decollator 412 be arranged in described the first noumenon 411, first opening for feed 413 being arranged on the sidewall of described the first noumenon 411, one through described taper decollator 412 and for 414, one, conduit inputting chlorine for discharge to produce because preparing methylpyridine phosphorus the passage 415 of waste gas (as HCl) and one be arranged on as described in the first discharge port 416 of the first noumenon 411 sidewall.
Described the first noumenon 411 hollow arranges thus is surrounded by its internal surface and forms first reaction chamber, and namely the synthesis of described side chain chloro-product completes in this first reaction chamber.Described first reaction chamber was made up or was formed to described the first noumenon 411 internal surface of acid resisting material is coated with acid resisting material.The shape of described reaction chamber is not limit, and can be barrel-like structure, also can be conical structure.In the present embodiment, described reaction chamber is the conical structure of a handstand, and the direction that the diameter defining the round tangent plane of described first reaction chamber in axial direction reduces gradually is first direction.It is to be noted, this section and even conical structure mentioned in this article, one end that its diameter is less still has one fixed width, namely the diameter of its circle tangent plane is non-vanishing at microcosmic, and just the ratio of the diameter of the round tangent plane of the diameter of the round tangent plane of one end that diameter is less and the larger one end of diameter is less.Therefore from macroscopically, described first reaction chamber is conical structure, and from microcosmic, described first reaction chamber is frustum cone structure.
Described taper decollator 412 is connected with described the first noumenon 411 by one end that circle tangent plane diameter is less, and the internal surface interval of the outside surface of this taper decollator 412 and described the first noumenon 411 is arranged.Wherein, the axis of described taper decollator 412 and the dead in line of the first noumenon 411, and the diameter of the round tangent plane of described taper decollator 412 increases gradually along first direction, make the space between the first reaction chamber and taper decollator 412 outer side wall more and more less along first direction, thus nationality is by the unique texture of described first reaction chamber and taper decollator 412, forms a space and keep away the back cavity walking and narrow between the first noumenon inwall and taper decollator 412 outer wall.Described raw material can not only be made can to form " whirlwind " rotation at described back cavity fall, delay the raw material skyborne residence time, thus the lowering speed of the contact area be conducive to for increasing powder liquid and reduction powder liquid, improve reaction efficiency.Described taper decollator 412 is a hollow structure, to pass described conduit 414.That is, described chlorine passes through from described taper decollator 412 inside, and other raw materials then pass through from the space between described first reaction chamber and taper decollator 412 outer side wall.Be appreciated that same the first noumenon 411, this taper decollator 412 is also made up of acid resistant material or its Surface coating has acid resistant material.As a same reason, round tangent plane non-vanishing at microcosmic of one end that described taper decollator 412 diameter is less.Therefore from macroscopically, described taper decollator 412 is conical structure, and from microcosmic, described taper decollator 412 is frustum cone structure.
Described first opening for feed 413 is arranged on larger one end of diameter of described first reaction chamber circle tangent plane, flows to the larger one end of taper decollator 412 diameter to make raw material from one end that taper decollator 412 diameter is less.Behind one end less to taper decollator 412 diameter after raw material injects the first reaction chamber from the first opening for feed 413 under stress, major part raw material can rotate around described taper decollator 412 and declines in the space between described the first noumenon 411 internal surface and taper decollator 412 outer side wall, small portion raw material can drop on outside surface or the first noumenon 411 internal surface of taper decollator 412 under gravity, and the outside surface along described the first noumenon 411 internal surface or taper decollator 412 rotates decline.And the internal surface of space between described first reaction chamber and the taper decollator 412 outer side wall outside surface that drops on taper decollator 412 more and more along with highly declining around the raw material that described taper decollator 412 rotates or the first noumenon 411.Because the diameter of taper decollator 412 circle tangent plane increases gradually along first direction, and the diameter of described first reaction chamber circle tangent plane reduces gradually along first direction, this setting can slow down the dropping velocity of the material of outside surface or the first noumenon 411 internal surface dropping on taper decollator 412, can disperse its contact area simultaneously.Meanwhile, because the space between the first reaction chamber and taper decollator 412 outer side wall is more and more less along first direction, when described raw material declines toward first direction, space is more crowded, thus can slow down the dropping velocity of described material further.Be appreciated that described raw material is longer in the residence time in space, the contact area between each raw material is larger, and contact more abundant, reaction efficiency is higher.
In the present embodiment, for making described raw material longer in the residence time in space, described first opening for feed 413 is a shower nozzle with hollow tubular structure, and the axial direction due of described shower nozzle and described first direction have an angle, and described angle is more than or equal to 45 degree.Please also refer to Fig. 6, preferably, the axial direction due of described shower nozzle and the angle of described first direction are 90 degree, and the internal surface of the axial direction due of described shower nozzle and described the first noumenon 411 is tangent.Thus make the raw material shot out from this shower nozzle substantially can along the internal surface rotating fluid of this first noumenon 411, and at the internal surface of this first noumenon 411, there is speed of rotation faster, utilize the centripetal force of himself to rotate around the internal surface of this first noumenon 411, thus delay the time under described feedstream.
Described conduit 414 can be a Venturi tube, its hermetically passing the first noumenon 411, and be plugged in the taper decollator 412 of hollow structure, thus fix the position of this conduit 414, the chlorine entered from conduit 414 can also be made to rising simultaneously, and then fully contact with defluent raw material, reach the object of fully reaction further.Be appreciated that, evenly flowing out from described taper decollator 412 for enabling described chlorine and increase the contact area of being detained skyborne raw material with the first reaction chamber, the sidewall of described taper decollator 412 also evenly can be provided with multiple through hole (scheming not indicate).Further, when the larger one end of described taper decollator 412 diameter is covered by reaction solution (solution after raw material and chlorine reaction), by described through hole, described chlorine can directly and contact raw.
Described passage 415 is also salable to be arranged on the first noumenon 411, and when chlorine and the oxazole pyridone taking DMF as dissolution with solvents, paraformaldehyde, when the raw material reactions such as sulfur oxychloride generate waste gas (as HCl), described waste gas can be discharged from this passage 415.
Described first discharge port 416 is communicated with described first powder liquid mixing pump 450 and the 3rd reaction member 600 simultaneously.For controlling, from described eddy flow still 410 raw material out or product stream to the first powder liquid mixing pump 450 and the 3rd reaction member 600, to be provided with control valve (scheming not indicate) between the first import 451 of described first powder liquid mixing pump 450 and described first discharge port 416.Because first entrance 451 of described first discharge port 416 with described first powder liquid mixing pump 450 is communicated with.When reaction does not complete, unreacted completely raw material can carry out blending dispersion again by being sent to described first powder liquid mixing pump 450, directive eddy flow still 410 again after being uniformly dispersed, thus raising reaction efficiency, avoid deposits materials to contact bottom described eddy flow still 410 not exclusively, cause reaction not exclusively.When the reactions are completed, described reacted product can flow to the 3rd reaction member 600, carries out next step reaction.
Refer to Fig. 7, described second reaction member 500 comprises a reactor 510, multiple the second storage tank (scheming not indicate), one second powder liquid mixing pump 530 and whipping appts 540 communicated with this reactor 510.
Described second storage tank is for laying in the various raw materials of the described thiophosphatephosphorothioate of synthesis.Particularly, described second storage tank comprises sulphur storage tank 521, methyl alcohol storage tank 522, sodium methylate storage tank 523 and a dimethylphosphite storage tank 524.Described sulphur storage tank 521 is communicated with described reactor 510 by described second powder liquid mixing pump 530.Described methyl alcohol storage tank 522, sodium methylate storage tank 523 and dimethylphosphite storage tank 524 is directly communicated with described reactor 510, directly enter the second powder liquid mixing pump 530 to avoid described raw material and then corrode described second powder liquid mixing pump 530, described raw material also can be avoided simultaneously to react in the second powder liquid mixing pump 530.In order to control switch and the flow of described sulphur storage tank 521, the connecting pipe of this sulphur storage tank 521 and the second powder liquid mixing pump 530 is respectively arranged with control valve (scheming not indicate).Understandably, for controlling switch and the flow of described methyl alcohol storage tank 522, sodium methylate storage tank 523 and dimethylphosphite storage tank 524, this methyl alcohol storage tank 522, sodium methylate storage tank 523 and dimethylphosphite storage tank 524 with the connecting pipe of reactor 510 are also provided with a control valve (scheming not indicate) separately.
Described second powder liquid mixing pump 530 has takes out material, feeding, and the function of blending dispersion, for by dispersed for Solid raw materials (as sulphur) and be sent to reactor 510.Particularly, this second powder liquid mixing pump 530 comprises second import 531 and one second outlet 532.Described second import 531 is communicated with described sulphur storage tank 521, and described second outlet 532 is communicated with reactor 510.Raw material (as sulphur) is sucked from the second import 531 and after dispersed, with certain pressure, the material fully disperseed is pressed to reactor 510 from the second outlet 532.Because Solid raw materials also can be carried out mixing press-in reactor 510 automatically by automatic material-absorbing by described second powder liquid mixing pump 530, thus without the need to hand-stuff (as manually added the sulphur in solid phase).Namely automatically carry out filler by the second powder liquid mixing pump 530, can reaction efficiency be improved, be conducive to the optimization of the healthy of employee and reaction process.
Described reactor 510 comprises the second opening for feed 512 and second discharge port 513 be arranged on bottom described second body 511 that second body 511, is arranged on the sidewall of described second body 511.
Described second body 511 hollow arranges thus forms second reaction chamber, and namely the synthesis of described thiophosphatephosphorothioate completes in this second reaction chamber.Described second reaction chamber was made up or was formed to described second body 511 internal surface of acid resisting material is coated with acid resisting material.The shape of described second reaction chamber is not limit, and can be barrel-like structure, also can be conical structure.In the present embodiment, described second reaction chamber is the barrel-like structure of a handstand.
The axis of described second opening for feed 512 and the axis at intervals of described second discharge port 513 are arranged, and preferably, the axis of described second opening for feed 512 is mutually vertical with the axis of described second discharge port 513.Described second opening for feed 512 exports 532 with second of described second powder liquid mixing pump 530 and is communicated with.
Described second discharge port 513 is communicated with described second powder liquid mixing pump 530 and the 3rd reaction member 600 simultaneously.For controlling from described reactor 510 raw material out or product stream to the second powder liquid mixing pump 530 and the 3rd reaction member 600, be provided with a control valve (scheming not indicate) between second import 531 of described second powder liquid mixing pump 530 and described second discharge port 513, between described second discharge port 513 and the 3rd reaction member 600, be also provided with a control valve (scheming not indicate).When reaction does not complete, unreacted completely raw material can carry out blending dispersion again by the second powder liquid mixing pump 530, directive reactor 510 again after being uniformly dispersed, thus raising reaction efficiency, avoid deposits materials to contact bottom described reactor 510 not exclusively, cause reaction not exclusively.When the reactions are completed, described reacted product can flow to the 3rd reaction member 600, carries out next step reaction.
Described whipping appts 540 is for stirring raw material when reacting, fully to disperse the raw material in reactor 510.This whipping appts 540 comprises the stirring rod 541 extended in described second body 511, the axis of described stirring rod 541 and the dead in line of the second body 511, to reach best mixing effect.
Step 2, prepares side chain chloro-product.
Chlorine is passed in eddy flow still 410, oxazole [4 is sucked from the first import 451 according to a definite sequence by described first powder liquid mixing pump 450,5-b] pyridine-2 (3H) ketone, N, dinethylformamide, paraformaldehyde dispersed, raw material after dispersion is exported from the first outlet 452 and injects described first reaction chamber, back cavity rotating fluid that the raw material make described in injected described the first noumenon 411 and taper decollator 412 between formed under from one end that described conical structure diameter is larger along the tangential direction of its circle tangent plane via described shower nozzle.Sulfur oxychloride is dripped at this first reaction chamber, make oxazole [4,5-b] pyridine-2 (3H) ketone, DMF, paraformaldehyde, sulfur oxychloride and chlorine completes nucleophilic chlorination, hydroxymethylation and side chain chlorination successively at the first reaction chamber thus obtains side chain chloro-product.
Described nucleophilic chlorination comprises the steps: raw material oxazole [4 further, 5-b] pyridine-2 (3H) ketone and solvent N, dinethylformamide is from described oxazole [4,5-b] pyridine-2 (3H) ketone storage tank 421 and solvent DMF storage tank 422 suck the first powder liquid mixing pump 450 and carry out mixing and dispersed.Mixed solution after dispersion or solution are injected eddy flow still 410 by the first opening for feed 411, carries out nucleophilic chlorination with the chlorine in eddy flow still 410 and obtain chloro-product.The reaction formula of described nucleophilic chlorination is as follows:
Described hydroxymethylation comprise the steps: further by paraformaldehyde from paraformaldehyde storage tank 423 suck the first powder liquid mixing pump 450 dispersed after inject eddy flow still 410, in eddy flow still 410, obtain methylolation product with described chloro-product generation hydroxymethylation.The reaction formula of described hydroxymethylation is as follows:
The described step preparing side chain chloro-product comprises the steps: that the solid-liquid two-phase raw material in eddy flow still 410 is sucked the first powder liquid mixing pump 450 from the first outlet material 412 to be disperseed further, then injects eddy flow still 410 by shower nozzle further.Be appreciated that and disperse by described raw material being sucked further the first powder liquid mixing pump 450, deposits materials can be avoided to contact bottom described eddy flow still 410 not exclusively, cause reaction not exclusively.Indirectly reach the effect stirring raw material, improve reaction efficiency.
Described side chain chlorination comprises the steps: directly to add sulfur oxychloride toward eddy flow still 410 by sulfur oxychloride storage tank 424 further, makes this methylolation product and sulfur oxychloride carry out side chain chlorination and obtains described side chain chloro-product.The reaction formula of described side chain chlorination is as follows:
Step 3, prepares thiophosphatephosphorothioate.
Suck sulphur with the second powder liquid mixing pump mixing pump 530 from sulphur storage tank 521, all with after dispersion sulphur described sulphur is injected reactor 510.In described reactor 510, add methyl alcohol, sodium methylate and dimethylphosphite and stir by described stirring rod 541, described sulphur and sodium methylate and dimethylphosphite being reacted, obtains thiophosphatephosphorothioate.The preparation feedback formula of described thiophosphatephosphorothioate is as follows:
The step that thiophosphatephosphorothioate is propped up in described preparation comprises the steps: that the solid-liquid two-phase raw material in reactor 510 is sucked the second powder liquid mixing pump 530 from the second outlet material 512 to be disperseed further, then injects reactor 510 further.Be appreciated that and disperse by described raw material being sucked further the second powder liquid mixing pump 530, indirectly can add the effect of strong mixing raw material, improve reaction efficiency.
Be appreciated that described step 3 can further include with filtration washing step and an incubation step in order to make the technique of described methylpyridine phosphorus more optimize.By filtration washing, the purity of the thiophosphatephosphorothioate sent from reactor 510 can be made higher.By insulation, the temperature of described thiophosphatephosphorothioate can be made to be more suitable for the temperature of reaction of step 4.
Step 4, prepares methylpyridine phosphorus.
Make described side chain chloro-product, thiophosphatephosphorothioate deliver to the 3rd reaction member 600 from the first reaction member 400, second reaction member 500 respectively, and carry out condensation reaction at the 3rd reaction member 600 and generate described methylpyridine phosphorus.The preparation feedback formula of described methylpyridine phosphorus is as follows:
Be appreciated that step 4 also can comprise a washing step further in order to obtain purity higher methylpyridine phosphorus, by washing, waste products or raw material are processed, 4-methyl pyridine phosphorus carries out purifying.White or white crystals sprills can be obtained after methylpyridine phosphorus drying after washing.
Not only further, the hermetically sealed technique preparing methylpyridine phosphorus that cleans in the application is not only applicable to for the preparation of methylpyridine phosphorus, and other need the chemical substance that uses mechanical stirring device but also can produce obnoxious flavour to be also applicable to preparation.
Compared to prior art, provided by the present inventionly hermetically sealedly clean the technique preparing methylpyridine phosphorus, by the first powder liquid mixing pump by oxazole [4,5-b] raw material such as two-phase such as solid-liquid such as pyridine-2 (3H) ketone, DMF etc. is dispersed utilizes the inwall along this eddy flow still in pressure directive eddy flow still to flow down afterwards, and nationality is arranged by the gradient of the first reaction chamber of described eddy flow still and the position of nozzle, described raw material helically can be declined at the inwall of this first reaction chamber, delay the time that described raw material flows down along the inwall of described first reaction chamber.Be appreciated that one is make the first reaction member without the need to hand-fed, and all reinforced processes all can be carried out in a sealed meter environment by introducing the first powder liquid mixing pump and having the eddy flow still of taper first reaction chamber; Two is by dispersed for the raw material of solid-liquid two-phase and make raw material spiral in the first reaction chamber stay by the first powder liquid mixing pump; increase the duration of contact between chlorine and raw material; raw material can be made to reach the effect of stirring; thus can accomplish in eddy flow still without whipping appts; fundamentally stop poisonous gas leakage, be conducive to environment protection.To sum up; the device preparing methylpyridine phosphorus provided by the present invention; because described side chain chloro-product can be prepared by the eddy flow still under hermetically sealed environment; therefore, described eddy flow still, when preparing described side chain chloro-product, can be accomplished to seal completely; there will not be the situations such as run, drip, leak in preparation process; the toxic gas produced also can not leak out, thus it is healthy to affect production environment and human body, is beneficial to cleaning of environment protection and whole production environment.
Be appreciated that, not not being only applicable to for the preparation of methylpyridine phosphorus for the hermetically sealed technique preparing methylpyridine phosphorus in the application, also can be applicable to major part produce in the chemical reaction of waste gas, be especially applicable in other reaction process of preparation and produce with obnoxious flavour and need to use the chemical substance of mechanical stirring device equipment.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all do in the spirit and principles in the present invention any amendment, equivalent to replace and improvement etc., all should be included in protection scope of the present invention.
Claims (10)
1. hermetically sealedly clean the technique preparing methylpyridine phosphorus, it comprises the steps:
One reaction unit is provided, it the 3rd reaction member comprising one first reaction member, one second reaction member and be communicated with respectively with first, second reaction member described, this first reaction member comprises an eddy flow still, one first powder liquid mixing pump, an oxazole [4,5-b] pyridine-2 (3H) ketone storage tank, a DMF storage tank, a paraformaldehyde storage tank, monochlor(in)ate sulfoxide storage tank, a gas-holder and a waste gas recovery tank; Described sulfur oxychloride storage tank is directly communicated with described eddy flow still, and described gas-holder and waste gas recovery tank are all communicated with described eddy flow still; Described first powder liquid mixing pump comprises one first import and one first outlet, described oxazole [4,5-b] pyridine-2 (3H) ketone storage tank, N, dinethylformamide storage tank and paraformaldehyde storage tank and described first inlet communication, described first outlet is communicated with described eddy flow still; Described eddy flow still comprises a first noumenon, and described the first noumenon hollow arranges formation one first reaction chamber, and described first reaction chamber is the conical structure of a handstand, and described sulfur oxychloride storage tank is arranged on the larger side of the round tangent plane diameter of described first reaction chamber; Described eddy flow still comprise be separately positioned on described the first noumenon sidewall on the first opening for feed and the first discharge port, this first opening for feed is near the larger side of the round tangent plane diameter of described first reaction chamber, and this first discharge port is near the less side of the round tangent plane diameter of described first reaction chamber; Described first opening for feed is a shower nozzle, and the direction that the diameter defining the round tangent plane of described first reaction chamber in axial direction reduces gradually is first direction, and the axial direction due of described shower nozzle and described first direction have an angle, and described angle is more than or equal to 45 degree;
Prepare side chain chloro-product: make the chlorine in gas-holder be sent to described eddy flow still, oxazole [4 is sucked from the first import according to a definite sequence by described first powder liquid mixing pump, 5-b] pyridine-2 (3H) ketone, N, dinethylformamide, paraformaldehyde dispersed, raw material after dispersion is exported from the first outlet and injects described first reaction chamber via described shower nozzle, and along under the first noumenon inwall rotating fluid; Sulfur oxychloride is dripped at this first reaction chamber, make oxazole [4,5-b] pyridine-2 (3H) ketone, DMF, paraformaldehyde, sulfur oxychloride and chlorine completes nucleophilic chlorination, hydroxymethylation and side chain chlorination successively at the first reaction chamber thus obtains side chain chloro-product;
Prepare thiophosphatephosphorothioate: in a kettle. with dimethylphosphite and sulfur reaction, under the effect of sodium methylate, obtain thiophosphatephosphorothioate;
Prepare methylpyridine phosphorus: make described side chain chloro-product, thiophosphatephosphorothioate deliver to the 3rd reaction member from the first reaction member, the second reaction member respectively, and carry out condensation reaction at the 3rd reaction member and generate described methylpyridine phosphorus.
2. hermetically sealedly as claimed in claim 1 clean the technique preparing methylpyridine phosphorus, it is characterized in that: described nucleophilic chlorination comprises the steps: raw material oxazole [4 further, 5-b] pyridine-2 (3H) ketone and solvent N, dinethylformamide is from described oxazole [4, 5-b] pyridine-2 (3H) ketone storage tank and N, dinethylformamide storage tank sucks the first powder liquid mixing pump and carries out mixing and dispersed, mixed solution after dispersion is injected eddy flow still by the first opening for feed, carry out nucleophilic chlorination with the chlorine in eddy flow still and obtain chloro-product.
3. hermetically sealedly as claimed in claim 2 clean the technique preparing methylpyridine phosphorus, it is characterized in that: described hydroxymethylation comprise the steps: further by paraformaldehyde from paraformaldehyde storage tank suck the first powder liquid mixing pump dispersed after inject eddy flow still, in eddy flow still, obtain methylolation product with described chloro-product generation hydroxymethylation.
4. hermetically sealedly as claimed in claim 3 clean the technique preparing methylpyridine phosphorus, it is characterized in that: the described step preparing side chain chloro-product comprises the steps: the solid-liquid two-phase raw material in eddy flow still to disperse further from the first outlet material suction first powder liquid mixing pump further, then injects eddy flow still by shower nozzle.
5. hermetically sealed as described in claim 3 or 4 cleans the technique preparing methylpyridine phosphorus, it is characterized in that: described side chain chlorination comprises the steps: to add sulfur oxychloride by sulfur oxychloride storage tank toward eddy flow still further, makes this methylolation product and sulfur oxychloride carry out side chain chlorination and obtains described side chain chloro-product.
6. hermetically sealedly as claimed in claim 1 clean the technique preparing methylpyridine phosphorus, it is characterized in that: the axial direction due of described first discharge port overlaps with the axial direction due of the first reaction chamber.
7. hermetically sealedly as claimed in claim 1 clean the technique preparing methylpyridine phosphorus, it is characterized in that: the axial direction due of described shower nozzle and the angle of described first direction are 90 degree.
8. hermetically sealedly as claimed in claim 1 clean the technique preparing methylpyridine phosphorus, it is characterized in that: the axial direction due of described shower nozzle and the internal surface of described the first noumenon tangent.
9. hermetically sealedly as claimed in claim 8 clean the technique preparing methylpyridine phosphorus, it is characterized in that: described shower nozzle is hollow tubular structure.
10. hermetically sealedly as claimed in claim 1 clean the technique preparing methylpyridine phosphorus, it is characterized in that: described eddy flow still comprises a channel setting further at the sidewall of described the first noumenon and is communicated with described gas sampling tank, described passage near the larger side of the round tangent plane diameter of the first reaction chamber.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386741A (en) * | 2001-05-22 | 2002-12-25 | 中国科学院福建物质结构研究所 | Process for synthesizing methylpyridyl phosphide |
| JP2011106857A (en) * | 2009-11-13 | 2011-06-02 | Toppan Forms Co Ltd | Kit and method for separating chemical substance |
| CN102336783A (en) * | 2010-07-18 | 2012-02-01 | 李坚 | Isomerization reaction |
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| CN1386741A (en) * | 2001-05-22 | 2002-12-25 | 中国科学院福建物质结构研究所 | Process for synthesizing methylpyridyl phosphide |
| JP2011106857A (en) * | 2009-11-13 | 2011-06-02 | Toppan Forms Co Ltd | Kit and method for separating chemical substance |
| CN102336783A (en) * | 2010-07-18 | 2012-02-01 | 李坚 | Isomerization reaction |
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